THE OXFORD HANDBOOK OF

ARCHAEOLOGICAL
CERAMIC ANALYSIS

Edited by
ALICE M. W. HUNT

OXFORD
UNIVERSITY l?RBSS
 OXFORD
UNIVERSITY PRESS

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 AcKNOWLEDGMENTS

'CJ
""
0:)
~ THIS Handbook would not have been possible without the hard work and expertise of its
~ contributors. I also owe a debt of gratitude to Hilary O'Shea, Charlotte Loveridge, Annie
---,_ Rose, Michael De Ia Cruz, and the rest of the OUP team for helping to bring this volume to

{ fruition with minimum stress and maximum enjoyment. Special thanks to Jeff Speakman
and the Center for Applied Isotope Studies, University of Georgia, for a publication subven·
tion that allowed us to include the colored plates. Many of the individual contributors wish
to thank various colleagues and asso·dates for reading and commenting upon their contribu-
tions, and sharing unpublished materials; space limitations preclude acknowledging each
individual by name, and so consider this a heartfelt, if general, round of thanks and apprecia-
tion to all involved behind the scenes.
 CONTENTS

List ofFigures xi
List of Tables xix
List ofPlates xxi
List ofAbbreviations xxiii
List of Contributors XXV

PART I INTRODUCTION

1. Introduction to the Oxford Handbook of Archaeological

Ceramic Analysis 3
ALICE M. W HUNT

2. History of Scientific Research 7

MICHAELS. TITE

PART II RESEARCH DESIGN

AND DATA ANALYSIS

3· Designing Rigorous Research: Integrating Science and Archaeology 19

]AUME BUXEDA I GARRIGOS AND MARISOL MADRID I FERNANDEZ

4· Evaluating Data: Uncertainty in Ceramic Analysis

RoBERTo I-IAZENFRATZ- MARKS

s. Statistical Modeling for Ceramic Analysis ss

GULSEBNEM BISHOP

6. Recycling Data: Working with Published and Unpublished

Ceramic Compositional Data 73
MATTHEW T. BoULANGER

PART III FOUNDATIONAL CONCEPTS

7· Ceramic Raw Materials

GIUSEPPE MoNTANA
viti CO:S:TENTS

8. Ceramic Manufacture: The chaine operatoire Approach 101

VALENTINEROUX

9. The Organization of Pottery Production:

Toward a Relational Approach 114
KIM Du!STERMAAT

10. Provenance Studies: Productions and Compositional Groups 148

YONA WAKSMAN

11. Mineralogical and Chemical Alteration 162

GERWULF SCHNEIDER

12. Formal Analysis and Typological Classification in the Study

of Ancient Pottery
DANIEL ALBERO SANTACREU, MANUEL CALVO TRIAS,
AND JAIME GARciA ROSSELLO

13. Fabric Description of Archaeological Ceramics 200

IAN K. WHITBREAD

14. Analytical Drawing 217

PRABODH SH!RVALKAR

PART IV EVALUATING CERAMIC

PROVENANCE

15. Petrography: Optical Microscopy 233

DENNIS BRAEKMANS AND PATRICK DEGRYSE

16. Ceramic Micropalaeontology 266

IAN P. WILKINSON, PATRICK S. QUINN, MARK WILLIAMS,
}EREMY TAYLOR, AND IA:-1 K. WHITBREAD
q. Electron Microprobe Analysis (EMPA) 288
CORJNA lO:-iESCU A:-ID VOLKER HOECK

18. Isotope Analysis 305

BETTINA A. WIEGAND

19. X-Ray Powder Diffraction (XRPD)

ROBERT B. HEIMANN
 CONTENTS iX

20. X-Ray Fluorescence-Energy Dispersive (ED-XRF) and Wavelength

Dispersive (WD-XRF) Spectrometry 342
MARK E. HALL
21. Handheld Portable Energy-Dispersive X- Ray Fluorescence
Spectrometry (pXRF)
ELISABETH HOLMQVIST

22. Particle Induced X-ray Emission (PIXE) and Its Applications

for Ceramic Analysis 382
MARCIA A. RIZZUTTO AND MANFREDO H. TABACNIKS

23. Inductively Coupled Plasma-Mass Spectrometry (ICP-MS)

and Laser Ablation Inductively Coupled Plasma-Mass
Spectrometry (LA-ICP-MS) 399
MARK GOLITKO AND LAU!tE DUSSUBIEUX

24. Instrumental Neutron Activation Analysis (INAA) in the Study

of Archaeological Ceramics 424
LEAH D. MINC AND )OHANNES H. STERBA

25. Synchrotron Radiation 447

ALAN F. GREENE

PART V INVESTIGATING
CERAMIC MANUFACTURE

26. Ethnography
KENT D. FowLER

27. Experimental Firing and Re-firing

MALGORZATA DASZKIEW!CZ AND LARA MARITAN

28. Fourier Transform Infrared Spectroscopy (FT-IR) in Archaeological

Ceramic Analysis 509
SHLOMO SHOVAL

29. Raman Spectroscopy and the Study of Ceramic Manufacture:

Possibilities, Results, and Challenges 531
)OLIEN VAN PEVENAGE AND PETER VANDENABEELE

30. X-Radiography of Archaeological Ceramics 544

INA BERG AND )ANET AMBERS
X CONTENTS

31. Organic Inclusions

MARTA MARIOTTI LIPPI AND PASQUINO PALLECCHI

PART VI ASSESSING VESSEL FUNCTION

32. Formal Typology oflberian Ceramic Vessels by Morphometric

Analysis 585
ANA LUISA MARTINEZ-CARILLO AND ]VAN ANTONIO BARCELO

33· Mechanical and Thermal Properties 603

NOEMI S. MULLER

34· Assessing Vessel Function by Organic Residue Analysis

HANS BARNARD AND ]ELMER W. EERKENS

PART VII DATING CERAMIC ASSEMBLAGES

35· Typology and Classification

EuGENIO BoRTOLINI

36. Direct Dating Methods

SOPHIE BLAIN AND CHRISTOPHER HALL

Index
 LIST OF FIGURES

3.1 Diagram flow of the states of ceramics from manufacture to the

archaeological record. 20

3.2 Bar chart of Hispanic Terra Sigillata from Tritium Magallum recovered at
Baetulo, Tarraco, and Ilerda, classified according the range of estimated
equivalent firing temperatures. 28
3-3 Bar chart of Hispanic Terra Sigi!latafrom (a) context LL85b context
and (b) context TV83, and (c) a bivariate diagram of integrity (H,) vs
fragmentation (FI). 37
3-4 Scatter plots of evenness for Hispanic Terra Sigillata from (a) context LL85b
and (b) context TV83, and (c) evenness of the rarefaction experiment. A bar
chart of the richness after the rarefaction experiment is presented in (d). 40
3.5 Binomial probabilities for n = 15 and p = 0.1. 41

5.1 Bar charts describing the (a) distribution and (b) relative frequency of vessel
types in an assemblage. 61
5.2 Pie charts describing the relative distribution of vessel types in funerary
assemblages from Athens and Sparta. 61
5·3 Histogram of amphora capacity measurements from a hypothetical shipwreck. 63
5-4 Common shapes of data distribution. 63
5·5 Bimodal distribution of mineral inclusions in a ceramic fabric. 64
5.6 Stem-and-leaf plot (worked example) of vessel weights. 65
5-7 Back-to-back stem-and-leaf plot comparing cooking pot volumes from two sites. 65
6.1 Timeline of a selection of former and current nuclear archaeometry
laboratories, and estimates of the total numbers of archaeological specimens
analyzed. Data compiled primarily from val. 49(2) of Archaeometry. 77
7.1 "Integrated approach'' for characterizing and sourcing ceramic raw materials. 89
7.2 Examples of primary and secondary clays: (a) kaolinite deposits in the crater
of Mount Gibele at the volcanic island of Pantelleria (Italy); (b) outcrop of
Upper Miocene marine clays in southern Sicily. 91
7·3 Brick and roof tile makers in western Sicily traditionally using NaCl as
deflocculating agent. 97
8.1 Classification chart of roughing out and preforming techniques. 105
8.2 Diagnostic features taken into account for reconstructing an Early Bronze Age
chaine operatoire from the site of Tell Arqa (Lebanon). 106
xii I,..IST OF FIGURES

8.3 Example of technostylistic trees obtained after dassifying ceramic assemblages

according to the concept of chaine optratoire. 108
9.1 Entanglements of the materials used to make a carinated bowL 127

9.2 Chaine operatoire for a Middle Assyrian carinated bowL 130

9.3 Entanglement of the life-history of carinated bowls, from production until
deposit in the archaeological record 132

10.1 Local reference samples, late Byzantine workshops, 'Thessaloniki, Greece, 151

10.2 Beirut medieval wares: main compositional groups as determined by

hierarchical clustering analysis, and corresponding wares. 155
10.3 Beirut medieval wares: binaryplotiron-silicon (top) and histogram of
Mahalanobis distances (bottom). 157
11.1 Correlation of barium and phosphorus in Roman and Germanic pottery
from two sites in Germany. 170

n.2 Leaching of calc.ium in two samples of calcareous pottery. 173

12.1 Sunomary of the different le~els to approach pottery form and typological
analyses discussed in the text. 182

12.2 Isomorphic relation between the decorative motifs recorded on Late Iron Age
pottery and bronze discs in Ma!lorca (Spain). 187
12.3 Format translation related to hybridization phenomena between Punic
wheel-thrown vessels and hand-made indigenous pottery in the Late
Iron Age in MaUorca (Spain). 194

14.1 Art-historical period pottery illustrations. 218

14.2 Steps of traditional pottery illustration (partr). 220

14.3 Steps of traditional pottery illustration (part 2). 221

14.4 Various aspects of pottery illustration. 222

14.5 Steps of new pottery illustration (part 1). 225

14.6 Steps of new pottery illustration (part 2). 226
14.7 Steps of new pottery illustration (part 3). 22.8
15.1 A standard polarizing light microscope with rotating sample stage.
The camera and imaging software are essential tools for data output 235
15-2 High relief and cleavage of a pyroxene mineraL 238
15.3 Photomicrograph of a Late Roman, quartz-tempered cooking vessel from
Carthage (Tunisia). 258
16.1 The earliest known image of a microfossiL 267
16.2 Examples of the main microfossil groups that may be found
in ceramics. 268
16.3 Examples of microfossils in ceramic matrices that can be applied in
provenance studies. 273
16.4 Degradation of microfossils during firing. 274
 LIST OF FIGURES xiii

17.1 (a) Origin ofBSE, SE, and characteristic X-rays emitted by the interaction
between the fOcused electron beam and sample. (b) BSE image of a ceramic
sample from Ibida (Roman- Byzantine period). (c) SE image of the same. 290
17.2 BSE images of various compounds of a ceramic body. 294
17-3 X-ray maps ofCucuteni ceramics (Copper Age). 295
86
18.1 Distribution of 87 Sr/ Sr ratios in ceramic samples from archaeological sites of
different regions. 315
18.2 Distribution of 87Sr/ 86 Sr and eNd values in ceramic samples from Turkey,
Greece, Bulgaria, and China. 316
18.3 Pb isotope data oflead-based glazes from New Mexico, USA, China, and
various European locations. 319
19.1 (a) Permitted electron transitions to generate X-rays of the K series. (b)
Interpretation ofX-ray diffraction as the result of simple reflection. (c)
Seemann- Bohlin focusing geometry for Debye-Scherrer and Straumanis
methods. (d) Bragg-Brentano focusing configuration for scintillation counter
(powder diffractometer) method. 329
19.2 X-ray diffraction charts of an archaeological calcareous illitic clay from
Otter bach, Palatinate, Germany. 335
19-3 X~ray diffraction charts of archaeological ceramics buried under arid and
humid conditions. 337
19-4 X-ray diffraction chart (CuKa) of stoneware from Sawankhalok, Thailand
(14th-15th centuries AD). 338
21.1 SEM- ESE micrographs of heterogeneous ceramic matrices showing sand~
temper. 364
21.2 Correlation of pXRF net peak area values to quantitative NAA data. 366
21.3 PCA biplots of the variance-covariance matrix of the pottery samples
measured by pXRF and INAA. 370
21.4 PCA biplots with density ellipses for clusters indicated by low-dimensional
pXRF data and high-dimensional ICP-OES and NAA datasets. 371
22.1 Parameters and coordinates of the experimental PIXE geometry. 384
22.2 Typical thin film yield curve of the Sao Paulo PIXEsystem with a Si(Li) X-ray
detector and a 55 ~m thick beryllium X-ray filter. 386
22.J General view of LAMPI with the ion sources on the right and the 5SDH
accelerator tank in the center. 387
22-4 The external beam setup at the LAMPI with the different detectors assembled.
The lower part of the figure shows in detail the assembly of the coupled
detectors. 388
22.5 Chimu ceramics at the Museum of Archaeology and Ethnology of the
University of Siio Paulo (MAE- USP) collection. 390
XiV LIST OF FIGURFS

22.6 (a) PIXE spectra of two ceramic vessels (3635 and 3601) of the Chimu culture;
(b) comparison of the concentrations values obtained by FIXE at different
points, analyzed in the two ceramic pieces. 391
22.7 (a) Graph of the correlation between At Si, K, Ti and Fe elements giving rise to
4large groups; (b) graph of the correlation between AI, Si, K and Ti elements,
suggesting the origin of three major groups. 392
22.8 Sun ray plots of the elements Al, Si, K, and Ti showing the correlations in the
groups and the respectively vessels in each group. 393
23.1 An ICP- MS laboratory, with both laser ablation and liquid sampling
equipment visible. 401
23.2 Schematic diagram of plasma~ion source and common mass spectrometer
types. 402
23.3 Examples of calibration lines for Fe, Rb, and Pr using NIST610, 612, and 679 as
SRMs. 407
23.4 Surface geology of the Sepik coast of Papua New Guinea, with ceramic and
clay sampling locations indicated. 416
23.5 Backscatter SEM-EDS image of a sherd cross-section from Worn (Papua New
Guinea) analyzed by LA-ICP- MS. 417
23.6 Discriminant function plot summarizing the results ofLA-ICP-MS analysis of
all ceramic and clay pastes analyzed from the Sepik coast of Papua New Guinea. 418
24.1 Schematic overview of neutron activation and subsequent decay. 426
24.2 TI1e core of a research reactor provides a high-intensity source of neutrons to
activate samples. 428
24.3 The build-up and decay of radioactivity in an isotope according to its half-life
and decay constant A. 431
24-4 Complex gamma-ray spectrum resulting from the irradiation of an
earthenware vessel from Oaxaca, Mexico. 432
24.5 Ceramic composition groups defined for the central Valley of Oaxaca, Mexico,
for the Late~Terminal Formative period. 440
24.6 (a) The industrial potteries and bottle kilns ofNorth Staffordshire, England,
c. 1900 (from an historic postcard labeled "Fresh Air from the Potteries").
(b) Each pottery manufacturer developed one or more paste recipes, with a
distinctive trace-element composition. 443
25.1 Schematic of the Australian Synchrotron's small- and wide-angle X-ray
scattering beamline by David Cookson and Jonathan de Booy. 448
25.2 One potential schematic of an experimental setup for SR pottery analysis, here
micro-X-ray fluorescence, showing the positioning of the SR beam, sample,
and solid-state detector. 450
25.3 Reflected light micrograph, SEM micrograph, and~- XR diffractogram of the
yellow-glazed area of a sherd from Mission San Luis (Florida, USA) collected
during the analysis of American majolica by SR. 452
 LIST OF FIGURES XV
·····~~··~··--~

25.4 'Ihe three microregions of interest on a "black gloss" or "red ftguren potsherd,
as investigated by Walton and colleagues with a diverse set ofSR methods. 456
25.5 An example of a high-temperature XRD pattern collected during "live" time-
resolved temperature experimentation. 458
26.1 The domains of ethnographic and archaeological inquiry into pottery
manufacturing practices and the two principle areas of contribution
ethnographic observations and explanations may lead to the understanding of
past ceramic production systems. 470
26.2 The distances travelled to ceramic resources (day and temper} by potters from
117 communities. 475
26.3 Range of firing temperatures and soaking times for firings in West Africa. 479
26.4 Models of the technical and social influences on ceramic manufacturing based
upon African case studies, 481
27.1 Examples of open firing and of a traditional updraft kiln. 491
27.2 Sketch of a typical firing diagram used when programming an experimental
firing in a laboratory with a furnace. 492
27.3 Bar charts showing the changes in the mineral composition as a function of
the firing temperature. 494
27.4 Determination of the original firing temperature using the K-H method
(Teq900-10oooC). soo
27.5 Two samples made oft he same marly clay re-fired at 1200,C. 501
28.1 Curve-fitted FT-IR spectra of the ceramic material of representative Iron Age
pottery from Levan tine sites. 513
28.2 FT-IR spectra and second-derivatives of the spectra of the ceramic material of
representative Bronze Age pottery from Canaanite sites, 514
28.3 FT-IR spectra and second-derivatives of reference standards of firing silicates. 516
28.4 FT-IR spectra and second-derivatives of reference standards of carbonate and
silica minerals. 517
28.5 FT-1R spectra and second· derivatives of reference standards of minerals
typicaily found in initial or unfired raw materials. 518
28.6 FT-IR spectra and second~derivatives of reformed minerals in pottery. 521
28.7 FT-!Rspectra of paints and pigments. 524
29.1 Energy-level diagram explaining the different types of scattering. 532
29.2 Raman spectrum of calcite (CaCOJ 533
29.3 Formation and decomposition of calcite (CaC03). 537
29.4 Plot of the polymerization index as a function of the main Si-0 stretching
component wavenumber, 539
30.1 Characteristic X-ray features of the main pottery forming techniques. 548
30.2 Inclusion alignment in a clay coil. 548
xvi L!ST Of FIGURES

30,3 Xeroradiographs of two stirn.1p jars showing both the blue color and edge
enhancement inherent to the technique. 551
30.4 Examples of types of radiographic equipment available. (a) Portable medical
Sirio uolwo CR system; (b) Faxitron single-cabinet X·ray unit 552
30.5 Radiographs of a Middle Minoan amphora (BM registration number
G&R1906,1112.90) from the British Museum. 554
30.6 Radiographs of a bell-shaped handled cup (Middle Minoan I) from Knossos
(BM registration no G&R195o,no6.16). 557
30.7 Radiographs of a Mycenaean krater (BM registration number
G&Rt898,!20J.H2) taken from the side (a) and above (b). s6o
31.1 Fan-shaped phytolith from modern rice (1 mm). 567
31.2 Thin section of rice-tempered ceramic from Sumhuram, Sultanate of Oman. 568
31.3 Shell-tempered ceramic from Sumhuram, Sultanate of Oman. 570
31.4 Fracture surface of a potsherd from Surnhuram, Sultanate of Oman. 571
31.5 Renaissance ceramic tefnpered with wool (polarized 1 mm). 572
31.6 Rice-tempered ceramic from Sumhuram, Sultanate of Oman: epidermis of the
rice husk with evident silicized tubercles (SEM). 574
31.7 Karnataka rice winnowing in South India. 577
32.1 Map of the study area. 592
32.2 Profiles of the eleven classes of vessels determined by preliminary descriptive
analysis. 593
32.3 Erosion, dilation, opening and dosing characteristic curves of a profile of the
database, using an isotropic (circular) structural element, normalized by the
area of the profile. 595
32.4 Segmentation of a profile into rim, hody, and base. 595
32.5 A given ceramic and the ten most similar shapes, with the measure of the
distance. 598
33.1 Typical load-displacement curves for di!Terent types of fracture observed in
archaeological ceramics: (a) unstable; (b) semi-stable; (c) stable. 614
34.1 Schematic overview of different organic residues in archaeological ceramics,
and techniques frequently employed to investigate these (34.1). 626
34.2 Schematic flow diagram showing the position of organic residue analysis in
anthropological and archaeological studies. 628
34-3 The general principles of"microscopic (a)" and "molecular (b)" methods for
organic residue analysis. 629
34·4 Schematic of the chromatography arrays used on mass spectrometers to
separate the sample into its components and convert them into a form fit to
enter the ion source. 631
34·5 Schematic representation of the antibody-antigen reaction. 633
 LIST OF FIGURES XVii

35.1 Two graphical representations of Petrie's chronological ordination of

archaeological types. 654
35.2 An example of frequency seriation. 656
35.3 '!be original diagram by which Krieger explained in detail the procedure for a
correct application of his typological method. 658
35-4 Some quantifiable formal dimensions in pottery. 662
35.5 An example of categorical classification of pottery surface decoration from a
Central European Neolithic context. 664
36.1 Schematic of the archaeological clock and radiation doses used in
luminescence dating. 673
36.2 TL glow curve on quartz grains with the various characteristic peaks and a
total OSL decay curve, made of its different components. The surface under
the peaks or signal is function of the number of traps occupied before the
stimulation. 674
36.3 TL glow curve on quartz grains with the various characteristic peaks and a
total OSL decay curve, made of its different components. 674
36-4 Luminescence reader. 677
36.5 Microbalance data obtained on a Werra earthenware specimen excavated at
Enkhuizen (1979). 685
 LIST OF TABLES

1.1 Analytical methods included in this Handbook, and which of the four primary
research questions they contribute toward answering. 5
4-1 Uncertainty values calculated for a ceramic chemical group from the Central
Amazon. 54
j.1 Frequency distribution table describing a small assemblage of Greek pottery. 6o
j.2 Random number table (excerpt). 67
7-1 Chemical composition of the "average terrigenous marine clay" (after Clarke,
1924) and of some representative Italian and Greek clays. 94
11.1 Chemical alteration of Roman sigillata from Arezzo, Lyon, and La
Graufesenque found at Velsen and Nijmegen in the Netherlands. 169
15.1 Mineral identification table derived from the integrated information of
various geological handbooks. They represent a concise list of characteristics
in thin section. 242
17.1 Mean atomic number for common minerals in ceramics. 292
17.2 Selected electron microprobe analyses (in mass%) and calculated structural
formulae for illite (illitic matrix), albite (Ab ), plagioclase (excluding albite),
alkali-feldspar, K-feldspar, and muscovite. 297
19.1 Chemical composition of calcareous illitic clay from Otterbach, jockgrim,
Palatinate, Germany. 334
19.2 List of measured diffraction angles 0 28 of mullite and quartz, d values
calculated according to the Bragg equation. 334
23.1 Comparison of measurements on NIST679 (brick clay) by LA-ICP-MS,
MD-ICP-MS, and other bulk techniques. 411
23.2 Comparison of measurements on New Ohio Red Clay (NORC) by
LA-ICP-MS, MD-ICP-MS, and other bulk techniques. 413
24.1 The sensitivity of INAA in the analysis of ceramics varies by element, from
percent level to parts-per-trillion. 425
27.1 Basic atmospheric conditions during firing in antiquity. 489
29.1 Based on the lp ratio, the processing temperature of glass structures can be
estimated. 538
30.1 Exposure times and kV for clay objects using a Faxitron cabinet X-ray
machine with a 0.5 mm focal spot, 6o em focus-to-film distance, 3 rnA, and
Agfa Structrex D4 Film. ss6
XX LIST Of TABLES-

32.1 Vesseis in the study by context 591

3.2.2 Classification rates obtained by the method with one, three, and five
suggestions and one, three, and five neighbors. 597
32..3 ~ormalized confusion matrix resulting from the application of
the method to the database, using two subprofiles: rim and the combination
ofbody with base. 597
32-4 Normalized confusion matrix resulting !rom the application of the method to
the database, using the rim and body subprofiles. 598
33.1 Examples of material requirements placed on different ceramic products. 6o6
34.1 Schematic overview of the characteristics of selected techniques to investigate
organic residues in archaeological ceramics. 627
 LIST OF PLATES

Experimental firings of different day raw materials (Sicily, Italy).

2 Photomicrographs of thin sections of medium-high fired sherds with
calcite (incompletely crossed polarized light, width of field 0.7 mm).
3 Late Bronze Age pottery sample 133 in (a) hand specimen and (band c)
thin-section photomicrograph in plane polarized light.
4 Photomicrographs of thin sections with a basalt-andesitic volcanic rock
fragment under plane polarized light (a) and crossed polarized light (b).
5 Photomicrographs illustrating microstructural changes with increasing
ceramic firing temperature. (For explanations see text in Chapter27.)
6 MGR~analysis of six ceramic sherds, carrJed out to determine original firlng
temperatures. Sample 1 represents a briqueue cut from a model ceramic
sample; samples 2.-6 represents archeological samples. (For explanations
see text in Chapter 27; photographs were taken with a macro lens by
M. Baranowski.)
7 Structural MGR-analysisoftwo ceramic samples {Photographs taken
under a reflected light microscope). A~ pottery fragment originally fired
at Teq < 70d'C; B""' pottery waste) fragment over-fired at uoo-1150°C. (For
explanations see tex:t in Chapter 27; photographs were taken with a macro lens
by M. Baranowski.)
8 MGR-analysis {8oo"C, 9oo"C, 120o'C) of five samples belonging to two
MGR-groups-a fact which only becomes apparent after re-firing at uoo'C.
(For explanations see text in Chapter 27; photographs were taken with a macro
lens by M. Baranowski.)
9 Examples of matrix types (samples re-fired at uoo'C) of non-calcareous
sherds (iron-rich red-firing or iron-poor whitish-firing) and of calcareous
pottery (yellowish-greenish firing). (For explanations see text in Chapter q;
photographs were taken with a macro lens by M. Baranowski.)
 LIST OF ABBREVIATIONS

AAS Atomic Absorption Spectroscopy

BSE Backscattered Electrons
EDS Energy Dispersive Spectrometry
EMPA Electron Microprobe Analysis
ICP Inductively Coupled Plasma
INAA Instrumental Neutron Activation Analysis
LA Laser Ablation
MGR Matrix Groups by Re-firing
MS Mass Spectrometry
OES Optical Emission Spectrometry
OM Optical Microscopy
OSL Optically Stimulated Luminescence
PIXE Particle Induced X- Ray Emission
ppb parts per billion (10-9)
PPL Plane Polarized Light
ppm parts per million (10-6)
RHX Rehydroxylation
SE Secondary Electron
SEM Scanning Electron Microscopy
SR Synchrotron Radiation
TL Thermoluminescence
WD Wavelength Dispersive
XPL Crossed Polarized Light
XRD X- Ray Diffraction
XRF X-Ray Fluorescence
8 stable isotope ratio expressed relative to a standard
measure of isotopic composition relative to a mantle reservoir
-

LisT oF CoNTRIBUTORS

Daniel Albero Santacreu is Assistant Lecturer in Prehistory and Archaeology at the

University of the Balearic Islands (Spain). He has developed archaeometrical and techno-
logical analysis of hand-made prehistoric pottery vessels from the Balearic Islands, Sardinia,
Andalusia, and Ghana. His current research concerns the role of technology in the inter~
pretation of ceramics and the application of concepts such as agency, habitus, technolog-
ical choices, and identity in the study of ancient societies. His most recent publication is
Materiality, Techniques and Society in the Pottery Production (De Gruyter Open).
Janet Ambers is a scientist in the Department of Conservation and Scientific Research at
the British Museum. She currently works mostly on the imaging of museum-related mate-
rials, with a specific interest in radiography, and on the analysis of museum objects using
various techniques but with an emphasis on Raman spectroscopy. Her particular interests
include pigment analysis with particular emphasis on the palettes of Ancient Egypt and the
Middle East, the identification of gemstones, jades, and geological materials by Raman spec-
troscopy, and the radiography of ceramics and other similar materials. She also has a profes-
sional interest in all forms of archaeological dating and analyses of human remains.
Juan Antonio BarcelO is an Associate Professor of Prehistory at the Universitat Auto noma
de Barcelona (Spain). He carries out specialized research in archaeological techniques and
theory, developing computer applications in archaeology, notably in the domains of spatial
analysis, statistics, artificial intelligence, modeling, and computer-aided visualization. He is
the director of the Quantitative Archaeology Laboratory (<http://grupsderecerca.uab.cat/
laqu/> ). He has directed and participated in archaeological projects in Spain, Portugal, Italy,
Syria, Nicaragua, Ecuador, and Argentina.
Hans Barnard is Adjunct Assistant Professor at the Department of Near Eastern Languages
and Cultures and Assistant Researcher at the Cotsen Institute of Archaeology, both at
UCLA. He has worked on sites in Armenia, Chile, Egypt, Iceland, Panama, Peru, Sudan,
Syria, Tunisia, and Yemen as archaeological surveyor, photographer, and ceramic analyst.
Currently he is involved in research projects investigating the interaction between the
Tiwanaku and Wari polities in the Vitor Valley (near Arequipa, Peru), and between the
Phoenician and Roman empires in Zita (near Zarzis, Tunisia).
Ina Berg is Senior Lecturer in Archaeology at the University of Manchester, UK Her main
areas of research are ceramic studies, the archaeology of Bronze Age Greece, the Cyclades
in particular, and island studies. While interested in all aspects of ceramics, her current
research focus is predominantly on the application ofX-radiography to pottery to explore
forming techniques as a means to understanding past potting traditions, workshop organi-
zation, learning networks, and knowledge transfer.
 -
XXVi LIST OF CONTRIBUTORS

Gulsebnem Bishop is a full-time CS!T faculty member and a program leader for the
Doctoral Program in Information Technology at Stratford University, VA. She holds a doc-
torate degree in Computer Science and Information Systems from Pace University, NY,
where she was able to combine her two passions: computing and archaeology. Her interests
are data analysis and interpretation, database development, and administration, as well as
future of data analysis. She has worked at a number of not-for-profit organizations such as
the American Museum of Natural History, the Human Rights Campaign, and the National
Cathedral in New York City and Washington, D.C., specializing in database systems devel-
opment, administration, and management.
Sophie Blain was a FNRS researcher at the University of Liege, Belgium. Her researches
focused on medieval building archaeology and more particularly on dating methods applied
to building materials, such as dendrochronology on wood beams and luminescence (TL!
OSL) dating methods on ceramic building materials and mortar. She worked on a number of
medieval churches in south-eastern England, northern France, Belgium, and northern Italy.
Eugenio Bartolini is currently a member of CaSEs Research Group (Complexity and
Socio-Ecological Dynamics) as Research Fellow at the Department of Archaeology and
Anthropology, IMF-CSIC (Spanish National Research Council, Barcelona, Spain) and Visiting
Research Fellow at the Department of Humanities, Universitat Pompeu Fabra (Barcelona,
Spain). His main research interests and topics include the adoption and transmission of cul-
tural variants, the coevolution of culture and genes (Dual Inheritance Theory), the develop-
ment and application of quantitative methods in archaeology, archaeological theory, and the
prehistory of the Arabian Peninsula.
Matthew T. Boulanger is a Lecturer in the Department of Anthropology at Southern
Methodist University and a Research Associate at the Archaeometry Laboratory at the
University of Missouri Research Reactor. He has published in Antiquity, American Antiquity,
Journal ofArchaeological Science, and Archaeometry. His research interests include composi-
tional analysis of archaeological materials, digital data management and preservation, evo-
lutionary archaeology, experimental archaeology, and Paleoindian lithic technology.
Dennis Braekmans is Assistant Professor at the Faculty of Archaeology, Leiden University,
and Department of Materials Science, Delft University ofTechnology. He runs the laboratory
for ceramic studies, where mineralogical and geochemical laboratory analysis is linked with
production studies, mechanical research, and ethnoarchaeological observation. The current
research focus is geared to ancient ceramics from North Africa, the Eastern Mediterranean,
and the Near East. Teaching activities include materials science, archaeometry, and experi-
mental archaeology.
Jaume Buxeda i Garrig6s is Lecturer in Archaeology and Director of the Cultura Material
i Arqueometria UB (ARQUB) research unit at the Universitat de Barcelona. His recent
work is mainly related to research projects in historical archaeology (ARCHSYMB and
TECNOLONIAL) designed to deepen our knowledge in aspects related to the interaction,
influence, and cultural change during the colonization process, through the archaeological
and archaeometric study of technical/technological impact, and issues of technical/techno-
logical traditions and change. Other research interests are classical archaeology, the effect
of weathering, and the role and treatment of compositional data in archaeological research.
 LIST OF CONTRIBUTORS xxvii

Manuel Calvo Trias is Lecturer in Prehistory and Archaeology at the University of the
Balearic Islands (Spain). He is head of the ArqueoUIB Research Group and PI of a research
project focused on the Balearic Islands Prehistory, as well as the project Archaeology in the
Upper White Volta basin (north-east of Ghana). His research is centered on the analysis
of material culture and technology. He is co-author of 'l\cci6n tecnica, interacci6n social y
pr<ictica cotidiana: propuesta interpretativa de la tecnologia" (Trabajos de Prehistoria 71) and
"Ceramic Transactions in a Multi-Ethnic Area (Upper East Ghana)" (Applied Clay Science
82).

Malgorzata Daszkiewicz works in collaboration with Warsaw University of Technology

and, since 1994, with Arbeitsgruppe Archaeometrie (FU Berlin). In 1998 she set up her own
company-ARCHEA-as a laboratory for archaeometric analysis and research, participat-
ing in international projects with many institutions. In 2009 and 2012 she was Senior Fellow
at the Cluster of Excellence TOPOl at FU Berlin, where she is now a part-time employee. Her
main research interests are in determining the technology and provenance of archaeological
ceramics (using MGR-analysis, thin sections, WD-XRF and pXRF) as well as devising tech-
niques for the classification of bulk ceramic finds and the development of methods for form-
ing techniques and functional properties (she has created a joint databank with Gerwulf
Schneider of G.30,ooo WD-XRF analyses).
Patrick Degryse is Professor of Archaeometry at the Department of Earth and
Environmental Sciences and Director of the Center for Archaeological Sciences at the
Katholieke Universiteit Leuven (Belgium). His main research efforts focus on the use of
mineral raw materials in ancient ceramic, glass, metal, and building stone production, using
petrographical, mineralogical, and isotope geochemical techniques. He teaches geology,
geochemistry, archaeometry, and natural sciences in archaeology, is an A. von Humboldt
Fellow and European Research Council Grantee, and is active in several field projects in the
eastern Mediterranean.
Kim Duistermaat is guest researcher at the Faculty of Archaeology, Leiden University. Her
interests include the organization of pottery production, and the study of seals and sealings.
Kim has worked and lived in Syria and Egypt and is currently resident in China.
Laure Dussubieux is a Laboratory Scientist at The Field Museum's Integrative Research
Center.
)elmer W. Eerkens is a Professor of Anthropology at the University of California, Davis,
where he runs the Archaeometry Laboratory. His research focuses on small-scale societies,
the evolution of material technologies, 'and the reconstruction of ancient subsistence and
settlement systems. Towards this end, he has applied a number of archaeometric techniques,
including gas chromatography-mass spectrometry, instrumental neutron activation analy-
sis, stable isotope analysis, and luminescence dating to ceramic assemblages from Western
North America and Peru.
Kent D. Fowler is an Associate Professor of Anthropology at the University of Manitoba in
Winnipeg> Canada. Since 1996, his research interests have centered on the ceramic traditions
of southeastern Africa from archaeological and ethnographic perspectives. His archaeologi-
cal research has focused upon ceramic manufacture and use in first millennium AD farming
societies of South Africa. He has conducted long~term ethnographic research in Zulu and
xxviii LIST OF CONTRIBUTORS

Swazi potting communities, examining how technical and social factors influence variation
in manufacture. His recent research interest is in how petrographic and chemical analyses of
ceramics are affected by potters' behaviors and the use of ceramics. Representative publica-
tions include "Zulu pottery production in the Lower Thukela Basin, KwaZulu-Natal, South
Africa" (zooS); "Clay acquisition and processing strategies during the first millennium AD in
the Thukela River basin, South Africa: An ethnoarchaeological approach'' (zou); "Ceramic
production in Swaziland" (2014); "Zulu ceramic production in the Phongolo River Basin,
South Africa'' (2015).
jaime Garda Rossell<\ is Lecturer in Prehistory and Archaeology at the University of the
Balearic Islands (Spain). His ethnoarchaeological research focuses on the analysis of pot-
tery forming methods in several potter communities from Chile, Ecuador, Egypt, Tunisia,
Morocco, and Ghana. He is co-author of Making Pots: El modelado de la ceramica y su poten-
cial interpretativo (BAR International Series 2540, Archaeopress) with Manuel Calvo.
Mark Golitko is a visiting Assistant Professor in the Department of Anthropology at the
University of Notre Dame, and a Research Associate at the Field Museum of Natural History
in Chicago. He utilizes chemical methods to explore how human social networks evolve in
response to environmental and social forces. His field and laboratory research has spanned
several regions, including Papua New Guinea, Europe, and the Americas. His publications
include "Mapping prehistoric social fields on the Sepik coast of Papua New Guinea: ceramic
compositional analysis using laser ablation-inductively coupled plasma-mass spectrometry"
(2012, Journal of Archaeological Science) and the book LBK Realpolitik: An Archaeometric
Study of Conflict and Social Structure in the Belgian Early Neolithic (2015, Archaeopress).
Alan F. Greene is a Postdoctoral Scholar in the Department of Anthropology and Stanford
Archaeology Center at Stanford University. His field research based in Armenia focuses
on the habitual economic transactions, production chains, and value transfo'rmations
of Bronze Age and Iron Age communities in the South Caucasus (q5oo-8oo BC). He is
also co-director of the Malting of Ancient Eurasia (MAE) Project, a research consortium
involved in the radiographic, tomographic, and synchrotron radiation-based analysis of
ceramic materials from across the Eurasian landmass. He is co-editor, with Charles Hartley
(University of Chicago), of a forthcoming volume on the structural analysis of archaeologi-
cal pottery.
Christopher Hall is Professor Emeritus and Professorial Fellow in the School of
Engineering, University of Edinburgh. He is a Fellow of the Royal Society of Edinburgh,
and a Fellow of the Royal Academy of Engineering. His research interests are in the chem-
istry and physics of materials used in construction engineering. Recent work includes
synchrotron-based diffraction methods, scanning-probe microscopy of mineral/water reac-
tions, and engineering analysis and chemistry in archaeology and building conservation.
Publications include Polymer Materials (1981, znd edn 1989 ); Water Transport in Brick, Stone
and Concrete (with W D. Hoff, 2002, znd edn 2012); Materials: A Very Short Introduction
(2014); and numerous scientific papers in professional journals.

Mark E. Hall is Assistant Field Manager of the Black Rock Field Office in the Winnemucca
District of the Bureau of Land Management. His research and field work has spanned sev-
eral geographic areas, from California and the Great Basin, Ireland, japan, Mongolia, and
 LIST OF CONTRIBUTORS XXiX

the Russian steppes. He is the author of more than fifty research papers, many focusing on
north-east Asian pottery production.
Roberto Hazenfratz-Marks is a collaborator of the Archaeometry Group at the Nuclear
and Energy Research Institute in Sao Paulo, directed by Dr. Casimiro S. Munita. He con-
centrates on the analysis of archaeological ceramics and geological material from Central
Amazon. He has experience with instrumental neutron activation analysis, X-ray diffrac-
tion, optically stimulated luminescence dating, electron paramagnetic resonance, and mul-
tivariate data analysis. He is also Professor of Engineering.
Robert B. Heimann is Professor Emeritus of Applied Mineralogy and Materials Science
at Technische Universitat Bergakademie Freiberg, Germany. From 1979 onward he worked
in Canada as a research associate (McMaster University), visiting professor (University
of Toronto), staff geochemist (Atomic Energy of Canada Limited), and research manager
(Alberta Research Council). From 1993 to 2004 he was a full professor at TU Bergakademie
Freiberg in Germany. He has authored and coauthored more than 300 scientific publications
including several books, and in 2001 was awarded the Georg- Agricola Medal of the German
Mineralogical Society (DMG). Research activities and interests are in advanced ceramics,
single crystal growth, and thermal spraying of environmental and biomedical coatings, as
well as archaeometallurgy and archaeoceramics.
Volker Hoeck is a retired professor. He was Professor of Geology at Paris Lodron University
of Salzburg, Austria, and Associate Professor at Babe~-Bolyai University of Cluj-Napoca,
Romania. His research interests include geochemistry and petrography of magmatic and
metamorphic rocks from the Alps, Carpathians, Dinarides, and Central Asia, as well as
petrography and geochemistry of archaeoceramics. His recent publications are "Insights
into the EPR Characteristics of Heated Carbonate-rich Illitic Clay" (2014, Applied Clay
Science); "Burnishing versus Smoothing in Ceramic Surface Finishing: A SEM Study"
(2015, Archaeometry), and "Geochemistry of Neogene Quartz Andesites from the Oa> and
the Gutai Mountains, Eastern Carpathians (Romania): A Complex Magma Genesis" (2014,
Mineralogy and Petrology).
Elisabeth Holmqvist works as an Academy of Finland Postdoctoral Fellow at the
Department of Philosophy, History, Culture and Art Studies, University of Helsinki. Her
research interests deal with ancient technologies and exchange systems, and geochemi-
cal provenancing of archaeological materials by ED-XRF, SEM-EDS, PIXE, ICP-MS, and
INAA. Holmqvist has worked on archaeological ceramics from the Near East, Europe, and
Latin America. In her PhD (UCL Institute of Archaeology, 2010), Holmqvist concentrated
on Byzantine-Islamic pottery manufacture and trade in the Near East, while her current
research focuses on Scandinavian and Baltic potting traditions and inter-regional ceramic
exchange from the Neolithic into medieval times.
Alice M. W. Hunt is a Assistant Research Scientist at the Center for Applied Isotope Studies,
University of Georgia. Her PhD in archaeological materials analysis developed cathodolu-
minescence spectrometry of quartz as a method for differentiating raw material sources in
fine-grained ceramics. Currently, her research focuses on developing analytical calibrations
and protocols for bulk chemical characterization of cultural materials (ceramics, anthropo-
genic sediments, copper alloys, and obsidian) by portable XRF. Recent publications include
 ,
XXX LIST OF CONTRlBUTORS

"Portable XRF analysis of archaeological sediments and ceramics" (Journal ofArchaeological

Science, 2015) and a monograph Palace Ware across the Neo-Assyrian Imperial Landscape:
Social Value and Semiotic Meaning (E.). Brill).
Carina Ionescu is Professor at Geology Department at Babe.-Bolyai University of Cluj-
Napoca, Romania, and Associate Professor at Kazan (Volga Region) Federal University,
Tartarstan, Russia. Her research interests focus on archaeoceramics and ophiolite petrol-
ogy and geochemistry. Her recent publications include "Burnishing versus Smoothing
in Ceramic Surface Finishing: A SEM Study" (2015, Archaeometry); "Insights into the
Raw Materials and Technology Used to Produce Copper Age Ceramics in the Southern
Carpathians (Romania)" (2016, Archaeological and Anthropological Sciences).
Marisol Madrid i Fernandez is a Researcher at the Cultura Material i Arqueometria UB
(ARQUB) research unit at the Universitat de Barcelona. Her work focuses on the application
of analytical techniques to the study of archaeological materials, especially ceramics. She has
participated in more than forty research projects highlighting the current TECNOLONIAL
project on historical archaeology and archaeometry. She is author/co-author of more than
fifty publications and has been co-organizer of two scientific international conferences. She
has had longlasting activity in the field of classical archaeology in several excavations, espe-
cially in the research project at the Roman town of Cosa, Italy, leading the study of Roman
pottery and its archaeometric characterization.
Marta Mariotti Lippi focuses on archaeobotany, palynology, and reproductive biology. She
has carried out archaeobotanical investigations at sites in Italy (Pompeii and Vesuvian area,
Paestum, Tuscany) and abroad (Russia, Czech Republic, jordan, Lybia). Since 2001 she has
cooperated in research projects in the "Land of Frankincense" UNESCO site ofSumhuram/
Khor Rori, and at Salut, Sultanate of Oman.
Lara Maritan was, between 1999 and 2005, a visiting scholar at the University of Glasgow
(UK) and the University of Cardiff (UK), funded by scholarships from the Gini Foundation,
the Italian Society of Mineralogy and Petrology (SIMP), and the Accademia Nazionale dei
Lincei/Royal Society. From 2003 she was a postdoctoral research assistant at the University
ofPadova before joining the faculty in the Department of Geosciences as an assistant profes-
sor in georesources and minero-petrographic applications for the environment and cultural
heritage (GEO/o9) in 2007.
Ana LuisaMartinez-Carillo is a researcher at the Research Institute oflberian Archaeology,
University ofJaen. She is a specialist in the application of new technologies in archaeologi-
cal analysis, in particular in ceramic studies, and has also participated in several regional,
national, and European research projects focused on three-dimensional modeling, integra-
tion of datasets, and on-line dissemination of the cultural heritage.

Leah D. Mine is an Associate Professor in the College of Liberal Arts at Oregon State
University, and INAA Research Coordinator at the Oregon State University Archaeometry
Laboratory.
Giuseppe Montana has been Associate Professor at the University of Palermo since 2005.
His re!earch activity covers topics in the field of mineralogy and petrography applied to
cultural heritage (archaeological ceramics, natural and artificial stones). Significant recent
-
LIST OF CONTRIBUTORS XXXi

publications include "Characterization of Clayey Raw Materials for Ceramic Manufacture

in Ancient SicilY:' Applied Clay Science, 53 (2011): 476-488; 'An Original Experimental
Approach to Study the Alteration and/or Contamination of Archaeological Ceramics
Originated by Seawater Burial;' Periodico di Mineralogia, 83 (2014): 89-120; "Different
Methods for Soluble Salt Removal Tested on Late-Roman Cooking Ware from a Submarine
Excavation at the Island ofPantelleria (Sicily, Italy);' Journal of Cultural Heritage, 15(2014):
403-413.

Noemi S. Miiller is Scientific Research Officer at the Fitch Laboratory of the British School
at Athens. She has held postdoctoral positions at NCSR Demokritos, where her research
focused on mechanical and thermal properties of archaeological ceramics, as well as in
Nicosia, Cyprus, and Barcelona, Spain. She is interested in applying analytical methods to
investigate inorganic archaeological artifacts and materials, focusing on the study of prov-
enance and technology and with a special interest in archaeological ceramics. Her research
also examines the affordance of utilitarian ceramics, focusing on cooking vessels, using
material testing to explore the influence of technological choices in manufacture on material
properties.
Pasquino Pallecchi is Adjunct Professor at the University of Florence and Head of the
Laboratory of Archaeological Heritage in Tuscany, Italy.
Patrick S. Quinn is an archaeological materials scientist working on ceramics and related
artifacts from a range of different periods and regions including prehistoric and later Britain,
pre-contact California, and the prehistoric Aegean. His early research focused on the occur-
rence of microfossils within ancient ceramic pastes and their research potential in terms of
pottery provenance and technology on Minoan Crete. He subsequently worked on the pal-
aeontology and ecology of microfossil-producing organisms before rejoining the University
of Sbeffield, then the Institute of Archaeology, University College London, as a permanent
member of the research staff, undertaking research, teaching, and Consultancy on archaeo-
logical ceramic analysis.
Marcia A. Rizzutto has been a Professor at the Physics Institute of the University of Sao
Paulo since 2001. She is also the coordinator of the Research Center of Applied Physics to
the Study of Artistic and Historical Cultural Heritage of the University of Sao Paulo. Since
2003 she has been devoted to the use of applied physics to the study of cultural heritage
objects connected with different areas such as archaeology, history, art history, paleontol-
ogy, chemistry, conservation, and restoration. As coordinator of the research group she has
a wider investigation program using non~destructive physics analyses in different museum
collections of the University of Sao Paulo, in partnership with teachers/researchers from the
museum's institutions.
Valentine Roux is Director of Research at the CNRS, Nanterre, France. Her work com-
bines methodological research on technical skills and an anthropological approach to
ceramic assemblages, archaeological research on the history of technology and people in
the Southern Levant, and ethnoarchaeological research in India on specialization and dif-
fusion of potting techniques. Selected recent publications include a handbook, in collabo-
ration with M.-A. Courty, entitled Des ceramiques et des hommes: Decoder les assemblages
archeologiques (2016); an edited issue of Journal of Archaeological Method and Theory (2013,
XXXii LIST OF CONTRIBUTORS

20/2), with Courty, entitled "Discontinuities and Continuities: Theories, Methods and
Proxies for an Historical and Sociological Approach to Evolution of Past Societies"; and
an edited issue of Paleorient (2013, 39!1) with Braun, entitled "The Transition from Late
Chalcolithic to Early Bronze in the Southern Levant: Continuity and/or Discontinuity?':
GerwulfSchneider has since 1975 been involved in archaeornetric research and the teaching
of archaeometry, from 1980 to 2003 at the Institute of Inorganic and Analytical Chemistry
(Arbeitsgruppe Archaeometrie), and currently as a research associate at the Cluster of
Excellence Topoi at the Free University of Berlin. His main focus is on chemical and min-
eralogical analysis of archaeological ceramics and the interpretation of data in archaeologi-
cal terms. His research interests encompass Roman pottery in Germany, Hellenistic to Late
Antique pottery in the Mediterranean region, and various projects on Neolithic to medieval
pottery in Europe, Mesopotamia, and Sudan (he has created a joint databank of qo,ooo
WD-XRF pottery analyses with M. Daszkiewicz).
Prabodh Shirvalkar is currently working as an associate professor in the department
of Archaeology, Deccan College Post Graduate and Research Institute, Pune, India. His
research interest focuses on the Harappan Civilization, particularly in regards to ceramic
technology, provenance, and trade networks. At present, he is working on creating a model
for the rural economy of Harappans. In addition, he has expertise in field archaeology and
the application of processualism.
Shlomo Shoval is Professor of Earth Sciences at the Open University of Israel. He is also
Guest Professor at the Institute of Earth Sciences of the Hebrew University of jerusalem
and Visiting Scientist at the Institut Lumiere Matiere ofUniversite Claude Bernard Lyon-1,
France. He is an expert in the analysis of archaeological ceramics, ceramic raw materials, and
clay minerals by infrared spectroscopy (FT-IR) and other scientific methods (LA-lCP-MS,
XRF). Among his current research projects are studies of the technologies used in manufac-
ture and in paint decoration of Levantine Bronze and Iron Age ceramics.
Johannes H. Sterba has been working in neutron activation analysis for more than a
decade, starting with geological samples and soon moving to archaeologically relevant mate-
rials such as pumice, obsidian, and later ceramics. He is interested in the statistical analysis
of the gathered data and in the intercomparability of different analytical methods. Recent
publications include "NAA and XRF analyses and magnetic susceptibility measurement of
Mesopotamian cuneiform tablets" (Scienze dell'Antiquita, 2011); "Raising the temper-fl·
spot analysis of temper inclusions in experimental ceramics" (Journal ofRadioanalytical and
Nuclear Chemistry, 2011); and "Volcanic glass under fire-a comparison of three comple-
mentary analytical methods" (X-RaySpectrometry, 2013).
Manfredo H. Tabacniks is a full professor at the Physics Institute of the University of Sao
Paulo. In 1994 he served as a postdoctoral researcher for two years at the IBM Almaden
Research Center, San jose, California, on the application of ion beam methods (PIXE and
RBS) for tbe analysis of thin films. Since 1996 he has been head of the Ion Beam Analysis
facility of the Institute of Physics at USP. His main research interests deal with ion beam
methods for advanced material analysis and for the modification of materials.
jeremy Taylor took up a Leverhulme Research Fellowship at the School of Archaeology,
University of Leicester, in 1999, before being appointed a Lecturer in Archaeology in 2001.
 LIST OF CONTRIBUTORS xxxiii

He is currently a director of the major field project at Burrough Hill, Leicestershire. His
research interests center on social change in Iron Age Britain and the Western Roman prov-
inces through study of their rural landscapes, and on interrelationships between theory and
method in survey-based archaeological research, such as geophysics, geochemistry, and
aerial survey.
MichaelS. Tite was, before retiring, the Edward Hall Professor of Archaeological Science and
Director of the Research Laboratory for Archaeology and the History of Art at the University
of Oxford, where he is now Professor Emeritus and Fellow of Linacre College. Formerly he
served as Keeper of the Research Laboratory at the British Museum, and has been a Fellow of
the Society of Antiquaries since 1977- The underlining theme of his research during the past
thirty years has been the study of the technology involved in the production of (1) faience and
related early vitreous materials from Egypt and the Near East, and (2) glazed pottery from the
Bronze Age through the Roman period in the Near East, Europe, the Islamic world, and China.
Jolien Van Pevenage is currently a PhD candidate in the Raman Spectroscopy Research
Group. She is interested in the application of Raman spectroscopy to the study of ceramic
artifacts for their identification and classification in order to define, for example, the ori-
gin or the composition of the materials and production techniques. Her research combines
the use of Raman spectroscopy with X-ray fluorescence spectroscopy and advanced data
processing methods. Her work is presented at international conferences and is published in
leading scientific journals.
Peter Vandenabeele was appointed as research professor in the Department of Archaeology
at Ghent University, where he applies his analytical skills to the study of archaeological and
artistic objects. His research focuses mainly on the application of Raman spectroscopy in
art analysis. He has authored more than a hundred research papers on Raman spectroscopy
and its application in archaeometry, along with several book chapters and conference pre-
sentations. Recently, he has published, together with Howell Edwards, Selected Topics in
AnalyticalArchaeometry (RSC Publishing, 2012).
Yona Waksman is a Senior Researcher at the French National Research Center (CNRS)
in Lyon. She specializes in archaeometric approaches to medieval ceramics in the Eastern
Mediterranean and the Black Sea, through provenance and technological studies. Her publi-
cations include major sites such as Constantinople/Istanbul, and lay new foundations for the
investigation of economic, cultural, and social phenomena in the Byzantine world and the
medieval Middle East.
Ian K. Whitbread read Archaeology and Geology at the University of Bristol before under-
taking a research fellowship at the Fitch Laboratory, British School at Athens, Greece.
Formerly he was a Principal Research Scientist at the Center for Materials Research in
Archaeology and Ethnology, Massachusetts Institute of Technology, USA, and then
Director of the Fitch Laboratory. He joined the School of Archaeology and Ancient History,
University of Leicester, in 2001. His current research interests lie in the analysis of ancient
ceramic materials with respect to issues of trade/exchange and the socially embedded nature
of technology.
Bettina A. Wiegand has long-term experience in isotope geochemistry at the University
of Goettingen, Germany, and Stanford University, USA. Application of isotope methods
 -
xxxiv :UST OF CONTRIBUTORS

to various research fields include ceramic provenance studies, human migration studies,
and hydrogeological and environmental research. Related publications include "Strontium
Isotopic Evidence for Prehistoric Transport of Gray-Ware Ceramic Materials in the Eastern
Grand Canyon Region, USA;' Geoarchaeology 26 (2011): 189-218; and "Reconstructing
Middle Horizon Mobility Patterns on the Coast of Peru through Strontium Isotope
Analysis;' (Journal ofArchaeological Science 26 (2009): 157-165).
Ian P. Wilkinson was a principal scientist with the British Geological Survey before retiring,
and is now an Honorary Research Associate at both the BGS and the University of Leicester.
He is a specialist in Mesozoic and Cenozoic-Recent ostracods and foraminifera, working on
mapping, hydrocarbons, geohazards, and palaeoenvironmental and archaeological projects.
Although focusing principally on the UK, he also has experience in, for example, Ecuador,
USA, Antarctica, Hong Kong, the Persian Gulf, Papua New Guinea, Armenia, and Russia.
Mark Williams is Professor of Geology at the University of Leicester, where he researches
climate and environmental change reflected in the fossil record. He has worked at the
Universities of Frankfurt, Lyon, and Portsmouth, and for the British Geological Survey and
the British Antarctic Survey. He has a strong interest in the geology of the Arabian Peninsula
and has consulted for Saudi Aramco.

!ill

!r
 PART I

·································································································

INTRODUCTION
.................................................................................................
 CHAPTER 1

INTRODUCTION TO
THE OXFORD HANDBOOK
OF ARCHAEOLOGICAL
CERAMIC ANALYSIS

ALICE M. W. HUNT

CERAMIC is one of the most complex and ubiquitous archaeomaterials, occurring around
the world at prehistoric through industrial sites and used to fashion everything from resi-
dences and technological installations to utilitarian wares and decorative/votive figurines.
It is not simply the range of cultures and functions that ceramics serve but the diversity in
materials and manufacture technology that makes archaeological ceramic analysis as chal-
lenging as it is essentiaL
In this volume we address the sociocultural, geochemical, and mineralogical complex-
ity inherent in archaeological ceramic analysis and provide insight into the uncertainties
by providing concrete guidelines for designing rigorous research strategies and develop-
ing sophisticated and answerable anthropological research questions. Part II is dedicated
to issues related to designing ceramic research and evaluating the varied types of data this
research generates. jaume Buxeda i Garrig6s and Marisol Madrid i Fernandez (Chapter 3)
outline the two essential types of research for archaeological ceramic analysis, advancing
the discipline and answering archaeological questions, and provide tools and guidelines for
approaching each. In Chapter 4, Roberto Hazenfratz Marks discusses how to identify and
report the uncertainty inherent in ceramic analysis with particular emphasis on interpreting
geochemical data. In Chapter s, Gulsebnem Bishop discusses the types of data generated in
archaeological ceramic analysis, the strengths and weaknesses of each, and the appropri-
ate model/statistical tools for describing and analyzing this data. Many of the most inter-
esting and important anthropological questions involve comparing ceramic datasets, often
from different excavations or laboratories and separated by decades. In Chapter 6, Matthew
Boulanger offers insight into working with these datasets and how to preserve data for future
analysis.
Part Ill, Foundational Concepts, provides a detailed discussion of, and recommends
best practices for, the definition, description, and illustration of archaeological ceram-
ics. In Chapter 7, Giuseppe Montana defines ceramic raw materials and describes their
4 AUCF.M.\V.HUNT

compositional and physical properties, such as plasticity and swelling, and how these prop-
erties are manipulated by human behavior. Chapters 8 and 9 both investigate the social
and economic organization of ceramic manufacture: Valentine Raux (Chapter 8) evalu-
ates ceramic manufacture using the chaine operatoire approach, while Kim Duistermaat
(Chapter 9) offers a relational approach to ceramic manufacture based on network analy-
sis models. Both approaches discuss how to locate the technical behaviors associated with
ceramic manufacture within the socioeconomic and cultural constraints in operation.
Yona Waksman tackles ceramic provenance in Chapter 10, providing unambiguous defini-
tions and practical guidelines for forming production and/or compositional groups within
a ceramic assemblage. In Chapter 11, Gerwulf Schneider details the geochemical and min-
eralogical uncertainty created by alteration of archaeological ceramics during their use-life
and as a result of post-depositional processes, and discusses methods for identifying these
changes during analysis.
1be last three chapters in Part III provide practical skills, definitions, and guidelines for
the description and illustration of archaeological ceramic artifacts. Daniel Albero Santacreu,
Manuel Calvo Trias, and jaime Garcia Rossell6 (Chapter 12) discuss formal classification and
analysis of ceramics, offering universal definitions and insight for the interpretation of for-
mal data, while remaining sensitive to the practical and cultural factors influencing vessel
shape and size. Ian Whit bread (Chapter 13) similarly establishes guidelines for best practice
in describing ceramic fabrics both in hand specimen (macroscopic analysis) and thin section
(microscopic analysis), along with methodologies for preparation of samples and reporting/
publishing fabric descriptions. In Chapter 14, Prabodh Shirvalkar provides a primer for con-
structing accurate and informative analytical illustration of archaeological ceramics.
The remainder of the volume is dedicated to the analytical techniques used in archaeo-
logical ceramic analysis and is organized broadly by anthropological questions. There are
many ways in which these techniques could be categorized (see Chapter 35 on Typology and
Classification), especially since each technique or method provides data relevant to more
than one line of inquiry and most anthropological questions require more than one type of
data (see Table 1.1). However, for reasons both practical and functional we present each ana-
lytical technique according to the fundamental anthropological question to which it most
often or significantly contributes. These four fundamental research areas are Provenance
(Part IV), Manufacture (Part V), Function (Part VI), and Date (Part VII). Each technique- or
method-specific chapter includes its scientific and/or theoretical background, discussion of
practical issues, such as cost and sample preparation, and case studies emphasizing the util-
ity of the technique in addressing anthropological questions of provenance. When possible,
guidelines for best practice of collecting and interpreting the data are provided.
Ceramic provenance is typically evaluated using compositional data. In Part IV, bulk
chemical, phase, and mineralogical analysis, as well as micropalaeontological analysis, are
discussed. Chemical methods include chapters on isotope analysis by Bettina Wiegand
(Chapter 18), X-ray fluorescence by Robert Heimann (Chapter 19) and Mark Hall (Chapter
20), handheld portable energy-dispersive X-ray fluorescence spectrometry by Elisabeth
Holmqvist (Chapter 21), particle induced X-ray emission spectrometry by Marcia RiZ2utto
and Manfredo Tabacniks (Chapter 22), inductively coupled plasma-mass spectrom-
etry by Mark Golitko and Laure Dussubieux (Chapter 23), neutron activation analysis by
Leah Mine and johannes Sterba (Chapter 24), and synchrotron radiation by Alan Greene
 INTRODUCTION 5

Table 1.1 Analytical methods included in this Handbook, and which of the four
primary research questions they contribute toward answering
Provenance Manufacture Technology Function Date
-------
EPMA X X X
Ethnography X X X
Experimental Firing/Re-firing X
FT-IR X
ICP-MS/LA-ICP-MS X

INAA X
!so tope Analysis X
Mechanical Properties X X
Micropalaeontology X X
Morphometric Analysis X X X
Organic Inclusions X X X
Organic Residue X X
Petrography X X X
PIXE X X
pXRF X
Raman Spectroscopy X

RHX Dating X
Tl Dating X
Typology X X X
X-Ray Radiography X X
XRD X X
XRF-EDS/WDS X X

(Chapter 25). Mineralogical and phase analysis methods include chapters on petrography
by Dennis Braekmans and Patrick Degryse (Chapter 15), electron probe microanalysis by
Carina Ionescu and Volker Hoeck (Chapter 17), and X-ray diffraction by Robert Heimann
(Chapter 19). Micropalaeontology (Chapter 16) is written by Ian Wilkinson, Patrick Quinn,
Mark Williams, jeremy Taylor, and Ian Whitbread.
In Part V, methods and techniques on ceramic manufacture include chapters on eth-
nography (Chapter 26) by Kent Fowler, experimental firing and re-firing (Chapter 27) by
6 ALICE M. W. HUNT

Malgorzata Daszkiewicz and Lara Maritan, X-ray radiography (Chapter 30) by Ian Berg
and janet Ambers, and organic inclusions by Marta Mariotti Lippi and Pasquino Pallecchi
(Chapter 31). Chapters on Fourier transform infrared spectroscopy (Chapter 28) by
Shlomo Shoval, and Raman spectroscopy (Chapter 29) by )alien Van Pevenage and Peter
Vandenabeele, are also included in Part V because they can provide valuable information
about mineralogical alteration in ceramic fabrics and surface treatments.
Vessel function can be assessed from the formal attributes and performance charac-
teristics of a vessel or artifact, as well as any organic residues preserved on their surfaces.
Therefore, Part VI includes discussion of morphometries (Chapter 32) by Ana Martinez-
Carillo and juan Antonio Barcelo, mechanical properties (Chapter 33) by Noemi Suzanne
Muller, and residue analysis (Chapter 34) by Hans Barnard and )elmer W Eerkens.
Part VII investigates the direct and indirect or relative dating of ceramics, and includes
chapters on typology and classification (Chapter 35) by Eugenio Bertolini, and direct dating
techniques of luminescence and rehydroxylation dating in a chapter by Sophie Blain and
Christopher Hall (Chapter 36).
 CHAPTER 2

HISTORY OF SCIENTIFIC
RESEARCH

MICHAELS. TITE

AIMS

THE primary aim of scientific research into archaeological ceramics is the investigation of
the overalllife~cycle of surviving ceramics starting with their production and continuing
through their distribution to their use, reuse, and ultimate discard (Tite, 1999, 2008). The
first step involves reconstruction of the production, distribution, and use of ceramics. The
second step then involves interpretation of this reconstructed life-cycle in order to obtain
a better understanding of the behavior of the people who produced, distributed, and used
these ceramics.
Reconstruction of the production technology of archaeological ceramics involves the
investigation of raw materials, tools, energy sources, and techniques used in the procure-
ment and preparation of the clay, forming of the pot, and its surface treatment, decoration,
and firing. Such information can be inferred from the observed macrostructure, microstruc-
ture, and chemical and mineral/phase compositions of the ceramics. The reconstruction of
distribution (i.e. provenance studies) involves trying to establish, on the basis of thin-section
petrography and/or chemical composition, whether ceramics were locally produced or
imported, and if the latter, to identify the production center and/or source of the raw mate-
riaL The determination of the use to which ceramic vessels were put involves their examina-
tion for surface wear and the presence o.f soot deposits, the analysis of surviving organic
residues, and the investigation of their physical properties.
In the interpretation of the reconstructed production technology of archaeological
ceramics, the primary questions that need to be considered are why ceramics were first
adopted for use in different parts of the world, and why, when adopted, a particular produc-
tion technology was chosen. The interpretation of the reconstructed distribution of ceramics
is concerned both with trying to determine patterns of trade or exchange away from any
identified production center or source of raw material, and the underlying sociocultural rea-
sons for that pattern.
8 MICHAELS. TITE

OVERVIEW OF HISTORY

Leaving aside isolated examples of scientific research into ancient ceramics in the nineteenth
and first half of the twentieth centuries, a coherent and continuing program of such research
really only began in the 1950s. This occurred as part of the emergence of the overall field of
archaeological science which, at that time, included the application of geophysical prospec-
tion and scientific dating methods to archaeology as well as the scientific study of the full
range of archaeological artifacts (Aitken, 1961). It is generally considered that the starting
point for present-day scientific research into archaeological ceramics was the groundbreak-
ing volume by Anna Shepard (1956) entitled Ceramics for the Archaeologist. However, two
further crucial, and more or less contemporary, developments were the founding in 1955 of
the Research Laboratory for Archaeology and the History of Art at the University of Oxford
with E. T. (Teddy) Hall as its first Director, and the beginning of instrumental neutron acti-
vation analysis (INAA) of ceramics at the Brookhaven National Laboratory (Long Island,
New York) under the direction of(Ed) Sayre (Sayre and Dodson, 1957).
The Oxford Research Laboratory, which was founded through the combined efforts of a
physicist (Lord Cherwell) and an archaeologist (Professor Christopher Hawkes), went on
to become a focus for archaeological science, or archaeometry as it was termed in Oxford,
both in the United Kingdom (UK) and internationally, 1hus, the publication Archaeometry,
which was started in 1958 as the Bulletin of the Research Laboratory for Archaeology and the
History of Art, went on to become an international research journal. Similarly, the train-
ing course in 1962, and subsequent annual reunions, organized for archaeologists who had
purchased proton gradiometers from the Laboratory, went on to become the International
Symposium for Archaeometry, initially held annually, but now held biennially, of which the
40th Symposium was held in Los Angeles in 2014.
The continuing development of archaeological science, including scientific research into
archaeological ceramics, has depended, first, on the provision of funding for research spe-
cifically into aspects of this new discipline, and second, on the inclusion of the teaching of
archaeological science in university archaeology degree courses. Although such crucial
developments bave now occurred, to a varying extent, throughout the world, the UK has
always been at the forefront in this respect. Thus, in 1976, the UK Science and Engineering
Research Council established a Science-based Archaeology Committee which was provided
with funds to support the development of new scientific techniques and approaches to the
study of archaeological material, and such research funding has continued in the UK in
one form or another up to the present day. Furthermore, during the 1970s, the University of
Bradford introduced one-year MA and three-year BTech courses in archaeological science,
and now, few students in the UK can emerge from an undergraduate archaeology course
without some knowledge of archaeological science, and many can be classed as true archae-
ological scientists.
As discussed in detail in the next section in this chapter, progress in the reconstruction
of the life-cycle of archaeological ceramics has depended mainly on the development and
availability of new methods of scientific investigation.ln contrast, progress in the interpreta-
tion of the life-cycle of archaeological ceramics has been, in large part, the result ofimproved
communication and collaboration between the scientists involved in the reconstruction,
 HISTORY OF SCIENTIFIC RESEARCH 9

and archaeologists from across the discipline, including field archaeologists, theoretical
archaeologists, and ethnoarchaeologists.

RECONSTRUCTION OF THE CERAMIC LIFE-CYCLE

In her book Ceramics for the Archaeologist, Shepard (1956) provided a description of the raw
materials and processes involved in the production of archaeological ceramics, together with
a summary of their physical properties. She then went on to describe how the raw materials
used might be identified and production processes revealed. The analytical methods avail-
able to Shepard were essentially limited to binocular microscopy, petrographic microscopy,
and optical emission spectroscopy (OES).
As evident from the contents of the current volume, the range of analytical tools avail-
able for the study of archaeological ceramics has increased dramatically during the subse-
quent fifty or so years (Pollard et al., 2007). Of these, scanning electron microscopy (SEM),
a range of methods for the determination of chemical composition, and organic residue
analysis, using gas chromatography in combination with mass spectrometry (GC-MS), have
had wide-ranging applications. In addition, there are a number of new analytical techniques
which, by their nature, have had a more limited application for the study of archaeological
ceramics.

Scanning Electron Microscopy

Examination of polished sections using SEM has provided extremely valuable informa-
tion on the production technology of archaeological ceramics, supplementary to that
provided by optical microscopy (Tite, 1992). This is, in part, because the SEM provides a
higher magnification (typically used in the range xwo to xsoo). However, more impor-
tantly, either an analytical SEM with attached X-ray spectrometer or an electron micro-
probe (EMP) can determine quantitatively the chemical composition of the different
phases or components present. For example, the extent of vitrification in earthenware
bodies can provide an estimate of the firing temperature, and the composition of the high
temperature phases observed in porcelain bodies can provide information about the raw
materials used in their production. Additionally, in cross-section, it has been possible to
determine, for the first time, the composition of a slip or glaze entirely separately from that
of the underlying ceramic body. It has ·thus been possible to distinguish between alkali-
lime, high lead, and lead-alkali glazes (Tile et al., 1998), and identify the different opaci-
fiers and colorants used.
During the 1980s, the application of SEM analysis to archaeological ceramics facilitated
research into a wide range of ceramics (earthenwares, stonewares, porcelains, and quartz-
paste bodies), which resulted in significant advances in our understanding of their pro-
duction technologies. Pioneers in this research include Kingery and Vandiver (1986) at
Massachusetts Institute of Technology, and Tite and colleagues (Tile, 1992) at the British
Museum.
 ,
l0 MICHAELS. TIT£

Determination of Chemical Composition

Initially, OES, INAA and X-ray fluorescence spectrometry (XRF) were the primary ana-
lytical techniques used in the study of archaeological ceramics. Of these techniques, INAA
and XRF have continued in use until the present day, but OES was replaced first by atomic
absorption spectroscopy (AAS) in the 198os, then by inductively coupled plasma spectrom-
etry with OES (ICP-OES) in the 1990s, and finally, by ICP with mass spectrometry (ICP-
MS) at the beginning of the current millennium. In comparison with INAA, ICP-MS has
similar detection limits but can analyze for a much wider range of elements. In addition,
ICP-MS does not require access to nuclear reactors, which are becoming less widely avail-
able. However, INAA, in using a powder sample rather than the acid dissolution required
with ICP- MS, retains significant advari.tages in terms of easy interlaboratory comparisons
and rapid sample preparation.
The primary role of these techniques has been the determination of the chemical com-
positions of ceramics for provenance studies with the aim of establishing where the ceram-
ics were produced. Initially, chemical analysis was regarded as an alternative to thin-section
petrography, especially in the case of fine-grained ceramics or when only the more ubiqui-
tous non-plastic inclusions, such as quartz and shell, were present. However, Shepard, in the
Preface written for the fifth printing (1965) of Ceramics for the Archaeologist, was highly criti-
cal of the use of chemical analysis in isolation. As a result, a more fully integrated approach to
provenance studies has been progressively developed (Heidke and Miksa, 2000). A crucial
first step in any such study should now be to group the entire assemblage from a site into pot-
tery types on the basis of observed style (e.g. shape, surface decoration) and temper type, as
determined by examination with a low-power binocular microscope. Second, the local geol-
ogy should be assessed, and fieldwork undertaken to identify and collect samples oflocally
available clays and sands. Only then should both thin-section petrography and chemical
analysis be undertaken on representative sherds of each pottery type.

Organic Residue Analysis

From the 1990s onwards, GC-MS has been extensively used for the analysis of the organic
residues surviving in archaeological ceramics (Heron and Evershed, 1993). Lipids, present
as fats, oils, waxes, and resins, are the most useful surviving organic compounds for resi-
due analysis, and can be used to establish whether animal, vegetable, or fish products were
the original contents of pottery vessels. As well as contributing to the investigation of past
human diets, organic residue analysis is particularly valuable in helping to understand the
reasons for adoption of the first ceramics (Craig et al., 2013). In addition, the distribution of
the bulk quantities oflipids over the interior of vessels has provided information on how dif-
ferent cooking pots were actually used (Charters eta!., 1993).

Analytical Techniques with More Limited Application

In the context of microscopy, the very high magnification possible with transmission elec-
tron microscopy (TEM) has played a crucial role in understanding the complex processes
 HISTORY OF SCIENTIFIC RESEARCH 11

involved in the production oflustre decoration on glazed Islamic ceramics (Perez-Arantegui

et al., 2001).
In the context of the determination of chemical composition, handheld XRF systems are
being increasingly used in the analysis of ceramic glazes. Although these instruments only
provide semi-quantitative data and do not analyze for the lighter elements, the particular
importance of this technique is that it is entirely non-destructive, and the instrument can
be brought to and used on archaeological sites and in museums where the ceramics are
located.
In the context of phase analysis, the well-established method of X-ray diffraction
(XRD), which identifies both mineral phases surviving from the raw materials and
those formed during firing the body, has continued to be used to provide informa-
tion about the raw materials and firing temperatures employed in ceramic production
(Heimann and Maggetti, 2014: 73). More recently, Raman spectroscopy, which is again
non -destructive, has been increasingly employed to identify the pigments used to deco-
rate ceramics, as well as the colorants and opacifiers used in ceramic glazes (Smith and
Clark, 2004).

INTERPRETATION OF THE CERAMIC LIFE-CYCLE

In order to achieve satisfactory interpretation of the reconstructed life-cycle of archaeologi-

cal ceramics, it is essential that collaboration between the scientist involved in the recon-
struction and the archaeologist who provided the ceramics is successful. Unfortunately,
there were some tensions between scientists and archaeologists when such research first
began in the 1950s (Preface to fifth printing of Shepard, 1965), and by the early 1990s there
was considerable criticism of archaeological science by archaeologists and curators, particu-
larly in the context of artifact studies (Dunnell, 1993).
However, by the end of the 1990s these tensions had significantly reduced, in large part as
a result of a more sustained dialogue between archaeological scientists and archaeologists.
Thus, a high proportion of university archaeology departments, and particularly those in
the UK, now include archaeological scientists on their staff, and a significant number of PhD
students are jointly supervised by an archaeological scientist and archaeologist. In addi·
tion, there are an increasing number of research excavations, such as Batao Grande in Peru
(Shimada and Craig, 2013), and <;:atalhoyiik in Turkey, excavated since 1993 by Ian Hodder
(<http:/ /www.catalhoyuk.com> ), on which archaeological scientists are actively involved in
the in situ examination of artifacts, the selection of samples for analysis back in the labora-
tory, and fieldwork to locate possible sources of the relevant raw materials, together with
participation in experimental artifact replications.
Fred Matson (1965), who introduced the concept of ceramic ecology, was one of the first
scholars to emphasize that the effective interpretation of the life-cycle of archaeological
ceramics requires an holistic approach. Such an approach takes into account the fact that pro-
duction, distribution, and use are firmly embedded within the overall environmental, tech·
nological, economic, social, political, and ideological contexts which in turn both impinge
on (i.e. constrain and drive) and are impacted by the production, distribution, and use of
ceramics.
12 MICHAELS. TITE

1~lking Matson's ceramic ecology concept as their starting point, Sillar and Tite (2ooo)
proposed a framework for the interpretation of the life-cycle of archaeological ceramics
and, in particular, the factors that determine technological choice and change. For example,
they believe that the first factors influencing technological choice are the availability and
performance characteristics of the raw materials, tools, energy sources, and procedures for
forming, surface treatment, and firing of the pottery. Secondary factors which influence
technological choices include patterns of trade and exchange, which impact the scale of
production and the extent of craft specialization (e.g. household, workshop, or factory pro-
duction) (Peacock, 1982). The intended use of the ceramics can also influence technological
choice by requiring specific performance characteristics, and hence, physical properties of
the ceramics (Tite et al., 2001).
When considering the factors that determine technological choice, it is important to
adopt an ernie approach in which one tries to understand what the artisans thought they
were achieving through their particular technological choice, and what the people using
the ceramics tbought were their important properties. In this context, ethnoarchaeological
studies (Longacre, 1991) have a definite contribution to make to archaeological ceramic anal-
ysis by exposing us to alternative ways of thinking about the world. Thus, ethnoarchaeology
reminds us that the choice of raw materials and production techniques can express aspects
of social identity and/or have ideological significance (Jones, zooo). Similarly, ceramics can
be used to establish bonds between social groups, and that, for this purpose, visual and tac-
tile characteristics can be more important than utilitarian properties, such as mechanical
strength and thermal shock resistance.
After production and technological choice, the second aspect of the ceramic life-cycle
requiring interpretation is the distribution of ceramics away from identified production cen-
ters or sources of raw material. For such "provenance" studies to make a significant contribu-
tion to our understanding of trade and exchange, large-scale, long-term projects are essential.
One example has been the study of Mayan pottery, which has involved more than 10o,ooo
fabric characterizations by binocular microscopy and more than w,ooo INAA analyses
(Bishop, 1994). Another example is the wide-ranging analysis, over a fifty-year period, of
Minoan and Mycenaean pottery, which started with OES analyses (Catling et al., 1963) but
subsequently made use of a fully integrated approach (Day et al., 1999). Both these studies
have demonstrated that, by interrogating provenance data beyond simplistic classifications
oflocal and non-local, they can provide significant insights into prehistoric social landscapes.
Further, quantification of the fall-off in the quantity of a particular ceramic type with
increasing distance from source can, in principle, be used to assist in distinguishing between
the different modes of trade or exchange (e.g. down-the-line, middleman, or central place)
although, in reality, an unambiguous result is rarely obtained (Renfrew, 1975).

FUTURE DEVELOPMENTS

For the investigation of unglazed archaeological ceramics (i.e. essentially earthenwares),

no major developments in the range of scientific techniques used are envisaged in the
 HISTORY OF SCIENTIFIC RESEARCH 13

immediate future. Instead, the emphasis will continue to be on the employment of an

holistic approach in which, as far as possible, production, provenance, and use of a com~
plete ceramic assemblage are investigated. For the future, greater use of handheld XRF for
body analyses is envisaged, together with more frequent fieldwork in an attempt to identify
sources of raw materials. Crucial to such studies is the continuing improvements in col~
laboration between archaeological scientists and archaeologists through greater involve-
ment of the former in fieldwork and excavation, and in defining the archaeological research
questions.
Additionally, using the methodology developed by Richard Evershed and colleagues at
the University of Bristol (Evershed, zooS), unglazed ceramics will be increasingly exploited
as a source of organic residues to detect the processing of different commodities and the
investigation of dietary change. Further research into the factors determining the mechani-
cal and thermal properties of unglazed ceramics is also envisaged (Heimann and Maggetti,
2014: 1S).
Conversely, it is in the investigation of glazes and high-gloss layers applied to earthen-
wares, stonewares, and porcelains that the more recent (and future) developments in meth-
ods of scientific examination are likely to have the greatest impact. In this context, the high
X-ray flux generated by synchrotron radiation sources can be used for high-resolution XRF
and XRD, as well as for both extended X-ray absorption fine structure (EXAFS) and X-ray
absorption near-edge spectroscopy (XANES), both of which provide information on ele-
ment valence state. Rutherford backscattering spectroscopy (RBS) using a high-energy ion
beam can provide information on composition depth profiles.
Following on from its use in the analysis of ancient glasses (Shortland et al., 2007), laser
ablation ICP-MS (LA-ICP-MS), because of its low detection limits and wide element range,
has considerable potential for supplementing EPMA analyses of ceramic glazes and high-
gloss layers, the same polished sections being used for both methods. However, because of
their inhomogeneity, the method will have only limited use in the analysis of ceramic bod-
ies, probable exceptions being some of the more homogeneous porcelain bodies (Wallis
and Kamenov, z013). Again, stable isotope analyses, previously used in the study of ancient
glasses to provide information on the sources of the raw materials (Degryse and Schneider,
zooS), could similarly be used in the study of ceramic glazes. Thus, strontium (Sr), neodym-
ium (Nd) and oxygen (0) isotopes could be used to investigate the sources of the silica and
alkali flux used to produce a glaze, and antimony (Sb) isotopes to investigate the source of
antimony used in the production of lead antimonate yellow and calcium antimonate white
opacifiers.
For example, in the investigation of the production technology for Islamic lustre deco-
ration, Pradell et al. (zoo8) have used rnicro-XRD to obtain information on the type and
size of the copper (Cu) and silver (Ag) nanoparticles, XANES and EXAFS to determine the
valence state of the Cu and Ag, and RBS together with TEM to determine the thickness of the
lustre layer. Similarly, in the investigation of the production technology of Athenian red-fig-
ure ware, Walton et al. (zo13) have used scanning transmission electron microscope (STEM)
methods to determine the microstructure and chemistry of the gloss layer, XANES to deter-
mine the valency of the iron in the gloss layer, and LA-ICP-MS to search for compositional
inhomogeneities within the gloss layer.
14 MICHAELS. TlTE

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 PART II

RESEARCH DESIGN
AND DATA ANALYSIS
 CHAPTER 3

DESIGNING RIGOROUS
RESEARCH
Integrating Science and Archaeology

JAUME BUXEDA I GARRIGOS

AND MARISOL MADRID I FERNANDEZ

INTRODUCTION

ARCHAEOLOGY, as social science, is a factual science; it deals with people and social systems,
natural resources, and artifacts, all of which must be considered concrete things, whether
natural or artificial, living or inanimate, individual persons or social systems. 1 Ceramic arti-
facts are one of the most important means (Neustupny, 1993) in the archaeological process of
inquiry because of their ubiquity and abundance in the archaeological record. Thus, a large
number of archaeological research questions are totally or partially based on the study of
pottery. However, several of the important research questions need to be answered not on
archaeological grounds, but by first considering the material nature of the ceramics under
investigation.
The previous statement illustrates the basic duality of archaeometric research. Even if the
problems under inquiry are of an archaeological nature, the objects of analysis are of a mate-
rial nature. Archaeological concepts do not necessarily map those of the material empirical
reality under study.
Ceramics, as artifacts, are concrete inanimate objects artificially (firewinduced) trans~
muted from the natural raw materials employed in their manufacture. All ceramics can be
considered as composite materials; they are made from two or more constituent materi-
als with significantly different physical and/or chemical properties that result in a material
with characteristics different from the individual components (e.g. clayey matrix, aplastic
inclusions, porosity). Some of those individual components might remain separate and dis-
tinct within the finished materials structure. Thus, ceramics are characterized by their main
intrinsic and essential source properties of composition/ structure,3 shape, and size, as well
as by their main intrinsic essential derived properties, such as mechanical, thermal, color,
and porosity.
20 J. BUXEDA I GARRIG6S AND M. MADRID I FERNANDEZ

SIMPLE CERAMICS COMPLEX CERAMICS

BOOY COMPOSITE DECORATIONS
Pigmtnts, gla~~s. yloss~s an~ slips r~w materials

C~l¢r ~ Color
M"hooicol- Thormal prepof1<<'
Por"'ity

Po•t•P">""'Iion
for~•i"g
I {$urf•oe trealm<nls) I I I

fired/Unfired pott<ry

Composition Color

I
I I

life finishtd pottery

As reedved state pott•ry

lntrinsio«st.,tialdtriv<dprop<Hi"
Color
Mothanical- Thormaipr¢portios
Poro•ity

FIGURE 3.1 Diagram flow of the states of ceramics from manufacture to the archaeological
record.

For the sake of simplicity, we divide ceramics into two general categories: simple and
complex (Figure p). A simple ceramic, even with added elements (spouts, handles, etc.),
is formed only by the materials of the body and the simple decorative forming techniques
(such as polishing or incising) made out of it (see e.g. Rye, 1981). Contrariwise, complex
ceramics exhibit distinct parts (such as glazes or glosses) made of materials other than those
of the body, called composite decorations.
The material nature of ceramics, therefore, is that of a composite material, which can
possess a complex structure composed of different parts made out of different materials for
different purposes. The material nature of ceramics needs then to be studied either as the
bulk composition of the body or as each of its different individual components (e.g. clayey
matrix, inclusions). And the same can be said for every one of the other parts that exhibit
 DESIGNING RIGOROUS RESEARCH 21

complex ceramics (e.g. glazes, which are composed with vitreous matrix, inclusions, poros-
ity, and pigments). This material nature can be addressed from the chemical, mineralogical
(and vitreous), or petrographic level, not as independent information, but as necessarily
related things.

CERAMICS AND THE ARCHAEOLOGICAL PROCESS

In order to be able to set up a representational numerical model (Hand, 2004) of the material
nature of ceramics for archaeometric research, we propose a general model for the empirical
system of their life history (Figure 3.1). A simple ceramic flows in a linear sequence starting
with the days and aplastic raw materials that will be used to produce first a paste, and then
the unfired ceramic, shaped through various forming techniques and, possibly, the addi-
tion of simple surface treatments. Paste preparation, forming, and surface treatments can
be considered processes that transmute the original natural facts into the artificial, synthetic
material; that is, the unfired ceramic 4 This process entails different degrees of complexity for
different ceramics, from a simple event to a large and difficult collection of events, involving
a variety of raw materials and auxiliary artifacts. Thus, ceramic complexity observed in the
natural raw materials is largely culturally induced by humans. Unfired pottery is always a
different shape and size than its raw material components, and the composition and struc-
ture may also be significantly changed. Thus, the derived properties of the ceramic are also
accordingly different from those possessed by the raw materials. The firing process will again
transmute the unfired vessel to ceramic (life-finished pottery) by firing-induced changes
that will further affect its composition and structure, and derived properties accordingly.
Changes in ceramics related to firing are dependent upon firing conditions, such as atmo-
sphere, temperature, and type of pyrotechnical installation, in a way that several unfired
ceramics sharing the same properties of composition and structure could end up with sig-
nificant differences. Thus, one paste could end up as several different fabrics and,' owing to
different firing conditions, exhibit different mineralogical compositions, microstructures,
and derived physical properties. Finally, ceramics in systemic contexts (Schiller, 1987)-that
is, in life assemblages (Orton, 2000 )-will be used until discarded, at which point they enter
into the archaeological context. Formation processes of the archaeological record, includ-
ing weathering, may also significantly change the intrinsic essential source properties.
Composition and structure of as-received-state pottery may have undergone major changes
(e.g. Buxeda, 1999; Secco et al., 2011); shape and size, after breakage and loss of complete-
ness, may become unknowable (e.g. Orton, 1993) 6 Obviously, derived properties will change
accordingly and/or may become non-determinable (e.g. the grayish color developed in
ceramics after pyrite crystallization induced by sulfate-reducing bacteria as in Buxeda et al.,
2005, or Secco et al., 2010).
Production of a typical Roman amphora is a good example of a simple ceramic; whatever
complexities exist in the manufacture process, paste preparation, forming, simple superfi-
cial treatments, and firing, it flows in a simple linear sequence (Figure 3.1, Simple Ceramics
body flows in straight sequence from "Clay and aplastic raw materials" to "Life-finished
pottery"). Other types of ceramics flow in sequences of increasing complexity in the sense
that they include composite decorations. For example, unfired Terra Sigillata is completed
22 J. BUXEDA I GARRIG6S AND M. MADRID I FERNANDEZ

with a simple decoration technique, the application of a layer that becomes a gloss after a
single firing (Figure 3.1, Simple Ceramics body flow from "Clay and aplastic raw materials"
to "Unfired pottery (shaped paste);' while Complex Ceramics-Composite Decorations flow
from "Gloss raw materials" to "Unfired pottery;' pre-firing decoration is added, and then
the complex ceramic is fired and flows to "Life-finished pottery"). The manufacture of some
decorated Attic black gloss vases flows along a similar path to Terra Sigillata, but after firing,
a second decorative cycle is employed, which adds several post-firing pigments but with·
out a second firing (Figure 3.1, like Terra Sigillata, but after firing it flows through "Multiple
cycles" again to Complex Ceramics-Composite Decorations and from "Gloss raw materials"
to "Unfired pottery;' and then through "Post-firing pigments" to "Life-finished pottery").
Another type of pottery, majolica, has a more complicated production sequence. First,
undecorated vessels are fired to produce what is called bisque pottery. Next, a decorative
layer, usually including pigments and opacifiers, is applied to the bisque pottery in order to
produce a decorated glaze during a second firing (Figure 3.1, like Roman amphora, but after
firing it flows to Complex Ceramics-Composite Decorations and then flows from "Glaze
raw materials" to "Fired pottery;' and through "Pre-firing decorations" it flows to a second
"Firing" and then to "Life-finished pottery"). An even more complex production sequence is
involved in the manufacture of lustre pottery; involving a second decoration cycle after the
bisque firing and glazing of the vessel during which powdered metal is applied to the glazed
surface, creating a metallic or iridescent sheen after a third firing (Figure 3.1, like majolica,
but after the second firing it flows again to Composite Decorations from "Glaze raw materi-
als" to "Fired pottery;' and, again, through "Pre-firing decorations" it flows to a third "Firing"
and then to "Life-finished pottery"). In all of these examples, the finished pottery exhibits a
body which is by itself a composite material. Moreover, complex ceramics also exhibit com·
posite decorations with distinct layers of complex composite materials added to it; that is,
the glosses, glazes, pigments, and metals. Minerals and microstructures formed at the inter-
faces among these distinct parts (body and composite decorations) also contribute to the
complexity of these ceramics and provide valuable information about their manufacture and
the sociocultural environment in which they were consumed.
Human-induced complexity may, in turn, be related to social complexity and to the devel·
opment of scientiftcally based technology. Thus, it can be hypothesized that higher complex·
ity in ceramics manufacture implies higher social complexity, as well as the development of
technology. At the same time, more sophisticated or complex production sequences may
also imply increased standardization of the manufacture processes and, consequently, a
decrease in the variability of the manufactured products.

RESEARCH PROBLEM§ AND ROUTINE PROBLEMS

IN ARCHAEOLOGY AND ARCHAEOMETRY

As discussed above, archaeometric analysis of pottery within archaeological studies is

focused on the material nature of the artifacts. From an analytical perspective, ceramic anal-
ysis is an inverse problem; we start with as-received-state pottery (i.e. the excavated, post-
depositional pottery), but all our research questions relate to earlier stages in its life history
 DESIGNING RIGOROUS RESEARCH 23

(life~finished pottery, unfired pottery, and raw materials) as well as the processes connecting
those states (Figure 3.1).
The methodological and theoretical difficulties arising from the inverse problem of
archaeological ceramic analysis, together with the necessity of establishing and continu-
ously developing critical background knowledge, methods, and theories, are archaeometric
research problems. These problems are essential for archaeological materials analysis as a
scientific discipline, but their solutions are not necessarily significant for archaeology in gen-
eral. Crucial research problems for archaeological materials analysis include:

Development of new analytical techniques and methods and/or the development and
application of existing techniques and methods to archaeological materials analysis.
For example, the increasing basic research on mechanical and thermal properties of
ceramics, the application of synchrotron radiation, or the use of portable X-ray fluo-
rescence spectrometry (XRF) (Kilikoglou and Vekinis, zooz; Hein et al., zooS; liiaiiez
et al., 2013; Hunt and Speakman, 2015).
Development of relevant background knowledge to facilitate the reconstruction and
interpretation of the processes involved in the manufacture, use, and post~depositional
environment of ceramics. For example, studies about weathering and its effect on the
chemical and mineralogical composition of archaeological ceramics (Buxeda, 1999;
Secco et al., zon).
Development of statistical methods and models for compositional data (Martin-
Ferm\ndez et al., 2015).
Ethnoarchaeometric studies enabling archaeological materials scientists to observe
directly the processes of pottery manufacture and more accurately reverse engineer
archaeological ceramic production (David and Kramer, 2001; Buxeda et al., 2003).

Archaeometric research problems enable the investigation of archaeometric routine prob-

lems. Routine problems, as opposed to research problems (Bunge, 1996: 81ff.), are well
posed, their approach is well defined, and the solution can be partially foreseen, on the
basis of the existing knowledge. Therefore, routine problems do not necessarily contribute
significantly to the development of archaeological materials analysis as a scientific disci-
pline, but they are essential for addressing relevant and important archaeological research
problems. Archaeometric routine problems could not be answered without archaeometric
research problems and their solutions, but the aim of routine problems is to be an active part
of an archaeological research program. Archaeometric routine problems typically address
two broad and related archaeological research questions: (1) identification of meaningful
ceramic groups and provenance, and (2) a'spects related to ceramic manufacture.
Focusing now on archaeology, it is clear that nowadays it is considered an increasingly sci-
entific discipline in terms of its methods and theories. However, it is still an undeveloped or
underdeveloped scientific field, because of the uneven knowledge of its almost endless case
studies from different places and times (in essence, the object of the study of archaeology is
the entire material remains of mankind in every place on Earth and from every time). Thus,
archaeometric routine problems may still contribute significantly to the advance of a par-
ticular case study when its archaeological background knowledge is still scarce by providing
an insight into previously unforeseen lmowledge. However, in archaeological issues already
well known, the only significant scientific contribution is to deepen such knowledge with
24 f. BUXEDA I GARRIG6S AND M. MADRID I .FERNANDEZ

archaeological research problems that necessarily increase in degrees of complexity; that is,
through large and well~designed archaeometric research programs.

Identification of Meaningful Ceramic Groups and Provenance

The first step in identifYing the provenance of archaeological ceramics is to objectively clas-
sify them into meaningful ceramic groups whose provenance can be identified in a second
step. Groups are inferred from the material nature of the ceramics themselves, their intrinsic
essential properties, and not from other relational and accidental properties, such as decora-
tive motifs or themes, potters' stamps, or the "criterion of abundance" (Harbottle, 1982) in
the archaeological record. These latter properties may, however, play an important role in the
background knowledge and evaluation of the archaeometric data.
The duality of archaeometric research means that there is not necessarily a correspon-
dence between the archaeological concept of a production center or workshop and the
meaningful ceramic group in material terms. As will be seen in what follows, identification
of ceramic groups and provenance ascription can be conducted mainly on the chemical and/
or petrographic levels.
Chemical characterization allows ceramics to be mathematically represented in the space
given by their elemental concentrations. In such space, the existing structure (i.e. the differ-
ential occurrence of points in this space, see Bishop and Neff, 1989) is assumed to represent
the existing different meaningful ceramic groups. However, as illustrated in Figure 3.1, this
mathematical space is that of the as-received -state pottery, in other words possibly weathered
after alteration of these during its use-life and/or post-depositional processes. Meaningful
ceramic groups are instead referred to the unfired pottery state (i.e. the mathematical space of
their elemental concentrations before firing); and from which the life-finished pottery state is
guessed not to differ in a significant way (i.e. in chemical terms, mainly changes related to loss
on ignition, but also in volatiles; see Kilikoglou et al., 1988; Bearat et al., 1989; Cogswell et al.,
1996). Unfired-pottery-state mathematical space is not the geographical space of archaeologi-
cal production centers, because paste preparation can be a complex human~induced process
of behaviors and expectations resulting in the procurement, combining, and processing of
d i:fferent raw materials in a single production center to create several different pastes, or con-
trariwise to create similar pastes in geographically distinct production centers. Meaningful
ceramic groups defined in the elemental concentrations of mathematical space, when map-
ping the unfired-pottery-state mathematical space (i.e. when there is no significant effect
from firing and weathering in the present-day chemical data), are the incertitude zone, or
non-resolution space (adapted from ·Picon and Le Miere, 1987), and must be considered the
smallest unit of a chemically based classification, referred to hereafter as paste compositional
reference units (PCRU) (adapted from Bishop et al., 1982).
After archaeological ceramics are classified into PCRUs, archaeological materials scien-
tists can address the question of provenance. In order to do this, reference groups (RG), also
called localized references (Picon and Le Miere, 1987), are needed for comparative analy-
sis. RGs are PCRUs defined from the study of ceramic materials recovered at production
centers (or workshops) and archaeologically identified, possibly together with extant raw
materials used in the manufacturing process also recovered on the site. Relating meaning-
ful ceramic groups (PCRUs) with production centers, RGs map groups from the elemental
 DESIGNING RIGOROUS RESEARCH 25

concentrations in mathematical space onto the geographical space where the production
center is located. If we can assume that the data treatment of the as-received-state pot-
tery elemental concentrations is close enough to what we could achieve if we could work
straight on the elemental concentrations of the unfired pottery (i.e. if the firing and weath-
ering effects are under control), provenance through chemical analysis is just a matter of
relating ceramic groups (PCRUs) to RGs. Thus, the understanding of the paste preparation
processes and the determination of composition of possible raw materials can be avoided.
Reverse engineering the paste preparation process, including selection and treatment of
raw materials, is a complex research problem by itself, the solution of which, while shed-
ding light on a technical problem of ceramic manufacture, is not necessarily relevant for
determining provenance. 1hus, analysis of potential raw materials becomes a complemen-
tary practice, the purpose of which is to inform on technical aspects of the production
sequence. However, raw-materials characterization is really advisable in those cases where
production centers are not easily identified in the archaeological record; for example,
because of the absence of kilns in pottery production (Hunt, 2012). It is important to high-
light that provenance based on RG is a provenance ascription to actual production centers
(or, more precisely, to the incertitude zone of the RG). Contrariwise, provenance based on
raw materials is a provenance ascription to possible geographical (geological) source areas,
not to actual production centers.
At the petrographic level, since ceramics are composite materials, the study of non-plastic
inclusions, as different individual components, might also enable provenance ascription in
the unfired-state-pottery space. In general, extant inclusions can be understood as remnants
of the raw materials not transmuted during manufacture and post-depositional processes.
In this way, identifying inclusions is, in effect, identifying some of the original raw materi-
als of the as-received-state pottery, partially canceling the inverse problem of archaeomet-
ric studies. However, since fabric characterization using petrography is not based simply on
extant inclusions (Whitbread, 1995), identification of meaningful ceramic groups (or fabrics,
in petrographic studies) is a far more complex problem because it is based on the whole
intrinsic essential source properties of composition and structure at a petrographic level
(i.e. including identification of extant non-plastic inclusions, frequencies, sizes and shapes,
groundmass, vesicles, vughs, channels, concentration features, and the like). It is important
to highlight that the state-space defined using petrographic methods is not the same as the
state-space defined using bulk chemical methods. Mapping elements from petrographic
onto the chemical state-space can be complicated; independent studies using petrographic
and bulk chemical methods on the same samples may even lead to the identification of dif-
ferent meaningful ceramic groups. Petrographic and bulk chemical analyses are compli-
mentary techniques, providing different but related types of information. Therefore, an
integrated methodology is advisable.
In short, archaeometric routine problems related to the classification and provenance of
ceramics must, necessarily, be based on bulk chemical and/or petrographic characterization
of as-received-state ceramics, and therefore subject to the problem of reverse engineering.
The ultimate goal, however, is to be able to infer the compositions of archaeological ceramic
assemblages (i.e. the diversity of meaningful ceramic groups in ceramic assemblages); a
complex research goal in which archaeological inquiry totally subsumes archaeometric
research. However, because of its importance and scope, this research aim will be considered
in detail below.
26 J. BUXEDA 1 GARRIG6S AND M. MADRID 1 FERNANDEZ

Aspects Related to Ceramic Manufacture

Archaeometric studies focused on understanding archaeological ceramic manufacture typi-
cally have one of the following fields ofinquiry:

a Research aims centered on understanding how life-fired pottery was made (i.e. the
manufacture process).
b Research aims related to the performance characteristics oflife-fired pottery.
c Research aims devoted to the study of manufacturing techniques/technological change.

In order to design research focused on :t;'econstructing how pottery was manufactured, we

must understand that ceramic manufacture is a complex human-driven process related
to social complexity and the development of techniques and scientifically based technol-
ogy. This distinction between techniques and technology is significant; techniques is pre-
scientific craftsmanship, while a technological process implies science-based research
and development (Bunge, 1996: 197ff.). For example, ceramic manufacture processes
can be placed on a continuum from earliest technical processes based on experience, to
more recent technological processes based solely on knowledge. Technology implies the
refinement of techniques using the results of pure and applied science (e.g. the new high-
technology ceramics).
Reverse engineering the processes of ceramic manufacture (research aim a) is an inverse
problem starting from the as-received-state pottery. Ideally, we would investigate ceramic
manufacture by studying excavated production centers or workshops, where in addition to
ceramics in different stages of the production process, extant raw materials may be found
together with artifacts used in those manufacture processes (e.g. kiln structures, potters'
tools, etc.). Guessing the role played by each of these elements (ceramics, raw materials, and
artifacts) in the ceramic manufacture process enables archaeological materials scientists to
reconstruct the entire manufacture sequence; nevertheless, this reconstruction is a hypoth-
esis which must be tested.
An important consideration when attempting to identify the intended performance char-
acteristics (Skibo and Schiffer, 2oo8) of the life-fired pottery (research aim b) is that most
of the pottery recovered from a production center corresponds to waste materials, particu-
larly over-fired ceramics or kiln wasters. These artifacts may obscure the identification of
the intended performance characteristics of the finished pottery because they are or were
considered defective in some way and were discarded. Therefore, it is better to study pottery
from consumption (or reception) cei?-ters (e.g. towns, residences, storage facilities) to under-
stand the intended or desired performance characteristics; vessels "in use" rather than waste
vessels.
Both research aims a and b, reconstructing manufacture processes and identifying per~
formance characteristics, must be conducted on well-defined meaningful ceramic groups
in order to contribute meaningfully to the complex empirical reality under study. Moreover,
the number of individuals analyzed should be large enough that significant statistical infer-
ences can be drawn from the data. The determination of the number of individuals that is
large enough depends upon the structure of meaningful ceramic groups, as well as the num-
ber of different firing-induced fabrics existing within each meaningful ceramic group. In
other words, ceramics at one production site may be stratified (in statistical sense) according
 DESTGNTNG RIGOROUS RESEARCH 27

to the existence of different meaningful ceramic groups. At the same time, each ceramic
group may be stratified according to different fabrics. Sample selection and other sampling
issues will be thoroughly discussed below.
Several examples can illustrate the previous points. As a first case study, we consider
research recently undertaken on materials from the Roman Terra Sigillata production
center of Andujar, which clearly show how one workshop may end up with different refer-
ence groups (i.e. different meaningful ceramic groups) in the life-finished pottery stage of
the manufacture process (Roca et al., 2013 and references therein). At this site, pottery and
molds corresponding to different stages of production of the workshop were identified and
sampled for archaeometric characterization. Bulk chemical analysis by X-ray fluorescence
and the statistical data treatment of these compositional data, together with mineralogical
analysis by X-ray diffraction, enabled the identification of six different pastes. One of them
was a low calcareous paste that was used for the manufacture of cooking ware throughout
the workshop's life. The other five pastes were used in subsequent periods: three of them dur-
ing the )ulio-Claudian period, the other two during the Flavian period. The three pastes used
in the )ulio-Claudian period are calcareous, but with significant differences. 'J:he most cal-
careous one was used to produce painted Iberian pottery, coarse pottery, lamps, thin-walled
pottery, and some forms of Italian Terra Sigillata-like pottery, together with a few examples
of Hispanic Terra Sigillata molds. The other two pastes were only used to produce Hispanic
Terra Sigillata pottery and molds. During the Flavian period, the two pastes in use exhibit a
drop in the calcium content. In fact, one of them, only used tor Hispanic Terra Sigillata pot-
tery and molds, can be classified as low calcareous. The other one was used for the manufac-
ture of Hispanic Terra Sigillata pottery and molds, but also for coarse pottery. These results
illustrate the existence of different RG (i.e. localized meaningful ceramic groups in the math-
ematical space) in just one single workshop (i.e. one archaeological meaningful point in the
geographical space), because of the existence of products for different purposes, and also
diachronic changes in the manufacture process. The chemical analysis of several local clays
(Picon, 1984) also suggests that at least four different raw materials could be exploited in
order to produce those six different pastes. Thus, all the analytical evidence indicates great
behavioral complexity related to the exploitation of raw materials and paste preparation pro-
cesses. However, since the scope of this research project was the identification of the mean-
ingful ceramic groups (six) in order to define their characteristics (i.e. the RG) to provide
localized references for provenance studies, an in -depth study of locally available potential
raw materials, and the actual manufacture processes leading to the different pastes, is not
necessary. This subject remains as a subject by itself, albeit one related to identifying the
technical/technological aspects of ceram~c manufacture, not to provenance necessarily. An
example of a rigorous and complete study that identified ceramic manufacture processes at
a production center, including the necessary experimental tests, was conducted by Montana
et al. (2007).
As we have seen, production centers are ideal for understanding ceramic manufacture pro-
cesses and establishing reference groups for provenance studies. Consumption centers, on
the other hand, are ideal for the study of performance characteristics of meaningful ceramic
groups; performance characteristics are given by the intrinsic essential derived properties
of color, mechanical properties, permeability/waterproof qualities, and the like, resulting
from the prepared paste and the firing process (Figure 3.1). One example is the Roman Terra
Sigillata production center of Tritium Magallum, the biggest ceramic production center on
28 J, BUXEDA 1 GARRIG6S AND M. MADRID I FERNANDEZ

the Iberian Peninsula identified to date. Despite the fact that an archaeological and archaeo-
metric research project of the entire production center in order to know the processes of
ceramic manufacture has yet to be conducted, its RG was chemically defined by Picon (1984)
after analyzing a substantial sample of individuals from Tritium Magallum. The establish-
ment of this RG has enabled its identification at several consumption centers throughout the
Iberian Peninsula. Characterization of a large number of individuals, recovered from three
different Roman cities in the Catalan area, facilitated identification of the preferred fabric
manufactured by potters at Tritium Magallum, as well as the corresponding final color, an
essential visual performance characteristic of these ceramics (Madrid, 2005; Buxeda et aL,
2013; Madrid and Buxeda, 2014). Once the meaningful ceramic group was identified and
linked to Tritium Magallum RG after the bulk chemical analysis by X-ray fluorescence, and
the subsequent compositional data treatment, several fabrics were established, after the min-
eralogical analysis by X-raydiffraction according to the association of crystalline phases and
their relation with mineralogical scales (Heimann, 1982; Maggetti, 1982). These fabrics were
the result of three different ranges of estimated equivalent firing temperatures (EFT). EFT
ranges affect the color of both ceramic paste and gloss, making it problematic to determine
which color was intentional for the life-finished pottery. Therefore, a statistically significant
sample of artifacts was considered with the aim of evaluating the distribution of ceramics

Tricio-EFT

Baetulo: Highly significant (x 2 "" 21.79}

Tarraco: Significant (x2 "" 5.63)
!I erda: Very significant (x 2 "" 6.7)

Frequency
significant (x 2 "' 2.99}
significant (x 2 "' 0.12)
significant (x 2 = 0.19)

Tarraco

x2 = 4.38, df =4, p-value ""0.36

FIGURE 3.2 Multiple bar chart of Hispanic Terra Sigillata from Tritium Magallum recov-
ered at Baetulo, Tarraco, and Herda, classified according the range of estimated equivalent
firing temperatures (R1 to R3). R1; 850-95o'C, R2; 950/woo'C, R3; 1050-1150'C.
 DESIGNING RIGOROUS RESEARCH 29

from each EFT range for each city As illustrated in Figure 3.2, the x' test for the contingency
table for the frequencies of Terra Sigillata in the three cities, according to the EFT range, does
not indicate significant differences in distribution (p-value = 0.36), suggesting that both
variables, city and EFT range, are not associated. More detailed statistical analysis, the x' test
among EFT ranges within each town, reveals no significant differences between the number
of ceramics classed in ranges Rr (EFT 8so-9so"C) and Rz (EFT 9SO-JOoo"C) for the three
cities. This means that Terra Sigillata fired at these EFT ranges are distributed in statistically
similar proportions of the assemblage at these three sites. However, significant, very signifi-
cant, and highly significant differences in distribution patterns are observed between Terra
Sigillata with EFT ranges Rz and R3 (roso-nso"C) at Tarraco, Herda, and Baetulo respec-
tively (Figure 3.2). These differences in distribution indicate that artifacts fired in EFT range
R3 are significantly more widely consumed than those fired at either range Rr or Rz. These
results further enable us to infer that Terra Sigillata, fired at range R3, was the intended com-
mercialized product manufactured at Tritium Magallum, even if Terra Sigillata fired at dif-
ferent EFT ranges and exhibiting different performance characteristics was also distributed
at the same time.
In contrast, the Gaulish Terra Sigillata workshop of La Graufesenque distributed ceram-
ics during the same period as Tritium Magallum, and could be considered its main rival
for the Terra Sigillata market on the Iberian Peninsula, but had a very different distribu-
tion pattern (see Madrid, zoos; Madrid et al., zoos; the former includes the comparison
with La Graufesenque RG defined by Picon on Terra Sigillata from this production center).
Characterization of a large number of individuals recovered from Emporiae, Baetulo, and
Tarraco enabled the estimate of just one range of EFT (wso-nso'C), although several min-
eralogical fabrics were identified. 1bis means that products distributed by La Graufesenque
are more standardized than those of Tritium Magallum, exhibiting a greater homogeneity in
the red color which characterizes this tableware.
In addition to providing the red color, transverse rupture strength and the waterproof
resistance of the gloss on Terra Sigillata are its most important intrinsic essential derived
properties providing its performance characteristics. Research aimed at the evaluation of
these properties must be conducted on a statistically significant number of samples recov-
ered from consumption centers. Taken together, all the main intrinsic essential derived
properties provide objective material-based criteria for quality, under which inferences
about consumption can be hypothesized. Looking again at Terra Sigillata from the cities of
Baetulo, Madrid, and Buxeda (2007) determined that there were several different grades or
degrees of quality present after evaluating the transverse rupture strength, and the adher-
ence and the sintering state of the gloss. The manufacture of different qualities of the same
pottery type may indicate different expectations of the consumers about these vessels and
their performance characteristics, and/or may be also related to different prices and uses of
the pottery. Evaluating the quality ofTerra Sigillata allows a deeper understanding ofboth its
consumption and the sociocultural expectations of its production: more complex anthropo-
logical questions than trade and/or regional distribution patterns.
The third aim (c) of ceramic manufacture studies is understanding and evaluating techni-
cal/technological change (Schiffer, 2011). These studies must be conducted on meaningful
ceramic groups whose performance characteristics have been determined by previous stud-
ies, enabling the researcher to readily identify the intended life-finished pottery, the degree
of standardization, and its quality in terms of consumption. Changes in the intrinsic essential
30 J• .BUXEDA I GARRIG6S A:-;rD M. MADRID I FERNANDEZ

source properties of composition, structure, and design (i.e. shape and size), and the intrin-
sic essential derived properties of the pottery, such as color, mechanical-thermal proper-
ties, and porosity, are potentially related to changes in performance characteristics and/or
changes in the behavioral chain, such as acquisition of new knowledge, experience, or tech-
nologies, changes in the economic structure, and so on. For example, the Romanization pro-
cess of the Catalan coast around the first century BC catalyzed drastic changes, impacting all
aspects of daily life, from the abandonment of Iberian settlements after Roman towns were
established, changes in land ownership and agricultural practices, and the end of!berian pot-
tery production. Roman pottery was manufactured locally in the newly established Roman
production centers, in some cases in large quantities. Roman amphorae, for the distribu-
tion of wine, were mass produced in Catalonia, beginning with imitations of Italic Dressel1
type amphorae and, subsequently, two new types unique to the Catalan area, Tarraconense
1 and Pascual 1. In order to understand these changes in Roman amphorae production on
the Iberian Peninsula, finite element analysis (FEA) was conducted in order to compare the
performance characteristics related to the design of the changing amphorae shapes and sizes
(Vila et al., 2007). The PEA results suggest that the new designs, Tarraconense 1and Pascual1,
improve the mechanical properties of the amphorae during ship transportation, possibly
the most important performance characteristic for a cargo container. Until now, these new
designs fOr amphorae manufactured in the Catalan area have been uniquely interpreted as
an attempt to show a new local identity in wine production. Whether or not issues of identity
expressed in design can still be conjectured, these new designs are, according to the results,
actual technical improvements.

fORMATION PROCESSES, THE ARCHAEOLOGICAL

RECORD, AND ARCHAEOMETRIC STUDIES

As stated above, one of the major aims of the archaeometric study of ceramics is to classify
pottery on objective grounds using the intrinsic essential properties of its material nature.
By first classifying pottery according to meaningful ceramic groups, researchers are able
to determine how many and which meaningful ceramic groups are present in an archaeo-
logical pottery assemblage, and in what proportions; that is, the composition of this assem-
blage. A second analytical step is evaluating provenance or the place of origin of the ceramic
materials used.
At this point, it is important to cladfy the meaning of several concepts related to the place
where artifacts are found. First, the provenance of an artifact is the empirical fact of its physi-
cal location> and, by inference of association, its context; the basic unit of provenance, or
context, in the archaeological record is the stratum (Lyman, 2012). A stratum is an empirical
fact in the archaeological record comprising the smallest unit resulting from site formation
processes (Schiffer, 1987). The materials belonging to each stratum form an assemblage. The
assemblage associated with a stratum is the basic unit of material association in the archaeo~
logical record (Orton and Tyers, 1990 ).
The importance of a context and the assemblage it contains is that its composition is
believed to be related to different social facts about past living societies, such as activity type,
 DESIGNING RIGOROUS RESEARCH 31

social status, and exchange of goods, and potentially provide chronometric information.
Ihe latter is an inference derived from the most modern artifact in the assemblage, provid~
ing a terminus post quem for the formation of the stratum. Whether or not the chronolo-
gies of those artifacts are accurately known is a different archaeological problem, as is the
life-span of those artifacts, something that can dramatically shift the terminus post quem.
Contrariwise, the guessed social facts reflected in an assemblage are not necessarily directly
observable. As has been acknowledged before (see e.g. Schiffer, 1987; Orton and Tyers, 1990;
Lyman, 2008), archaeological assemblages result from living or systemic assemblages and
formation processes of the archaeological record. It is not the scope of the present chapter
to examine this problem thoroughly, but several points need to be highlighted. First, the
assemblages directly related to the social facts of interest are the living or systemic assem-
blages not the archaeological assemblages. Second, archaeological assemblages, even if
originated in those, are ultimately the result of discard and formation processes. Discard
events may be complex and result in serious changes to the composition of the living assem-
blage. Hoards and funerary deposits can be archaeological assemblages intentionally cre-
ated by and for a living society. Most archaeological assemblages, on the other hand, are the
result of abandonment, discard, loss, and so on, obscuring and complicating the relationship
between living assemblages and the materials entering archaeological ones. Third, even after
archaeological assemblages are formed from materials departing a systemic context, new
cultural and natural formation processes may further distort or enhance differences between
the living and archaeological assemblages in a difference of degree. This is, for example, the
case of a primary deposit that has been distorted by a posterior construction in the area.
Thus, the archaeological assemblage is the as-received assemblage state, and reconstructing
its relationship with a living assemblage is, again, an inverse problem. As a consequence,
archaeometric research is, by necessity, conducted on archaeological assemblages; that is, on
the as-received state of the archaeological record.
The previous consequence has severe implications that may not have been sufficiently
considered for archaeometric research. The definition of an archaeological assemblage is
given by its link to an archaeological context, that is to a stratum. However} its intrinsic essen~
tial source properties are those of composition, fragmentation, and integrity. Composition
of an archaeological assemblage results from the partition of a domain into mutually exclu-
sive classes after a classificatory concept, such as ceramic classes or types. Compositions
have parts and components as intrinsic essential source properties. Parts are the labels of
each class or category of the partition; for example, Hispanic Terra Sigillata could be one of
the parts of an archaeological assemblage. Components are the number or frequency mea-
sured for each class. Size of a composition, therefore, is an intrinsic essential derived prop-
erty resulting from the sum of its components (Aitchison, 1986). Parts, components, and size
can be considered characteristic or non-structural properties as opposed to the structural
properties of composition, given by the intrinsic essential derived properties of richness and
evenness, derived from components. Richness stands for the number of meaningful ceramic
groups represented; that is, components whose frequency in the assemblage is higher than
zero. Evenness stands for the distribution of the individuals among the meaningful ceramic
groups in the assemblage: the greater the richness and evenness of the assemblage, the
greater its diversity (Hurlbert, 1971).
Fragmentation and integrity describe the state of ceramic artifacts extant in the archaeo-
logical assemblage as a result of formation processes. Ceramics are typically found broken
32 J. SUXEDA I GARRIG6S AND M. i.V!ADRID I FERNANDEZ

and, even after refitting (or reconstruction), may remain incomplete. It has been suggested,
therefore, that these properties could be used to shed light on the nature of formation pro-
cesses responsible for an assemblage (see e.g. Orton and Tyers, 1990, which calls these
properties brokenness and completeness). However, as discussed below, in our opinion frag-
mentation and integrity must be measured and used in order to evaluate the assemblages on
the basis of their own properties.
Thus, even if originated in living assemblages, studying archaeological assemblages linked
to the contexts resulting from formation processes one must acknowledge that almost all
intrinsic essential source and derived properties are related to the numerosity of ceramics
classes (i.e. their frequencies) and their state in terms of recovering. Measuring numeros-
ity or frequency is enumerating or counting the individuals present in an assemblage, fre-
quently called quantification in the archaeological literature. Because of that, quantification
methods are of primary importance in archaeometric studies. Several families of methods
of measuring numerosity are used for archaeological ceramic analysis: sherd count; weight
and related measures; estimated vessel-equivalents (EVEs); estimated vessels represented
(EVREP), and pottery information equivalents (PIEs) standing for pseudo-count trans-
formations (PCT). These methods and their properties have been widelydiscussed in the
literature, for example Orton (1993); however, some aspects of quantifying archaeological
ceramics still need to be considered.
Following our aim to set up a representational numerical model for archaeometric
research, it must be highlighted that the only representational numerical model for quan-
tifying archaeological ceramic assemblages must be based upon sherd count and/or the
maximum number of individuals (MxNI) (one of the EVREP measures): the first measure
quantifies the number of actual fragments or sherds in the assemblage, while the second
estimates the number of individuals in the assemblage after the refitting process, considering
as one individual any sherd or groups of joined sherds that do not positively join any other
sherd or group of sherds. Both measures are representational, since they correspond to facts
of the empirical reality. All other measures are operational in the sense that they infer, at least
partially, numbers of individuals on theoretical assumptions, not on the empirical reality.
The use of the operational measures to quantify ceramic assemblages has two important
consequences. First, most of these measures are based just on specific types of sherds, such
as rims, handles, and bases. Therefore, not all sherds are equally weighted in the archaeo-
logical analysis, despite the fact that all sherds possess the intrinsic essential source prop-
erties of composition and structure needed for archaeometric characterization. In several
situations we could even analyze individuals that were not counted at all, or we could even
have more individuals characterized in one assemblage than individuals estimated by the
archaeological study. For example, we could characterize archaeometrically a wall fragment
sherd that would not be used at all in a minimum number of individuals estimation based on
rim sherds. Similarly, there are even some assemblages that only provide wall fragments, or
similar, but no rims, bases, or handles used in such estimations. In those cases, the minimum
number of individuals estimate is o (or some scholars may apply a correction estimating 1
individual, see e.g. Raux, 1998). Whichever the case (o or 1) we could take several samples
from the extant wall sherds for archaeometric characterization with more individuals char-
acterized than estimated by the archaeological study. Second, and partially related to the
first, operational measures do not provide an appropriate sampling framework that can be
used to design rigorous sampling. One method is to estimate the number of individuals, and
 DESIGNING RIGOROUS RESEARCH 33

another method, with no necessary relation to the previous one, is to sample a set of indi¥
vi duals to be archaeometrically characterized. Representational measures ensure that there
is an appropriate sampling framework, based on the empirical reality that includes every
individual. Thus, every sampled individual has been counted when measuring numerosity,
and sampling fractions are meaningful.
This situation does not preclude the use of operational measures of numerosity for other
types of analysis (see e.g. Arcelin and Tuffreau-Libre, 1998) because there is no reason to
perform just one of them, but in order to conduct a sampling for archaeometric research rep~
resentational measures should be present. This is certain for all archaeometric studies, but it
is compulsory for studies devoted to the deep complexities of the archaeological record.
If we use the term "individual" for a vessel estimated from the archaeological assemblage,
whichever the quantifying method in use, and "true individual" for an actual vessel in the
living or systemic context, we can see that representational measures (sherd counts and
MxNI) are similar in the sense that both of them either estimate the number of true indi-
viduals or overestimate it (especially sherd counts). For example, we have two sherds and
each one belongs to a different vessel; the estimation of two individuals, by sherd counts or
by MxNI, would recover the number of true individuals. If we have two sherds belonging to
one individual but not joining, they would be counted as two different individuals, overesti-
mating the number of true individuals. Even ifboth measures can end up in overestimations,
only the maximum number of individuals (MxNI) should be used for sampling purposes
in archaeometric studies, since joined sherds are known to be part of the same vessel, and
this crucial information is retained. Nevertheless, the number of true individuals sampled
for archaeometric studies will be either the number of individuals included in the sample or
fewer. This is easily understood if we consider that the number of true individuals sampled
is the number of individuals in the sample, unless one or more true individuals are sampled
more than once, because their extant parts do not join and are considered as diftfrent indi-
viduals in MxNI terms. Strategies for avoiding sampling more than one true individual at
a time, such as sampling specific types of sherds (e.g. pointed bases in amphorae studies),
may imply a selection that may produce some uncontrolled bias. There is no simple solution
to that problem; not for samples based on the maximum number of individuals, neither for
samples based on any other measure. This situation becomes critical if no refitting process
has been performed because there is no control at all on whether different sherds may come
from the same true individual.
By using representational measures we can also describe the empirical reality providing
some measures for fragmentation and integrity. (1) Fragmentation can be measured (i.e.
quantified) using the number of fragments and the MxNI as follows:

where PI is the fragmentation index, N is the MxNI, and F is the number of fragments in
the ;th individual. (2) Integrity can be measured as the loss of information due to the same
formation processes responsible for the preservation of smaller parts or fragments of the
original vessel. Such processes can induce a gradual loss of information for each of the indi-
viduals estimated with the MxNI. For one individual estimated by MxNI, the maximum
34 J. BtJXEDA I GARR1G6S AND M. MADRID I FERNANDEZ

information retained corresponds to a complete vessel (CV), while the minimum corre-
sponds to an uninformative isolated sherd that cannot be identified or associated with the
general classification of vessels, such as rim, wall, or base. Between these two extremes of
retained information several categories are established for intermediate amounts of retained
information. Those categories are established according to the class of pottery under study
and the classification system in use, and will be explained in a Terra Sigillata case study later
in this section. Integrity of the assemblage, therefore, is based on the loss of information for
all MxNI in the assemblage. If all individuals estimated as MxNI are CV, evenness of the
assemblage will be maximized. Otherwise evenness will decrease according to the degree of
information lost. Evenness, therefore, is measured according to information entropy, also
known as the Shannon index (Shannon, 1948), by using in the calculation logarithms to base
2 (therefore, information entropy -H,- will be measured in bit). Thus, both measures for
fragmentation and integrity have a direct translation to the empirical reality of the archaeo-
logical assemblage under investigation.
The preceding discussion is based upon the basic units of context and assemblage; that is,
the stratum and the materials that it contains. Those basic units are empirical facts, but they
are not necessarily themselves the object of interest for an archaeological research problem.
Often, archaeological research questions require analysis of multiple units. In these cases,
the archaeological context of interest is built according to the inferential concept of asso-
ciation which allows for the aggregation of two or more -basic units; that is, more than one
stratum. Aggregation of strata implies the aggregation of assemblages, which may lead to an
estimation ofMxNI less than or equal to the sum of the MxNI of the individual assemblages,
since sherds or groups of sherds from different assemblages may join (providing further
valuable information on formation processes).
When the assemblage under study is quantified using representational measures a sam-
pling strategy can be devised, if needed at all, on the existing sampling frame which is equally
based on the empirical reality. In the case of a stratified assemblage, where the population
under study contains different meaningful ceramic groups, a stratified sampling strategy
is appropriate, taking a random sample of each stratum (in this case, a stratum is a sub~
population of the assemblage or meaningful ceramic groups). However, prior knowledge
of the stratification of an assemblage on an archaeometric basis is usually lacking. Instead,
what is not usually lacking is an stratification on an archaeological basis, based on (1) rela-
tional and accidental properties (such as decorative motifs, potters' stamps, or the criterion
of abundance), together with (2) an estimation of the intrinsic essential source properties of
composition and structure determined macroscopically or using a stereoscope microscope,
and (3) some indications on intrinsic essential derived properties such as color. As will be
seen in the example later in this section, the state space of such archaeologically based strati-
fication is not necessarily the same as the one defined by the intrinsic essential source prop-
erties of composition and structure provided by the archaeometric research. Therefore, it is
not appropriate to condition the whole sampling strategy using archaeologically based strat-
ification. What is more appropriate is to perform a probabilistic sampling in two or more
surveys (1) starting with either the archaeological stratification or without any stratification
at all. Then, an initial sample is taken using a stratified or a random sampling design, respec-
tively. After this initial sample is analyzed and the results evaluated, (2) a post-stratification
(i.e. stratification after a first survey) can be designed, now on an archaeometric basis. At
this time, more surveys can be performed if needed according to these new and subsequent
 DESIGNING RIGOROUS RESEARCH 35

post-stratifications, until the necessary (or the attainable) number of individuals has been
sampled.
Besides, the sampling strategy can be organized according to multiphase sampling. The
phases used in this strategy are related with stratification in the assemblage, not in terms of
different meaningful ceramic groups) but in terms of variability within a single meaningful
ceramic group. Typically, this variation exists because of (1) differences in ceramic fabrics
arising from firing conditions, (z) weathering processes (Buxeda, 1999; Secco et al., zon), (3)
the non-normal distribution of inclusions (Buxeda et al., 2003), and (4) other special prob-
lematics. 'Ibis stratification is not known before archaeometric characterization; therefore
in the first phase, every individual in the sample is analyzed for a particular set of proper-
ties (by applying the same analytical techniques); for example, chemical characterization by
means ofX~ray fluorescence and mineralogical characterization by means of X-ray diffrac-
tion. In the next phase of sampling, a subsample of individuals is taken from those included
in the first phase of sampling, not from the entire assemblage, and they are analyzed for dif-
ferent properties using different techniques, such as microstructural characterization by
means of scanning electron microscopy and optical microscopy on thin sections. Additional
phases, analyzing different properties, such as thermal shock resistance and hardness, can
be performed on subsequent subsamples of the previous phase. This multi-phase sampling
strategy avoids the often expensive and time-consuming analysis of a large number of indi~
vi duals using multiple techniques before the stratification of the assemblage is known. It also
ensures that techniques are not randomly applied to different individuals.
To illustrate the previous discussion, we look at two ceramic assemblages from the Roman
city of Baetulo. This example will show how two different contexts can be studied and com-
pared by using representational measures of quantification of the ceramic assemblage,
together with the determination of fragmentation and integrity. In a second step, the archae-
ological stratification used at the initial survey of the sampling process will be explained and
compared with the post-stratification based on the archaeometric research.
Focusing our attention on the archaeological research problem of the Terra Sigillata dis-
tribution at different contexts of the Roman town of Baetulo, the Terra Sigillata of two differ-
ent contexts, LL85b and TV83, was selected for archaeometric study (Madrid, 2005; Madrid
and Buxeda, 2014). Both contexts were dated to the end of the first century AD and were
inferentially formed by aggregating several archaeological strata.
LL85b was interpreted as fill from different parts of a Roman domus. The entire assem-
blage of 191 fragments, after refitting, contained 152 MxNI. One hundred and five of these
MxNI were classified archaeologically as Italian Terra Sigillata (ITS); three were classified
as Unknown Terra Sigillata (UTS). Both ITS and UTS were considered a single category
(U/ITS) because UTS is manufactured in shapes similar to ITS but with different visual
characteristics, especially the color of the gloss (orange-colored instead of the characteristic
reddish one). The remaining individuals were classified archaeologically as Gaulish Terra
Sigillata (GTS) for 31 MxNI and Hispanic Terra Sigillata (HTS) for 13 MxNI. These three
categories (or strata), U/ITS, GTS, and HTS, make up the archaeological stratification of the
population of interest.
After estimating MxNI, in a second step, each individual (in MxNI terms) was classified
according to several categories defined on the basis of the portion of information retained
of the complete vessel (i.e. a qualitative estimation of how much of the original vessel in
the systemic context has been recovered in the archaeological one). The first category is
36 ]. BUXEDA I GARRIG6S AND M. MADRID I FERNANDEZ

the actual MxNI, because the refitting process could not demonstrate that sherds assigned
to different individuals belong to the same vessel. In that sense, for all these individuals
(as MxNl) we have, at least, the information that they may belong to different vessels. The
second category, MxNINU (MxNI non-undetermined) is used to describe individuals
that could be identified as a part of a vessel, such as sherds from the rim, wall, or base. All
MxNI will again be included in this second category provided that this information is also
retained. On the contrary, those individuals that do not keep this information will only
appear in the first category (MxNI) but not in this second one (MxNINU). The third cat-
egory, MxNIA (MxNI associated), is for individuals that can be further classified as (associ-
ated to) a particular class of vessel, such as cups or bowls but not to a specific type (i.e. all
MxNINU that are associated to a particular class of vessel will be also included in this cat-
egory). The fourth category, MxNII (MxNI identified), corresponds to those MxNIA indi-
viduals that can be classified according to specific vessel type, such as Consp. 22 cup, but
not to a subtype. The fifth category, MxNIT (MxNI classified according to subtype), is used
for MxNII individuals which can be classified into subtypes, such as Consp. 12.2; MxNII
individuals whose type does not contain subtypes can also be classified as MxNIT, such as
Drag. 36. The penultimate category, CP (complete profile), is used to refer to MxNIT ves-
sels whose profile can be totally reconstructed after refitting, while the last one, CV, stands
for complete vessels. In the hypothetical case that the assemblage under study was formed
by ten unbroken and totally complete vessels, all the previous categories would account for
ten individuals. The breakage process and the loss of integrity would change this ideal situ-
ation to just ten (or even more than ten) in the first category and decreasing numbers in the
subsequent categories.
A bar graph illustrating the loss of information for the total ceramic assemblage from
LL85b by archaeological strata defined according to the classes of Terra Sigillata is shown in
Figure 3-3a. The information entropy (H,) for each class ofTerra Sigillata was also calculated.
This graph shows that most of the pottery in the assemblage is archaeologically classified as
U!ITS, a class considered older than the final chronology of the context. Moreover, the infor-
mation entropies are considered as relatively similar, ranging from 2.05 bit (GTS) to 2.24 bit
(HTS). These information entropies are considered as relatively low ones, far from the maxi-
mum attainable when facing seven categories (2.8073 bit, i.e. the logarithm to base 2 of 7),
and reflect a substantial loss of information in the assemblage. In the previous ideal case with
ten MxNI corresponding to ten complete vessels, the bar graph would show a maximum
evenness (all seven categories up to ten), and information entropy would be the maximum
attainable (2.8073 bit).
Another context at Baetulo, TV83, after the archaeological analysis, is believed to result
from the abandonment of a group of tabernae located in a building at one of the decumani
of the city. The total number of fragments (or sherds) in the assemblage ofTV83 was 259 and
the MxNI estimated after refitting was 182. Six out 182 were UTS and 14 were ITS, bringing
the total MxNI for class U/ITS to 20. GTS accounted for 99 MxNI, and HTS accounted for
63 MxNL The bar graphs and information entropies (Figure 3-3b) clearly illustrate a differ-
ent distribution pattern for Terra Sigillata in context TV83 than LL85b. U/ITS is not well
represented in the TV83 assemblage, while GTS and HTS, the Terra Sigillata classes syn-
chronic to the formation of the context, are abundant. Information entropies also present a
wider range, from 1.88 bit (UIITS) to 2.22 bit (GTS). It is important to highlight that U/ITS
from the TV83 context exhibits the lowest information entropy (i.e. the maximum loss of
 DESIGNING RIGOROUS RESEARCH 37

information or the lower integrity), something that seems to be expected for pottery much
older than the time of the formation of the context.
The bivariate plot of integrity, measured as information entropy, against fragmentation,
measured by the fragmentation index FI, is shown in Figure 3.3c. If we center our attention
on context TV83, this plot clearly illustrates that U/ITS is lying far away from the rest, hav-
ing both lower integrity and higher fragmentation than GTS and HTS. This combination of
traits, low integrity, and high fragmentation is hypothesized for ceramics heavily distorted

(a) _ _ _ _ _ _L_Ls_s_b----·-·-----,

(c)

GTS
-0.15 i 1---- ...........
HTS

1.9 2.0 2.2

FIGURE 3·3 (a) Multiple bar charts for LL8sb context. (b) Multiple bar charts for TV83
context. H, =information entropy (in bit). U/ITS =Unknown and Italian TS, GTS = Gaulish
TS, HTS = Hispanic TS. MxNI =maximum number of individuals, MxNINU = MxNI non-
undetermined, MxNIA = MxNI associated, MxNII = MxNI identified, MxNIT = MxNI
classified according to subtype, CP =complete profile, CV =complete vessel. (c) Bivariate
diagram of integrity (H,) vs fragmentation (FI). Black triangle: total ofLLSsb. Black circles:
strata ofLLSsb. Gray triangle: total ofTV83. Gray circles: strata ofTV83.
38 J. BUXEDA I GARRIG6S AND M. MADRID I PERNANDEZ

by formation processes that lead to a serious loss of information and a low rate of refitting
(i.e. a high fragmentation). Contrariwise, if we focus our attention on the LLSsb context,
U!ITS has integrity and fragmentation similar to that of GTS and HTS. This situation in
the LLSsb context can be related with the higher frequency that this U!ITS class presents in
front of GTS and HTS. These results suggest several viable hypotheses of Terra Sigillata dis-
tribution at Baetulo that are not directly related to consumption, but to formation processes
of both contexts. The assemblage from TV83 is dominated by the pottery types contempo-
rary to the hypothesized time of deposition. Few sherds of the older U!ITS group entered
into the assemblage, and they correspond to small, isolated fragments seriously distorted by
the intensive action of various formation processes. In contrast, the assemblage from LLSsb
contains U /ITS as its most frequent class, and its integrity and fragmentation are similar to
GTS and HTS, suggesting that the filling of this context included material from an older
context, already containing the U/ITS, that was simply redeposited in this secondary context
together with a few contemporary ceramics (GTS and HTS). This latter pattern suggests that
the filling of context LL8sb was intentional, removing a previous deposit, while that ofTV83
resulted from the natural infilling of a context after abandonment.
Summarizing, the archaeological study enabled us to inferentially define two contexts
TV83 and LLsSB dated back to the end of the first century AD aggregating, in both cases, sev-
eral archaeological strata. The sherds ofTerraSigillata of eacb assemblage were then archaeo-
logically classified into three categories (UIITS, GTS, and HTS), leading to an archaeological
stratification ofboth TS assemblages. Then, after a refitting process, MxNI was estimated and
each individual was then classified on the basis of the portion of information retained of the
complete vessel (from MxNI to CV). The calculation of the integrity, as information entropy
(H,), and the fragmentation, after the fragmentation index Fl, for each class of Terra Sigillata
within each one of the analyzed contexts (LL8sb and TV83) enabled the comparison ofboth
contexts. At this point, a dear differentiation of two synchronic contexts in terms of their
formation processes has been hypothesized. It seems that formation processes distorted in
different ways the original vessels by acting on their integrity and fragmentation, which in
turn affects the estimation of MxN!. All this information (estimation MxNI, archaeological
classification, integrity, fragmentation, and formation processes) is relevant for interpret-
ing archaeological contexts and must be taken into consideration before comparing them in
terms of consumption.
Moreover, the archaeological analysis conducted so far has also provided a valid sam-
pling frame, based on a representational model of the empirical reality that considers the
whole ceramic assemblage regardless of the information retained by different sherds (i.e. it
is not just based on especial shape.s such as rims, bases, etc.). All sherds have been used on an
equal basis in the archaeological analysis and have probabilities above zero to be sampled for
the archaeometric study. Thus, this sampling frame can be safely used to design the routine
archaeometric study that will provide information on the main intrinsic and essential source
properties of composition and structure that would enable the archaeometric classification
of this Terra Sigillata (i.e. its post-stratification). It is after this post-stratification that we will
get the necessary understanding of our ceramic assemblages in terms of meaningful ceramic
groups, to deepen the knowledge of our archaeological research problem (see Research
Problems).
Considering the financial and practical limitations imposed in the study of this Roman
town of Baetulo,7 the routine archaeometric study was performed on a sampling fraction
 DESIGNING RIGOROUS RESEARCH 39

of 9.9% at LL85b (15 out of 152 MxNl), and 10-4% at TV83 (19 out of 182 MxNI). The first
phase of this multiphase sampling was devoted to chemical characterization by X-ray fluo-
rescence analysis and mineralogical analysis by X-ray diffraction. In subsequent phases, as
stated above, complementary techniques (scanning electron microscopy and different tests
for the assessment of mechanical properties) were also used. In that way, different meaning-
ful ceramic groups were identified conducting to a post-stratification of the population (i.e.
the TerraSigillata in the ceramic assemblages of the TV83 andLL85b contexts) now based on
the intrinsic essential source properties of composition and structure.
It must be highlighted that there exists an important difference between the archaeo-
logical stratification (i.e. the classification in U/ITS, GTS, or HTS) and the archaeometric
post-stratification (i.e. the classification in meaningful ceramic groups). Archaeological strat-
ification is conducted on the whole ceramic assemblage under study (i.e. all MxNI are archae-
ologically classified). On the contrary, archaeometric post-stratification is only conducted on
the individuals included in the sampling (i.e. the individuals included in the archaeometric
study). Unless all MxNI have been archaeometrically characterized, post-stratification of the
population is a matter ofinference based on the results for the sampling fraction.
As will be seen in what follows, the post-stratification of the Terra Sigillata ceramic assem-
blage is a partition of this domain into different parts (i.e. the meaningful ceramic groups).
The numerosities of each part (i.e. their frequencies) are the components. As stated at the
beginning of this section, any part with a component higher than zero will contribute to
the richness of the assemblage, while the distribution of these components will define the
evenness of the assemblage. Both properties are intrinsic essential derived properties based
on components and serve to measure the diversity of assemblages (Buxeda et al., 2013).
Measuring and comparing diversities of both assemblages is thus the frrst step after the
archaeometric post-stratification.
The study of diversity after archaeometric post-stratification revealed a richness of five for
LL85b (Figure 3-4a) and six for TV83 (Figure 3.4b), which means that archaeometrically five
and six different Terra Sigillata meaningful ceramic groups were identified in each assem-
blage. As expected, the state-space of the archaeological stratification, based upon three
macroscopic/archaeological ceramic groups, is different than the state-space of the archaeo-
metric research, which identified twice as many strata (or groups, i.e. classes) in each assem-
blage. At LLSsb, three Terra Sigillata meaningful ceramic groups were identified in the Ul
ITS class: Arezzo, Production A, and Latium -Campania. Classes GTS and HTS correspond
to La Graufesenque and Tritium Magallum production centers respectively. The evenness
graph illustrates the information entropy for this context as 1.69 bit (72-7'Yo of the maximum
value for five classes) (Figure 3-4a).
In the Terra Sigillata assemblage froin TV83, two productions were identified within
each of the three macroscopic/archaeological ceramic groups: Arezzo and Pisa productions
were identified for the UJITS class; La Graufesenque and Montans productions for GTS;
and products from Tritium Magallum and the area of Tritium for HTS. In this context, the
evenness graph illustrates the information entropy of this context as 1.93 bit (74-7% of the
maximum attainable for six classes), a value quite similar to that of LLSsb. However, a fair
comparison between the contexts in terms of diversity requires a correction for the differ-
ence in sample size from the two contexts, using a rarefaction process simulating that all
compared samples had the size of the smaller one (Heck eta!., 1975). This process was per-
formed by random sampling without replacement for 15 individuals out of the 19 at TV83,
40 J. BUXEDA I GARRIG6S AND M. MADRID I FERNANDEZ

(o) LL8Sb(n '" 15) (b) 1V83(n"' 19)

Richness "' 5 Richness"' 6
14 14
H2 "'1.69 bit H2 "'1.93 bit
12 H2o;o"" 72.7 12 H20fo"' 74.67

10 10

4 4

OL,---~--~--~---,J
Arena la.Grauf. Prod.. A lat..cp. Tritium.M. La.Grauf Tritium Arezz Pisa Montans Area.of.T.

LL85b(n"' 15; R"' 5) -1V83(n "'1 9; R"' 6) 1V83(n ""19; R"' 6)

(<) Richness"' 5.176±0.75 (d) Richness "' 5 176· :1: 0 75
14
400
12

10
300

f
g.
8

.t 6 200

4
100

0
3 4 5 6 4 5 6
Resampling of 15 individuals 1000 times(± ls) Richness in resampling of 15 individuals 1000 times

FIGURE 3·4 (a) Evenness graph for LL85b. (b) Evenness graph for TV83. H, ~information
entropy, H,% ~relative H,. (c) Evenness graph of the rarefaction experiment. Gray: LL85b,
Black: TV83 (with 1 standard deviation error bars). (d) Bar chart of richness after the rarefac-
tion experiment.

repeated 1,ooo times. The results (Figure 3.4c) illustrate that the evenness graphs for the two
contexts cannot be considered significantly different from the rarefied samples at two stan-
dard deviations. A bar graph of richnesses in the rarefied sample (Figure 3.4d) also demon-
strates that there is not a significant difference in this richness after resampling.
Therefore, although both contexts appear to be derived from different formation pro-
cesses, the diversity of the assemblages from each context, based on the archaeometric study,
do not differ significantly.
Two complementary points to consider about inferring the composition of a target popu-
lation based on the results of the archaeometric characterization need to be addressed. These
two points examine, on the one hand, the probability that one meaningful ceramic group
that is present in the assemblage is included in the sample for the archaeometric study; on
 1
DESIGNING RIGOROUS RESEARCH 41

the other hand, in a reverse process, the reliability of the estimation of relative frequencies
in the whole assemblage after the relative frequency observed in the archaeometric sample.
For the first point let us imagine that LL85b contained a meaningful ceramic group making
up 10% of the total assemblage, in MxNI. What is the probability that any of the individuals of
this meaningful ceramic group is included in the sample for archaeometric study? ~lbe answer is
that in a sample of 15 individuals (i.e. one like our actual sample for this context), such meaning-
ful ceramic group could easily be represented from zero to three individuals, -with an accumu-
lated probability of 0.94; the higher probability being one individual (p = 0.34), followed by two
individuals (p = 0.27) (Figure 3.5). However, there is still a probability of 0.21 that none of the
individuals included in the sample will be from this 10% meaningful ceramic group.
As we have seen in the previous paragraph, it is highly probable that a meaningful ceramic
group accounting for 10% of the whole assemblage (i.e. the population) is represented in the
sample (sample size= 15 individuals) for the archaeometric study. Even so, in 21 out of 100 cases
none of the individuals would be sampled. Forthe rest (79 out of 100 cases) one, two, three, four,
and even five individuals could be included in the sample (Figure 3.5). Thus, provided that this
meaningful ceramic group is included in the sample, we would see in the post-stratification after
the archaeometric study that this meaningful ceramic group accounts for different percentages
of the sample, from 6.7% (when only one individual is included) up to 33.33% (when up to five
individuals are included). These enormous discrepancies that would end with very different
inferences about the assemblage arise because of the small sample size (15 individuals). Thus,
what would be the necessary sample size to make sound inferences? Since our target meaningful

Binominal Distribution:
binomial trials =15, probability of success= 0.1
0.35

0.30

0.25

~
ro

"&- 0.20 i
J3
ro
~
0.15
£
0.10

0.05

0.00 r ?

0 5 10 15
Number of Successes

FIGURE 3·5 Binomial probabilities for n = 15 and p = 0.1.

42 J. BUXEPA I GARRIG6S AND M. MADRID I FERNANDEZ

group in the assemblage accounts for 10% of the individuals, to identify a meaningful produc-
tion group with a true probability (p) of 0.1, with a confidence level of 0-95 (a= 0.05), and a
desired precision of estimate (e) of± o.o5, the sample size for the archaeometric study should be
73 individuals out of152 for context LL85b (if the assemblage of the context under study could
be considered a large population-in statistical terms-the sample size should increase up to
139 individuals). This number (73) is significantly larger than the actual number of samples (15)
selected for the study. This smaller sample size is able to estimate a true probability (p) of 0.1,
with a confidence level of o.8 (a= o.z), and a precision of estimate (e) of± 0.1 (the sample size
under such conditions, for a population of 152 individuals, would actually be 14; the sample size
of 15 would be the actual number for a large population).
As demonstrated above, the archaeometric results drastically changed the archaeological
stratification of Terra Sigillata at Baetulo, facilitating classification of the pottery into specific
meaningful ceramic groups that can, often, be identified with geographical provenances (in
the sense expressed above as minimum areas of provenance attribution). In this example,
Terra Sigillata identified as Arezzo, Pisa, La Graufesenque, Montans, and Tritium Magallum
can be associated with specific workshops or production centers, thanks to the existence of
already established RGs. In the other cases, such as the Production A, Latium-Campania, and
the area of Tritium, the meaningful ceramic groups cannot be identified with specific work-
shops (i.e. with geographical provenances), but are identified and hypothetically related to
geographic/geological areas based on several evidences (some of them archaeological ones
such as the names in potters' stamps, the existence of still not archaeometrically analyzed kiln
wasters, analytical results on Terra Sigillata molds from the town of Pozzuoli in the area of
Latium-Campania, etc.; some others are of geological nature, such as the volcanic inclusions
in the Production A whose origin is presumed in the BayofNaples). The small sample size for
both contexts impacts the desired precision of inferences about the composition of the whole
assemblages. Nevertheless, the existence of a valid sampling frame, together with the possibil-
ity of designing an appropriated sampling strategy, always under a representational model
close to the empirical reality, can lead to a significant improvement of understanding for an
archaeological research problem whose complexity increases as soon as we try to pass from a
general insight (the Roman town of Baetulo as a unique context) to a more detailed analysis
(consumption patterns in different contexts within the same Roman town).
Before we finish this section, we must emphasize that the archaeological research problem
is far from over. The previous example explains how to face the received state of the studied
assemblages in order to get an in-depth knowledge of the composition of our contexts. As
we have seen, the influence of formation processes is mandatory in the contexts we recover
during the archaeological excavation. Thus, moving to a life or systemic context (i.e. making
inferences on the leaving societies in terms, for example, of consumption patterns) is still an
inverse and complex archaeological problem whose solution needs to be approached with all
the information gathered so far.

CONCLUSIONS

Archaeological research based on the study of pottery remains is an inverse problem that
needs to address, first of all, the material nature of ceramics. As stated throughout this
 DESIGNING RIGOROUS RESEARCH 43

chapter, ceramics-simple or complex-are concrete inanimate things artificially trans~

muted from the raw materials employed in their manufacture. As composite materials,
ceramics are characterized by their main intrinsic and essential source properties of com-
position and structure, together with shape and size, as well as their main intrinsic essential
derived properties. This material nature of ceramics must be evaluated and understood from
the archaeometric point of view (i.e. chemical, mineralogical-and vitreous-or petro-
graphic level).
Archaeometry, as a scientific discipline, needs to solve archaeometric research problems
in order to establish and develop essential background knowledge, methods, and theories
to conduct archaeometric routine problems; facilitating the routine application of well-
established methods and techniques to generate the necessary data to address archaeological
research problems. Archaeometric analysis of ceramics is also an inverse problem: we start
with the as-received-state pottery, the end product of weathering and formation processes,
but all of our research questions relate to the states of life-finished pottery, unfired pottery,
and raw materials, and the manufacture processes connecting the three of them.
Archaeometric routine problems aim at identifying meaningful ceramic groups and prov-
enance, and aspects related to ceramic manufacture. Production centers and workshops
offer an ideal framework in which to recover the processes of ceramic manufacture, with
the necessary implication for technical/technological change, and to define reference groups
(and fabrics) that will function as localized references for provenance studies. Contrariwise,
consumption centers are ideal for addressing intended perfor"mance characteristics and the
interaction of vessels with things and people in the behavioral chain of use, including techni-
cal/technological change, as well as archaeological research problems based on composition
of assemblages.
Questions about the composition of archaeological assemblages cannot be answered
without understanding the formation processes which created the archaeological record.
We have argued that a representational approach is appropriate in order to model the empir-
ical reality in a numerical relational system, thus providing the necessary link between the
archaeometric research and the archaeological as received-state empirical reality. Context
and assemblage are the basic units of the representational approach, mirroring the basic
units of site formation processes, and providing a framework for assemblage compositions
based on archaeological stratification and estimation of components; that is, frequencies of
individuals. Archaeological stratification can be based on relational and accidental prop-
erties of ceramics, together with an estimation of intrinsic essential source properties of
composition and structure, and intrinsic essential derived properties determined or hypoth-
esized by macroscopic and stereoscope microscope observations. In the future, portable
analytical facilities and instruments may enable preliminary archaeometric stratification,
prior to laboratory analysis, that would improve the initial sampling frame for the archaeo-
metric study. Fragmentation and integrity must be considered, and proxy representational
measurements have been proposed based on the loss of information. Finally, archaeometric
results enable us to infer the composition of the as-received-state assemblage, creating a new
stratification (a post-stratification) and facilitating the study of diversity.
While archaeometric research problems must continue to be solved to push forward this
scientific discipline, the routine application of archaeometric studies on the thousands of
ceramic individuals, needed to generate the necessary data and the knowledge relevant to
archaeology, make its application routine. But these archaeometric routine problems are the
44 J. HUXEDA I GARRIGOS AND M. MADRID I FERNANDEZ

problems that would become significant in archaeological research, provided that they are
included in and designed for real archaeological research problems.

AcKNOWLEDGMENTS

The ideas of this work have been developed in the frame of the TECNOLONIAL research
project (HAR2oo8-02834 and HAR2012-33784) funded by the Ministerio de Economia y
Competitividad (Spain). We are very grateful to the editor of this volume, Alice M. W. Hunt,
for her valuable comments and corrections that have helped to improve the original text.

NOTES
--·-·-----··--·---
1. The philosophical foundation of this chapter draws on Bunge's thought. Several concepts
and ideas of his work (see especially Bunge, 1996) are used all through the text and will not
be acknowledged individually.
2. All materials are composed of atoms (chemical level). Those atoms are arranged (in an
ordered or unordered way) in crystalline or vitreous structures (mineralogical/vitreous
level). Those mineralogical and/or vitreous structures are then arranged in different ways
(petrologicallevel).Composition can then be addressed at these different but necessarily
related levels by appropriate methods.
3· How the components of this composite material are arranged (e.g. the microstructure of
the clayey matrix, sorting, packing).
4· For a concrete thing its state or change in the state.
5· Fabric is the end product of a paste after firing. As such, a paste can end in more than
one different fabrics. It must be taken into consideration that fabric is also used as a syn-
onym of paste in petrographic analysis, which can introduce some misunderstandings.
6. Pottery is usually recovered as sherds) not as complete vases. Moreover, even after refitting
processes vases are usually still incomplete.
7. The study of this Roman town of Baetulo included many more contexts besides the two
here presented as examples. The total number of individuals included in the sampling for
archaeometric analysis was 225 (Madrid, 2005).

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des dramiques. Conditions et protocole. Collection Bibracte 2 (Gluxen-Glenne: Centre
archeologique Europeen duMont Beuvray), 11-16.
Roca Roumens, M., Buxeda i Garrig6s, )., and Madrid i Ferm\ndez, M. (2013). "El centro pro-
ductor de Terra Sigillata Hispinica altoimperial de AndUjar. Nuevas datos y algunas pun-
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Rye, 0. S. (1981). Pottery Technology. Principles and Reconstruction. Manuals on Archaeology 4
(Washinton, D.C.: Taraxacum).
Schiffer, M. B. (1987). Formation Processes of the Archaeological Record (Salt Lake
City: UniversityofUtah Press).
Schiffer, M. B. (2011). Studying Technological Change: A Behavioral Approach (Foundations of
Archaeological Inquiry) (Salt Lake City: UniversityofUtah Press).
Secco, M., Maritan, L., Mazzoli, C., Lampronti, G. !., Zorzi, F., Nodari, L., Russo, U., and
Mattioli, S. P. (2011). ''Alteration Processes of Pottery in Lagoon-Like Environments:'
Archaeometry 53: 809-829.
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[ournal27: 379-423,623-656.
Skibo,). M. and Schiffer, M. B. (2008). People and Things. A Behavioral Approach to Material
Culture (New York: Springer).
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Fitch Laboratory Occasional Paper 4 (London: The British School at Athens).
 CHAPTER 4

EVALUATING DATA
Uncertainty in Ceramic Analysis

ROBERTO HAZENFRATZ-MARKS

INTRODUCTION

THE uncertainty associated with a measurement can be defined as a parameter that charac-
terizes the dispersal of the values attributed to a measurand ()CGM, 2012). Assuming the
instrument is accurate and correctly calibrated, the uncertainty can be determined by the
standard deviation of a group of measurements of samples.
Uncertainty affects the way the repetition of the analyses leads to the same results, con-
tributing significantly to the elemental variation observed in the context of ceramic analyses.
If all sources of variation in analytical determinations could be reduced to a minimum, there
would still be a non-reducible amount of error related to fluctuations associated with the
measurement process (Bishop et al., 1990).
Evaluating uncertainty in experimental results is an indispensable task because uncer-
tainty can affect the statistical treatment and interpretation of data. The nature of the ana-
lytical data obtained in ceramic analysis can be as simple as the weight of pottery sherds or
integral pieces, the determination of mineral phases, the concentration of a single chemical
element, or, more commonly, the concentrations of many elements that need to be analyzed
together (Baxter and Buck, 2000). This chapter focuses on sources of uncertainty in the
chemical characterization of archaeological ceramics.
Uncertainty, such as analytical error in the chemical analysis of archaeological ceramics,
can have a drastic impact on the interpretation of a dataset. For example, in the simplest case
in which the concentration of just one chemical element per specimen is of interest, uncer-
tainty may affect direct comparison of that variable among samples. A high degree of uncer-
tainty in the data may also hide patterns if, for example, the researcher plots a histogram in
order to verify the existence of a uni- or multimodal distribution to assess clustering of sam-
ples regarding the element analyzed (Baxter and Buck, 2000 ). When two chemical elements
are of interest, a bivariate case, uncertainties unrelated to the natural variability of raw mate-
rials could weaken or mask existing correlation between them, which could also mislead the
archaeological interpretation. Finally, in the most frequent multidimensional case, where
three or more chemical elements are of analytical interest, a high degree of uncertainty may
 EVALUATING DATA 49

affect not only the low-precision elements but also the general correlation structure, which is
an important feature in multivariate statistical analysis (Glascock, 2000 ).
Ideally, uncertainty evaluation in ceramic analysis needs to address errors from all pos-
sible systematic or random sources, from those introduced during ceramic manufacture up
to and including those which result from instrument error or analytical measurement in
the laboratory. Frequently, adequate information about the parameters which could aid in
the evaluation of analytical and/or instrumental error is not reported in archaeometric pub-
lications (Bishop et al., 1990). Possible reasons for this include the fact that experimental
uncertainties are not used directly in many multivariate statistical analyses and the accurate
numerical evaluation of all possible sources of errors is not a straightforward task; frequently,
only the error derived from the counting statistics is considered for single measurements.
A dataset with a high degree of uncertainty not derived from natural variability and cul-
tural behavior may mislead the researcher in answering questions regarding "provenance;'
dating, different pottery workshops, or choice of raw materials. The main purpose of analyz-
ing uncertainty in "provenance" studies is to evaluate and ameliorate its effects on the statis-
tical analysis of a chemical dataset (Harbottle, 1982). These effects also potentially influence
the priorities of future researchers, whose aims and questions will be based· on the initial
misinterpretation of the data. In integrated programs of ceramic analysis, adopted increas-
ingly since the 1980s and comprising the combination of different analytical techniques
(Buxeda i Garrig6s et al., 2001), assessment of uncertainty is crucial because it can lead to
resolving ambiguous relationships among data obtained by different analytical techniques
and prevent incorrect archaeological interpretation of the data.

THE GENERAL EXPRESSION OF UNCERTAINTY

Uncertainty in chemical compositional data derived from archaeological ceramics can be

evaluated using the following equation, first proposed by Harbottle (1976):

s;.
where is the total uncertainty, S~, is the natural uncertainty, S~ is the uncertainty related to
cultural aspects of ceramic manufacture, s:,
is the uncertainty related to post-depositional
s;
effects and alteration, is the sampling uncertainty, and s~ is the uncertainty introduced by
the analytical method of analysis.
This equation attempts to account for the natural, cultural, and analytical sources of vari-
ability or uncertainties associated with a particular archaeologically meaningful chemical
group of ceramic samples (Bishop, 2003). It is important to remember that this equation is
mainly an intellectual exercise for addressing possible sources of uncertainty. It may be diffi-
cult and impractical to determine precisely all the terms in the general equation for a chemi-
cal group. However, the general expression of uncertainty can and should be used as a guide
for identifying potential sources of uncertainty in archaeological ceramic analysis.
Frequently, archaeometric studies are guided by archaeological questions. For example,
the researcher may be interested in understanding ceramic manufacture behaviors and,
50 ROBERTO HAZENFRATZ-MARKS

therefore, will require the chemical data to reflect patterns regarding cultural choices, such
as selection, mixture, and moditlcation of raw materials, and minimize variation related to
post-depositional phenomena (S~), the sampling design (S;l, and the analytical procedure
employed (S!). In chemical characterization for provenance studies, the focus is the deter-
mination of elements measured at trace levels (in micrograms per gram, or even lower), such
as rare earth elements (REEs) and transition metals. Owing to the low concentration of these
elements in a ceramic matrix, minor contaminations and depletions can critically affect their
detection, measurement, and determination, and significantly increase their uncertainty.
To give a general idea of the typical total uncertainty values for chemical groups of archae-
ological ceramics, researchers at Brookhaven found coefficients of variation (_.j;f
I mean)
in the range of 4-9% for elements such as Sc, La, Ce, Hf, Th, and Fe, in an assemblage of
63late Bronze Age pottery sherds from Greece and 10-20% in ceramics from Mesoamerica
(Bieber eta!., 1976). Uncertainty or variance in ceramic chemical groups can be related to the
geochemical origin of the raw materials and/or pottery manufacture behaviors, such as the
addition of tempering materials (Harbottle, 1976).

NATURAL AND CULTURAL VARIANCE (s~ AND s~)

For any given element in a ceramic matrix, there is expected variation or uncertainty related
to geological, geochemical, and weathering processes affecting the raw materials used in pot-
tery manufacture, S~ (Bishop et al., 1982). Depending upon the region studied, the range of
chemical compositional variation may be inferred from the geochemical literature. In other
cases, prior chemical analysis of the regional argillaceous sediments could provide insight
into the elemental occurrence and variation in available raw materials, although these stud-
ies would be unlikely to determine the total range of this variation accurately (Bishop, 2003).
In "provenance" studies of ceramics it is important that there is sufficient natural elemen-
tal variation in the raw materials or ceramic pastes to form discrete groups during statis-
tical analyses; that is, the between-source variation exceeding the within-source variation,
known as the provenance postulate (Weigand eta!., 1977).
The elemental variation introduced during ceramic manufacture is regarded as the cul-
tural imprint of the artifact, S~ (IAEA, 2003). One of the cultural imprints of potential inter-
est is the addition of non-plastic inclusions that do not naturally occur in the raw materials.
The use of temper by potters can vary significantly, potentially diluting important trace ele-
ments and enhancing others. Even if the purpose of the analysis is not to investigate techno-
logical choices regarding the use of temper, the uncertainty introduced by tempers should be
considered anyway because of its effect in the elemental concentration data, or even in the
mineralogical analyses (Summerhayes, 1997).
The simplest solution would be to assess the elements most affected by tempering and
exclude them in the multivariate analysis. There are statistical procedures developed
to consider shifts in the original concentrations, such as the best relative fit (Harbottle,
1976), the modified Mahalanobis filter, which considers the precision of measurements
(Beier and Mommsen, 1994), and concentration ratios (Buxeda i Garrig6s, 1999; Dias
and Prudencio, 2008). These procedures facilitate the differentiation of chemical pat-
terns which are not strongly different and improve the geographical resolution for
 EVALUATING DATA 51

pottery "provenance" determination (Mommsen and Sjoberg, 2007), Grog, crushed pot-
tery sherds used as temper, may further attenuate the distinctiveness among chemical
groups (Neff et aL, 1989).
Even for well~established paste recipes, compositional differences occur between ceramic
objects and batches of objects manufactured in the same workshop, depending on the con-
trol of ceramic production parameters. These variations, related to the mixing of different
clays in varying proportions, pre-treatment of a clay paste in order to select particle sizes of
interest, the influence of firing on the chemical profiles, and so on, may increase S~. These
behavioral choices are often conditioned by geographic distance to suitable natural resources
and functional, social, religious, and economic requirements (Bishop, 2003),

PosT-DEPOSITIONAL VARIANCE (s;)

It is important to assess possible changes in composition and microstructure during burial,

prior to data interpretation in ceramic analysis (Tite, 2009). Alteration may occur as leach-
ing or enrichment of certain elements, the most susceptible of which are alkali and earth
alkali metals, such as Na, K, Ca, Rb, and Cs, although other elements may also be altered.
Many of these chemical and mineralogical alterations occur as a result of in~burial inter-
action of ceramic materials with rainfall and groundwater and depend on the technologi-
cal aspects of ceramic production, the type of raw material used, firing temperature, and
atmosphere, as well as conditions of the burial context, such as pH, proximity to water
sources, and rain regimes. Each of these factors can lead to alteration in the elemental pro-
files of archaeological ceramics, increasing compositional variability, chemical and mineral-
ogical, as a result of the formation of new minerals and destruction and alteration of others.
Chemical and mineralogical alteration can affect the formation of chemical reference groups
expected to reflect the chemical signature of an area or pottery workshop (Buxeda i Garrig6s
et aL, 2001; Schwedt et aL, 2004).

SAMPLING VARIANCE (s:)

Sampling is one aspect of research design that allows the investigator control over the repre-
sentativeness and size of the population selected for analysis, in order to adequately address
a specific archaeological question. The geographic scale of the research, from investigation
of a single site to a regional survey or interregional comparison, will influence sampling
strategy and population size for adequate characterization of ceramic groups (Bishop, 2003).
The ideal sample population is hardly ever analyzed in archaeometric studies. Most fre-
quently, samples are taken opportunistically from museum collections or active excava-
tions, which may vary in their representativeness of time and space of the ancient people
under study (Bishop, 2012). The reason for this is not necessarily the Jack of knowledge about
the best strategy, but that sampling is usually restricted by practical aspects of the research
design, such as which specimens archaeologists and museums make available for chemical
and mineralogical analysis, budget, and cost of analyses.
52 ROBERTO HAZENl?RATZ~MARKS
1
In terms of uncertainty, inadequate sample populations lead to badly characterized chemical
groups, or even unrealistic ones. However, determining the adequate size of a sample population
I
is not a straightforward task since little or no knowledge about the samples, in terms of elemental
and mineralogical composition, may be known a priori (Baxter and Buck, zooo). Nevertheless,
the researcher should be aware of this fact and assess how it can affect uncertainty in establish-
ing chemical reference groups or other aspects of analysis. Even in the case of a biased sampling,
useful analytical results for archaeological interpretation may be generated (Bishop et al., 1988).
The dangers of forming chemical groups based on the analysis of an inadequate sample
population are most critical for coarse-ware ceramics. The poor mixing and heterogeneity of
raw materials could result in the poor distribution of inclusions in the ceramic body, yielding
different chemical compositions for different parts of the artifact. In such cases, and if the
vessel cannot be adequately sampled, the analyst may obtain results that are not represen-
tative of the whole ceramic object (Baxter and Buck, zooo ), increasing the uncertainty of
data. To avoid this problem, a microstructure or petrographic analysis prior to any chemical
analysis is helpful in order to assess the quality of mixing of the raw materials. The com-
bined error regarding sampling from a ceramic body and other analytical uncertainties can
be determined by reproducibility experiments, combining measurements of aliquots from
the same ceramic object (Bishop et al., 1980).

ANALYTICAL VARIANCE (s~)

Variation and uncertainty related to analytical method is the most controllable source of
uncertainty in archaeological ceramic analysis. For the archaeologist, it is important to
obtain high-quality data, which, in terms of accuracy, involves the minimization of ana-
lytical uncertainties that could obscure interesting patterns that answer the archaeological
questions formulated. Analytical quality control can be used to identify possible analytical
inadequacies, which can be corrected for or used to eliminate a chemical element from con-
sideration (Bode and Dijk, 1997). Frequently, owing to restriction in the availability and/or
destructive sampling of ceramic material it is not possible to analyze samples in duplicate
or triplicate. Therefore, careful analytical quality control using certified reference materials
(CRMs) must be maintained to minimize analytical uncertainty.
The uncertainty introduced by the analytical method should be lower than the natural and
cultural uncertainty in the sample population (Harbottle, 1976). Chemical characterization
of ceramics in most cases involves trace element determination; therefore, limit of detection
(LOD) and limit of quantification (LOQ) of an instrument and/or calibration influence its
ability to accurately measure these elements and, ultimately, the differentiation of ceramic
pastes with only minor chemical differences.
When preparing samples for analysis, it is important to remove residual material, such
as soil and organic matter, in order to avoid adding chemical "noise" to the data (Baxter and
Buck, zooo ). For example, the removal of outer surfaces from shreds before sample prepara-
tion reduces the chance of contamination (IAEA, 2003).
In activation analysis studies, the analytical uncertainties may include errors due
to contamination in the aliquot extraction from a ceramic body, inadequate sample
 EVALUATING DATA 53

homogenization, weighing errors, impurities in the irradiation vials, the suitability and
homogeneity of reference materials, particle flux variations, absolute quantity of the analyte,
counting statistics, gamma spectrum processing, sensitivity, selectivity, spectral interfer-
ences, decay and background corrections, and counting geometry (Harbottle, 1976; Bishop
et al., 1990; Bode and Dijk, 1997; Bishop, 2003).
Prior to any application of statistical techniques, the first stage in data analysis should
be a visual inspection of columns in a dataset, representing different chemical elements
determined, in order to identify obvious discrepancies or errors. This preliminary evalua-
tion helps reduce analytical uncertainty, since these outliers would increase the dispersion
parameters of the samples and reduce the homogeneity of chemical groups. Concentrations
below the detection limit of the analytical technique for a specific chemical element should
be considered missing values. They may re.present a kind of uncertainty if an imputation
method is used. On the other hand, by excluding samples to eliminate such a problem, one
may lose information about the data structure, as that type of missing data appear in a non-
random fashion. If the quantity of missing values is above critical limits employed, such as
10% or 20% of the number of samples, it would be advisable to exclude the element (Baxter
and Buck, 2000).
One common approach for determining the termS~ and controlling the analytical uncer-
tainty is the analysis standard or certified reference materials (SRM/CRM) simultaneously
with the unknown ceramic samples. Reference materials are designed to have no natural
variability or sampling error, and the concentration of the chemical elements of interest in
the matrix is known from certificates. Furthermore, poor analytical precision can prevent
the comparison among datasets (Bishop et al., 1990).
Tools as control charts for identification of non-confOrmances, z-scores, and u-scores are
common approaches for the analysis of analytical results of standard reference materials
(Bode and van Dijk, 1997). One means of quantifying sources of errors other than the count-
ing statistics is by subtracting the latter out from the coefficient of variation of samples of a
reference material (Blackman and Bishop, 2007 ).
Finally, some caution is advised in physicochemical characterization studies of archaeo-
logical ceramic materials. While analytical instruments and calibrations may provide mea-
surements statistically significant for modern engineering applications, where the ceramic
production parameters are more controlled, these measurements may not be statistically
significant for the cultural context under study, the identification of differences in manu-
facture behavior, or evaluating relevant socioeconomic aspects of pottery production (Rice,
1987: 327).

EXAMPLE

As mentioned above, it may be difficult to calculate precisely each source of variability in the
general equation of uncertainty. In practice, it is easier to use the equation as an instrument
to evaluate possible sources of variation in a specific archaeometric study. However, in some
cases, it is possible to estimate values for each source of uncertainty and have a quantitative
idea of the overall reliability of the data.
 ,..

54 ROBERTO HAZE:\!FRATZ~MARKS

Table 4.1 Uncertainty values calculated for a ceramic chemical group from the
Central Amazon
Element Is, I(Ofo) s; (%) s's s!/ si (Ofo) (s~+sZ,)jsi (%) s,'I s;, (%)
-~~~~·-~•w ,. ··-~~ ..
Some elements of interest
La 11 "0 "0 10 90 "0
Lu 12 "0 "0 41 59 "0
Yb 11 "0 "0 33 67 "0
Cr 12 "0 "0 25 75 "0
Eu 13 "0 "0 50 50 "0
Fe 14 "0 "0 7 93 "0
Sc 11 "0 "0 12 88 "0
Th 11 "0 "0 32 68 "0

Altered elements

Na 67 "0 "0 35' 64

K 70 "0 "0 4 51' 45
Cs 50 "0 ~o 4 36' 60

*Estimated by the dispersion of elemental concentrations in clay sources.

In the following example uncertainty is calculated for the chemical data, obtained by neu-
tron activation analysis, of pottery from a large archaeological site in Central Amazon, Brazil,
located in a geochemically and hydrologically dynamic area. Two chemical groups were deter-
mined using multivariate statistics; however, the following discussion focuses on the uncer-
tainty in a single group. Analytical uncertainty was estimated for some of the elements of
interest for which there was good analytical quality control using standard reference materials.
In order to illustrate the effect of alteration on elemental concentration, the post-depositional
uncertainty was calculated for three elements, Na, K, and Cs. These three elements are pre-
sented only for illustrative purposes and were not used in the definition of chemical groups.
It is also important to note that the elements in Table 4.1 are only used to illustrate uncertainty
in geochemical data for this particular sample and are not necessarily ideal elements for group
determination in general; diagnostic elements vary according to the region, type of ceramic,
and analytical instrument.
In Table 4.1, the second column, !Sr
1, corresponds to the coefficient of variation calcu-
lated for this chemical group, which varies from 11 o/o to 14% for the elements of interest.
Uncertainty related to post-depositional alteration (third column) and sampling (fourth
column) were not calculated. In the latter case, this is because the sample population
derives from the most representative units of the excavation and different stratigraphic lev-
els within these units, making it as representative of the ceramic archaeological record of
the site as possible, reducing S,~ to zero. The proportion of total uncertainty represented by

li
 EVALUATING DATA 55

the analytical uncertainty, (5~1 I$.~.), is presented in the fifth column; analytical uncertainty
was estimated by the coefficients of variation calculated fOr a standard reference material
analyzed together with the unknown samples. In our test case, the proportion of uncer~
tainty related to the analytical method can be as low as 7% for iron or as bigh as 50% of
the total elemental variance for europium. The sixth column presents the amount of total
uncertainty related to the combined natural and cultural uncertainty, (S~ + S~) IS~. which
can be difficult to separate. For the elements of interest, this term was calculated by sub-
stitution of the other determined terms in the general equation; and for Na, K, and Cs it
was approximated by the coefficients of variation for some suitable clay sources analyzed.
Finally, the seventh column, s; Is:, represents the proportion of variance related to post-
depositional effect; assumed to be zero for the elements used in the defmition of chemical
groups but for Na, K, and Cs this term was determined by substitution of the other esti-
mated terms in the general equation.
A comment about Na, K, and Cs elements that were affected by post-depositional phe-
nomena according to previous studies: the analytical uncertainty for these elements
is relatively low (maximum of 4% forK and Cs), but the proportion of post-depositional
uncertainty is high, more than 50% for Na and Cs. Chemical groups differentiated on the
basis of Cs in this region, therefore, could potentially be based on post-depositional altera-
tion rather than raw material sources.

CONCLUDING REMARKS

This chapter demonstrates the importance of evaluating all possible sources of uncertainties
in ceramic analysis, as they can affect the statistical treatment and the archaeological inter~
pretation of data. Even in the cases where it is not possible to quantify precisely all sources of
variation in a dataset, it is important to consider their potential existence, so that the inves-
tigator can make the appropriate analytical and statistical choices to yield optimal data that
reflect mainly natural and cultural aspects of archaeological interest.

REFERENCES

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and Spoto, G. (eds), Modern Analytical Methods in Art and Archaeology. Chemical Analysis
Series 155 (New York: john Wiley & Sons), 681-746.
Beier, T. and Mommsen, H. (1994). "Modified Mahalanobis Filters for Grouping Pottery by
Chemical Composition:' ArchaeometrY36(2): 287-306.
Bieber, A. M., )r, Brooks, D. W., Harbottle, G., and Sayre, E. V. (1976). "Application of
Multivariate Techniques to Analytical Data on Aegean Ceramics:' Archaeometry 18(1): 59-74.
Bishop, R. L. (2003). "Instrumental Neutron Activation Analysis of Archaeological
Ceramics: Progress and Challenges:' In: IAEA-TRS416-Nuclear Analytical Techniques in
Archaeological Investigations (Vienna: IAEA), 35-44.
Bishop, R. L. (2012). "Sources and Sourcing:' In: Nichols, D. L. and Pool, C. A. (eds), "lhe Oxford
Handbook of Mesoamerican Archaeology (USA: Oxford University Press), 579-587.
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Bishop, R. L., Canouts, V, Crown, P. L., and De Atley, S. P. (1990). "Sensitivity, Precision, and
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Bishop, R. L., Canouts, V., De Atley, S. P., Qoyawayma, A., and Aikins, C. W. (1988). "The
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Saibal-Analyses of Fine Paste Ceramics, BNL-28105. doi: 10.2172/5258886.
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a Versatile System of Control Charts:' Journal of Radioanalytical and Nuclear Chemistry
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Tite, M.S. (2009). "Mastering Materials." In: Cunliffe, B., Gosden, C., and Joyce, R. A. (eds),
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 CHAPTER 5
.........................................................................................................

STATISTICAL MODELING
FOR CERAMIC ANALYSIS

GULSEBNEM BISHOP

INTRODUCTION

ANALYSIS of archaeological ceramics is one of the most important and complex tasks per-
formed by archaeologists. Information about manufacture, function, and date can be
inferred from the shape, decoration, and fabric of archaeological ceramics, in addition
to providing valuable information about technological and aesthetic changes over time.
Ceramic analyses, whether morphometric, typological, or geochemical, generate large,
complex datasets that need processing and interpreting before they can be used to answer
archaeological questions.
Statistical analysis is profoundly useful in processing large quantities of data to reveal
overall trends and commonalities. In this chapter, we focus on statistical analysis of compo-
sitional and formal ceramic data. Before we go into the relevant statistical models in detail it
is worth spending a little time defming "statistical analyses:'
In the broadest sense, statistics is a discipline that deals with making sense of data. Data
is factual information used to describe objects, processes, behaviors, and observations. As
such, data exists in many formats. It can be qualitative or quantitative, numerical or non-
numerical, discrete or continuous; however, only numerical data can be analyzed statisti-
cally. Qualitative or categorical data deals with descriptions or qualities; they can be observed
but not measured. The texture and color of ceramic sherds are an example of qualitative data;
they can be observed and described but not measured. Qualitative data can, however, be
numeric. Nominal qualitative data is data in which a numeric code is used as a label for the
quality or observation, such as the use of the Munsell Soil-Color Chart numbers to represent
the color of ceramics. Qualitative data can also be ordinal; observations or qualities can be
ranked or rated.
Quantitative data, on the other hand, deals with qnantity and can be measured.
Measurement, from a statistical point of view, simply involves assigning numbers to objects
or events. Therefore, measured data or quantitative data.is always numerical or expressed as
a number. Numerical data can be discrete or continuous. Discrete numerical data is used to
describe objects and events that can be connted as distinct and separate; they are assigned
 STATISTICAL MODELING FOR CERAMIC ANALYSIS 59

whole or discrete numbers, such as the number of students in a class or the values generated
when rolling a set of dice. Continuous numerical data is used to describe observations or
qualities of an object or event that are measured on a continuum of values, such as height,
weight, and length.
Data is powerful. It is the raw material for all inference and interpretation. However, it is
the understanding and analyzing of that data that provides knowledge. The first step in sta-
tistical analysis is to identify the problem or question that needs to be answered and gather
data accordingly. Next, the data needs to be described. During this process, appropriate sta-
tistical models and analyses are used to identify patterns in the dataset. Finally, the statistics
generated are used to make inferences about the data, predict outcomes, and/or answer the
research question.

STATISTICAL MODEL§

Statistical models are a mathematical representation of the data and/or its outcome. They
help us organize and examine data objectively by describing the data visually, enabling us to
see, literally, latent patterns and/or structures. The fundamental differences between quali-
tative and quantitative data require them to be described differently and will be discussed
separately.

Describing Qualitative Data

Qualitative data typically need to be converted into nominal data or categories which can
be counted before they can be described. For example, vessel types, such as vase, jar, and
bowl, are qualitative but the number of objects assigned to each category can be counted and,
therefore, described statistically. The most effective ways of organizing and describing quali-
tative data are frequency tables, bar charts, and pie charts.

Frequency Tables
One of the best ways to organize qualitative data is as a frequency table or frequency
distribution list. In statistics, frequency refers to the number of times an event occurred
in an experiment or study. A frequency table or frequency distribution list, therefore, is
a simple table that records or describes how often an event, value, or category of inter-
est occurred. Most often in archaeological ceramic analysis, frequency of a particular
observation is only meaningful relative to the total number of observations or the rela-
tive frequency (number of events in a category/total number of events). In the small
assemblage described in Table 5.1, the qualitative or categorical data, vessel type, has
been used to organize the assemblage, which is then described by frequency and relative
frequency.
Frequency tables describe the distribution of observations or events in a study popula-
tion. As such, they can be used to compare populations or particular categories/observations
within those populations. In archaeological ceramic analysis, frequency distribution tables
60 GULSEBNEM BISHOP

Table 5.1 Frequency distribution table

describing a small assemblage of
Greek pottery
Vessel Type Frequency Relative Frequency

Amphora 6 32%
Kylix 10 53%
Pyx is 3 16%

are often the first step in making sense of a ceramic assemblage and can be used to determine
activity area, by describing the relative frequency of different types of vessels in different
parts of the site, or changes in occupation of a site over time, by describing the relative fre-
quency of ceramic types in different strata.

BarCharts
Data described as a frequency distribution table can also be described as a bar chart or pie
chart. Bar charts are one of the most common visual representations of data. Bar charts use
rectangular bars, which can be vertical or horizontal, with lengths proportional to the val-
ues they represent to visually describe frequency and distribution of a dataset. For example,
using the data described in Table 5.1, we can plot the frequency distribution of vessel types
(Figure 5.1a) and the relative frequency of those types in the assemblage (Figure 5.1b ).
Bar charts, like frequency tables, can be used to describe the overall distribution of ceram-
ics or ceramic types at an archaeological site or context, identify activity areas, and/or com-
pare consumption of ceramic types across archaeological sites.

Pie Charts
Pie charts are used to visually describe the relative frequency distribution of categorical data.
The chart is a circle, representing the total number of observations in a study or test popula-
tion, divided into segments representing the categories of data in the study population. The
area of each segment is proportional to the number of observations in that category, relative
to the whole population or its relative frequency. 1berefore, pie charts always describe data
as a percentage distribution and cannot be used to describe frequency counts. This makes
pie charts particularly useful for comparing datasets with unequal population sizes; for
example, the types of vessels recovered at two different sites or from two different contexts at
the same site.
In Figure 5.2, a pie chart is used to describe the relative frequency distribution of vessel
types used in funerary assemblages in two contemporary Greek cities, Athens and Sparta.
While this data could also be described using a frequency distribution table, the pie chart
provides a simplified, visual representation of the data. We can easily identify that phiale
were included in burials at both cities in similar proportions; however, lekythoi were favored
in Athens while loutrophoroi were preferred in Sparta. Although this pattern would also be
 STATISTICAL MODELING FOR CERAMIC ANALYSIS 61

(a) Frequency Distribution

12

~
10
] 8
0
>
~
0 6
~
~
E 4
0
z
2
0
Amphora Kylix Pyx is

(b) Relative Frequency Distribution

FIGURE 5.1 Bar charts describing (a) the distribution and (b) relative frequency of vessel
types in a ceramic assemblage.
(Figure courtesy of A.M. W. Hunt)

Relative distribution of funerary vessels from Athens and Sparta

Athens
D Kernos
Lllekythos
0 loutrophoros
l±l Phiale

FIGURE 5.2 Pie charts describing the relative distribution of vessel types in funerary
assemblages from Athens and Sparta.
(Figure courtesy of A.M. W. Hunt)

present in the frequency distribution table, it is possible that it would be obscured by the fre-
quency counts if, for example, the number of lekythoi in Sparta was bigger than the number
in Athens. These assemblages can only be compared when their relative size is taken into
consideration and described as relative frequencies.
The strengths of pie charts include their ability to describe and compare datasets of dif·
ferent sizes and describe the overall composition of a population. 1be biggest weakness of
62 GULSEBNEM BISHOP

pie charts is that only a few categories of data can be described at a time before the segments
become too small to be useful. Similarly, pie charts can also only be used to compare datasets
with the same categories of data.

Describing Quantitative Data

Quantitative data are measurements that are already expressed numerically. However, con~
tinuous data, measurements which may take on any value within a range or interval, often
need to be grouped into discrete categories before they can be described statistically (see
Histograms). 1he simplest way to describe quantitative data is as a table of values or mea-
surements. Even though these tables can be very insightful, they can be difficult to inter-
pret, particularly if the dataset is large. Therefore, quantitative data are typically organized as
tables and then described as histograms and bar charts, stem and leaf plots, box and whisker
plots, and scatter plots.

Histograms and Bar Charts

Histograms and bar charts are visually similar; both use rectangular bars to represent the
frequency of an observation. However, histograms are used to describe continuous data
and bar charts are used to describe discrete data. Discrete data are typically already cat-
egorical; they are counts or scores of observations. In fact, when qualitative data is orga-
nized into categories and quantified, it is converted into discrete data. The distribution
of vessel types in an assemblage is an example of a discrete dataset. Continuous data are
measurements which exit on a continuum, such as length or height. These data must be
converted into discrete categories or groups before they can be described by a histogram.
Typically, the categories used to describe continuous data as a histogram are intervals or
ranges of measurement. All the observations contained by that interval are "counted" as
part of that category.
The capacity of wine amphorae recovered from a hypothetical shipwreck is an example
of a continuous dataset that can be described using a histogram. Roman amphorae held
approximately 27.8liters and, according to Matheson and Wallace (1982), Rhodian ampho-
rae held approximately 25.5 liters in 300 BC, 26.5 liters in 230 BC, and 24.4 liters in zoo BC.
Understanding the distribution of amphora capacities could, therefore, tell us (a) whether
the amphorae were from Rhodes and (b) how old the shipwreck was. By creating capac-
ity categories or groups, from 23-23.9 liters, 24-24.9 liters, and so on, we can organize and
describe the data graphically as a histogram (Figure 5.3).
In this fictitious example, the histogram shows a clear trend in amphora capacity; the
majority of the vessels hold between 25 and 25.9liters. Therefore, the amphorae are probably
from Rhodes and the hypothetical shipwreck dates to around 300 BC. It is also an example of
a unimodal distribution.
An important aspect of describing data using histograms and bar charts is its distribution
behavior or the shape of the data's distribution. Distribution behavior becomes extremely
important, particularly in inferential statistics where results or outcomes are predicted from
 STATISTICAL MODELING FOR CERAMIC ANALYSIS 63

Amphora Capacity Measurements

14

12 -

~ 10
0
~
0
E 8
ro
~
0
~ 6
~

,
E
z 4

0
23-23.9 24-24.9 25-25.9 26-26.9 27-27.9 28-28.9
Capacity measurement (L)

FIGURE 5·3 Histogram of amphora capacity measurements from a hypothetical shipwreck.

(Figure courtesy of A.M. W. Hunt)

Uniform Skewed right

Symmetric Skewed left

FIGURE 5·4 Common shapes of data distribution.

(Figure courtesy of A.M. W. Hunt)

the distribution behavior of the data. Data distribution can be either unimodal, with one
clear trend or mode visible in the data, or multimodal, two or more trends being visible in
the data, and typically conform to one of four basic shapes, uniform, symmetric or normal,
skewed left, and skewed right (Figure 5.4). The histogram in Figure 5-3 is an example of a
symmetric, unimodal distribution.
The most common multirnodal distribution behavior, and an important one in archaeo~
logical ceramic analysis, is a bimodal distribution, where two trends are clearly visible in the
data. In Figure 5·5> the size of mineral inclusions in a ceramic fabric is plotted as a histogram.
The bimodal distribution of the inclusions suggests the addition of a mineral temper, in this
case crushed limestone.
64 GULSEBNEM BISHOP

Mineral Inclusion Distribution

25
~
c
0
-~
20
u"
.s
jii 15
"c
'"
~
0
t
10 ---.. -,.-~•·o<- oh''O

~
E 5
0
z
0
-1--2 0--1 1-0 2-1 3-2 4-3 8-4
4J size

FIGURE 5·5 Bimodal distribution of mineral inclusions in a ceramic fabric.

(Figure courtesy of A.M. W. Hunt)

Stem and Leaf Plots

Stem and leaf plots or stemplots provide another way of representing quantitative data
graphically in order to visualize the shape of a distribution. Unlike histograms, stem and leaf
plots retain the original numerical data to at least two significant units. Therefore, stem and
leaf plots are able to display tbe relative density and shape of the data while retaining most of
their raw numerical integrity.
Stem and leaf plots are arranged like a table. The stem of the data, the first digit or digits
of the numeral, is organized in a vertical column on the left, from the smallest to largest
value. The leaves are usually the last digit or the digit(s) after a decimal point. Leaves are
organized as horizontal rows, from smallest to largest value, and aligned with the appro-
priate stem. To illustrate, refer to the worked example in Figure 5.6 in which the continu-
ous numerical data for vessel weight are listed as a table and corresponding stem and leaf
plot. The first step in creating a stem and leaf plot is to organize the raw data (Figure 5.6a)
from least to greatest (Figure 5.6b ). Next, the data is rounded to the nearest whole number
(Figure 5.6c) and broken into stems (tens digit) and leaves (ones digit) (Figure 5.6d). Stem
and leaf plots always require a key or code, which explains the units/digits of the stem and
leaves.
Figure 5.6 demonstrates the value of stem and leaf plots quite nicely: we can easily identify
that the majority of the vessels weigh between 6 and Slbs. Stem and leaf plots are particularly
useful for large numeric datasets in which patterns are not easily discerned from standard
tables, particularly when it is important to compare similar datasets without losing their
numerical resolution. Comparative stem and leaf plots or back-to- back stem and leaf plots
allow us to quickly identify similarities and differences in distributions between datasets. For
example, if we wanted to understand the level of standardization in cooking pot production
between two workshops, we could do a comparative stem and leaf plot of cooking pot vol-
umes (Figure 5.7).
 a b d
Vessel Weights least-greatest ' rounded stern leaf
82.15 44.45 44 4 4 6 7
63.678 46.4 46 5 0
47.43 47.43 47 6 4 7 8
66.87 49.678 so 7 2 2 5 6
68.326 63.678 64 8 2 2
72.28 66.87 67 10 6
46.4 68.326 68
72.183 72.183 72
75.3 72.28 72 key, 510=50
76.234 75.3 75 leaf unit: 1.0
49.678 76.234 76
stem unit: 10.0
81.934 81.934 82
44.45 82.15 82
106.35 106.35 !06

FIGURE 5.6 Stem-and-leaf plot (worked example) of vessel weights.

(Figure courtesy of A.M. W. Hunt)

a b
Akko Haifa Haifa Akko
Workshop Workshop 20 5
8.4 7.6 19 4
13.9 9.1 18 3689
14.3 9.2 17 29
15.3 9.7 16 48
15.7 10.5 15 379
16.4 10.8 2 14 3

16.8 ll.l 13
17.2 ll.4 9 12

17.9 11.7 874 I 11

18.3 ll.8 85 10

18.6 12.9 721 9

18.8 14.2 8 4
18.9 6 7
19.4
key: 814 = 8.4 mL
20.5

FIGURE 5.7 Back-to-back stem-and-leaf plot comparing cooking pot volumes from two
sites.
(Figure courtesy of A. M. W. Hunt)
66 GULSEBNEM BISHOP

In a back-to-back stem and leaf plot, the stem is the same for both datasets and is plotted
in the central column. The leaves are specific to each population being compared and are
placed to either side of the stem, as illustrated in Figure p. The back-to-hack stem and leaf
plot makes it easy for us to see that, while there is a high level of intraworkshop standardiza-
tion, interworkshop standardization is fairly low; each workshop manufactures two sizes of
cooking pot, but those sizes do not overlap, and vessels from Alcko are typically more than 2
mL larger than those from Haifa.

SAMPLING

In inferential statistics distribution lists are used when we do not have access to the whole
group of material we are interested in learning about. For example, we might want to analyze
ceramics from 120 sites in Greece but we might not have information about the entire assem~
blage for each of these sites. Instead of giving up the project, we can use statistical sampling
to make inferences about the entire population from a smaller sample population.
Sampling is the statistical selection of a subset of individuals from a population to estimate
characteristics of the whole population. TI1e first and most important step in statistical sam-
pling is defining the problem or question and the population from which the sample will be
drawn. In some cases, the population definition is obvious. For example, if we want to investi~
gate standardization of Greek transport amphorae in the sixth-fifth centuries BC, our statisti-
cal population will be Greek transport amphorae from contexts dated between the sixth and
fifth centuries. In other cases, the statistical population may be less clear and require careful
consideration and definition. For example, if we want to investigate changes in potting tech~
nology over time, both the observations of interest (the aspect(s) of potting technology we
are interested in) and the statistical population (the type(s) of vessels, the region and the time
period we are investigating) need to be refined and more clearly defined. Often the problem
and statistical population are partially defined by limitations inherent in the sample frame or
list of individuals available to be sampled. In our Greek transport amphorae example, if our
sampling frame contained only vessels from the fifth century BC, we would need to redefine
our problem and statistical population to reflect this limitation in the data.
In archaeology, we typically use probability sampling in which every individual in the sta-
tistical population has a chance (probability> o) of being selected in the sample. Since the
probability of an individual being selected can be accurately determined, probabilistic sam-
pling can produce unbiased estimates of population totals by weighing sampled individu-
als according to their probability of selection. The three most useful types of probabilistic
sampling for archaeologists are simple random sampling, stratified random, and sampling
systematic sampling.

Simple Random Sample

A simple random sample is one of the most straightforward sampling methods and can be
done without replacement (once a sample has been selected it is removed from the statisti-
cal population), or, less commonly, with replacement (where the sample is returned to the
 STATISTICAL MODELING POR CERAMIC ANALYSIS 67
' __ , ____ '"~- ---~·- -~ -----~-----

-----~~---

Table 5.2 Random number table (excerpt)

~·~----~

40603 16152 83235 37361 98783 24838 39793 80954 76865 32713
40941 53585 69958 60916 71018 90561 84505 53980 64735 85140
73505 83472 55953 17957 11446 22618 34771 25777 27064 13526
39412 16013 11442 89320 11307 49396 39805 12249 57656 88686
57994 76748 54627 48511 78646 33287 35524 54522 08795 56273
61834 59199 15469 82285 84164 91333 90954 87186 31598 25942
91402 77227 79516 21007 58602 81418 87838 18443 76162 51146
58299 83880 20125 10794 37780 61705 18276 99041 78135 99661
40684 99948 33880 76413 63839 71371 32392 51812 48248 96419
75978 64298 08074 62055 73864 01926 78374 15741 74452 49954
34556 39861 88267 76068 62445 64361 78685 24246 27027 48239
65990 57048 25067 77571 77974 37634 81564 98608 37224 49848
16381 15069 25416 87875 90374 86203 29677 82543 37554 89179
52458 88880 78352 67913 09245 47773 51272 06976 99571 33365
33007 85607 92008 44897 24964 50559 79549 85658 96865 24186
38712 31512 08588 61490 72294 42862 87334 05866 66269 43158
58722 03678 19186 69602 34625 75958 56869 17907 81867 11535
26188 69497 51351 47799 20477 71786 52560 66827 79419 70886
12893 54048 07255 86149 99090 70958 50775 31768 52903 27645
33186 81346 85095 37282 85536 72661 32180 40229 19209 74939
79893 29448 88392 54211 61708 83452 61227 81690 42265 20310
48449 15102 44126 19438 23382 14985 37538 30120 82443 11152
94205 04259 68983 50561 06902 10269 22216 70210 60736 58772
38648 09278 81313 77400 41126 52614 93613 27263 99381 49500
04292 46028 75666 26954 34979 68381 45154 09314 81009 05114

statistical population after selection and may be selected again). The best way to talk about
sampling is by working an example. Let us say we have 5,000 ceramic sherds from Area Q
at a site and we want to send 100 to the laboratory for chemical analysis. To take a simple
random sample, we assign sequential numbers to each of the 5,000 sherds (individuals) in
the statistical population (N). Since the largest number in population N has four digits, it is
helpful to list all the samples with four digits, such as ooo1, ooo2, 0003 ... 5000. The sample
population (n) is selected by using a random number generator (available in most statisti-
cal software packages) or a random number table (Table 5.2) to select four-digit numbers at
random untilwo samples have been selected. The four-digit random numbers are selected
by reading tour adjacent terms together or by selecting every n'h term to create groups of four.
These random numbers can be read in any direction/combination and do not need to begin at
the start of the table. For example, we will begin with the second row and select every fourth
term to generate our four-digit random numbers. 'ibis means that, using Table 5.2, the first
68 GULSEBNEM BISHOP

six random numbers generated are 4,596, 6,154, 5,031, 3,853, 5,423, and 1,771. Numbers 6,154,
5031, and 5>423 do not correspond to individuals in population Nand so they are discarded.
Individuals 4,596, 3,S53, and 1,771 become part of the sample population n, and the process
continues until population n contains 100 individuals.

Stratified Random Sampling

Most archaeological research questions involve comparing datasets in which differences
among populations are obvious or expected, such as vessel type or archaeological context.
These differences define subpopulations within the statistical population N. To ensure a rep·
resentative sample population n, it is necessary to ensure that each subpopulation is sam-
pled. To do this, we use a stratified random sample.
A stratified random sample is very similar to a simple random sample, except that the
sample is selected in accordance with the relative proportion of that subpopulation to the
total statistical population N. For example, Area Qat our hypothetical excavation has four
contexts, each of which contains both plain and painted wares: context A contains 20% plain
and So% painted; context B contains 32% plain and 68% painted; context C contains 50%
plain and 50% painted; and context D contains 6oo/o plain and 40% painted. For simplicity,
let us assume that each context has an equal number of individuals or 1,250 sherds. To take a
stratified random sample we need first to separate the statistical population N into subpopu·
lations according to context. Since we want a sample population n of 100 individuals, we
need to select 25 sherds from each context.
Next, we need to separate each subpopulation (context) into plain and painted wares. In
context A there are 250 plain sherds (zo%) and t,ooo painted sherds (So%). To ensure that
the sample population of 25 shreds selected from this subpopulation is representative, we
need to take zo% of the sample from the plain sherds and So% of the sample from the painted
sherds. For a sample size of z5, this means five plain and zo painted sherds need to be selected.
From here the process is the same as taking a simple random sample. Sequential numbers are
assigned to the sherds in the subpopulation for context A and random numbers created until
five plain and zo painted sherds are selected. Each of the subpopulations is sampled accord·
ing to the proportion of plain and painted ware it contains, generating a sample population n
that is representative of the diversity/heterogeneity in the statistical population N.
The advantages of stratified random sampling are that it improves the accuracy of a sam·
ple taken from a heterogeneous population, provides higher-resolution information about
the statistical population, and is often more cost effective since fewer observations/individu-
als are required for a representative sample.

Systematic Sampling
Systematic sampling is similar to simple random sampling in that every individual in the sta·
tistical population has a known and equal probability of selection and is most effective when
the statistical population N is logically homogeneous because the sample units are uniformly
distributed over the population. To take a systematic sample we must determine the sam·
pling interval k. To arrive at k, we simply divide the population size Nby the desired sample
 STATlSTICAL MODELING FOR CERAMIC ANALYSIS 69

size n. In our example, the statistical population size is s,ooo sherds and we want to send a
sample of 100 sherds for chemical analysis. This means that our sampling interval is so; every
soth sherd in population N is selected for analysis.

DESCRIBING COMPLEX DATA

Statistics can also be used to model or understand underlying structure in complex data
in which there are multiple variables, such as chemical compositions. Although there are
numerous statistical procedures and methods that can be used to describe complex data,
in this section we focus on the six most commonly used by archaeologists: multi-response
permutation procedure (MRPP), kernel density estimation (KDE), principal components
analysis (PCA), !-tests, and chi-square tests. Each of these procedures is able to detect
subtle differences among multivariable datasets, making them extremely valuable in
archaeological research where the observations of interest are often subtle. Although these
procedures involve complex mathematics and statistical theory, they are all available com-
mercially in most statistical software packages, making them accessible to laymen.

Multi-Response Permutation Procedure (MRPP)

MRPP is a non-parametric method that tests the hypothesis of no difference among pre-
existing groups (Mielke, 1984). Put another way, MRPP test whether the observed variation
among groups results from different populations of origin or arises from natural variation
within a single population of origin. The null hypothesis in MRPP is that there is no differ-
ence between groups; that is, they have the same population of origin. MRPP discriminates
between this "natural" and "artificial" variation by calculating the weighted mean within
group Euclidean distance or delta (8) for each pre-existing group and determining the prob-
ability tbat random Monte Carlo permutation (groups) of the individuals in all the groups
would have a smaller 8 than the observed 8. The acceptance or rejection of the null hypothe-
sis is determined by generating a p-value; if the p-value is equal to or smaller than the signifi-
cance level (a) the null hypothesis is rejected and the variation among groups is considered
to result from different populations of origin.
The major advantage of MRPP is that it is able to compare groups containing an unequal
number of individuals because 8 is a weighted mean distance. MRPP is also a more robust
alternative to normal theory-based parametric methods, such as t-tests, because it does not
require assumptions, such as multivariate normality and homogeneity of variances, that
archaeological data are seldom able to meet.

Kernel Density Estimation (KDE)

KDE is a non-parametric estimate of the probability density function of a random, continu-
ous variable. KDE is related to histograms, which as we have seen are used to describe the
distribution or density of a variable across a population. Histograms have a few flaws related
70 GULSEBNEM BISHOP

to the arbitrariness of their parameters; namely, group width and starting position. In addi-
tion, because histograms describe only available data, there are often discontinuities, mak-
ing it difficult to detect underlying structure in the data. KDE resolves at least two of these
issues. First KDE involves moving a smoothing function (the kernel) along the observations
to generate a continuous probability curve that reveals and predicts data structure despite
discontinuities. Second, by estimating results according to an average shifted histogram-
that is, the average of several histograms based on shifts in group edges-KDE eliminates
the arbitrariness of the steps between groups, which are often unrealistic in histograms.
However, the bandwidth of the kernel or size of the groups impacts the shape of the pattern
and, thus, the interpretation of the data. Wand and jones (1995) discuss a variety of complex
mathematical functions for determining the appropriate bandwidth for a dataset; however,
Shennan (1997) argues that these methods are no more appropriate/successful than simply
trying out bandwidths of several sizes and intuitively selecting the one with the best balance
of"srnooth" to "rough:'
Examples of how KDE has been used in archaeology data can be found in Baxter and
Beardah (1995a, 1997).

Principal Component Analysis (PCA)

PCA uses orthogonal transformations to convert a set of observations that are potentially
correlated into a set of linearly uncorrelated variables called principal components. These
principal components are orthogonal; that is, uncorrelated with each other because they are
eigenvectors of the covariance matrix. 1he number of principal components is always less
than or equal to the original number of variables and are defined by the transformation in
such a way that the first principal component has the largest possible variance (accounts for
as much of the variability in the data as possible) and each subsequent component has the
highest variance possible that is orthogonal to/uncorrelated with the variation described by
the preceding components. PCA is primarily used as a tool for exploratory data analysis in
order to reveal the internal structure of the data responsible for its variance.
PCA results are often evaluated in terms of components scores or factor scores and com-
ponent loadings. Component scores are the transformed variable values corresponding to
particular data points and loadings are the weight by which each standardized variable in
the original data should be multiplied to get the component score. By squaring the com-
ponent loading of a variable, we are able to determine the percentage of the total variation
in that variable that is accounted for by the component. In this way, PCA is able to pro-
vide high-resolution information about the structure and variation in complex and large
datasets.
In archaeological ceramic analysis, PCA can be used for many and diverse applications,
from understanding variation in vessel shape (Shennan, 1997) to evaluating geochemical
provenance groups. However, PCA has some limitations which can restrict its applicability
for archaeological data. First, PCA is sensitive to the relative scaling of the original variables;
every individual or sample in the population must have a value for every variable in order for
PCA to correctly determine variation distributions/ data structure. Second, PCA is a purely
descriptive technique; PCA does not and cannot make predictions about what future data
and observations willlooklike.
 STATISTICAL MODELING FOR CERAMIC ANALYSIS 71

T-Tests
A t-test is any statistical hypothesis test in which the test statistic follows a Student's t or
normal distribution if the null hypothesis is correct. Typically, !-tests are used to estimate
or determine whether two datasets are significantly different from one another. A Student's
t distribution is used instead of a normal distribution when the scaling term is unknown
and must be derived or estimated from the data itself. There are two types oft-test: indepen-
dent and paired. As the names indicate, an independent t-test is used when we want to com-
pare two independent and identically distributed datasets, one from each of the populations
being compared, and paired t-tests are used to compare paired data from the same popula-
tion, such as repeated measures or before and after studies.
When datasets are put through the t-test formula, at-statistic is generated. The !-statistic
is a measure of variance; more specifically, it is the ratio of an estimated parameter from its
notational value and its standard error. Next, the p-value for the desired significance level,
typically 5% or 1%, is calculated. The p-value is used to quantify the statistical significance of
an observation or hypothesis and is defined as the probability of obtaining a result equal to
or more extreme than what is actually observed.
One of the limitations of !-tests is that failure to find a statistically significant difference
between the datasets does not necessarily mean that the sample populations are the same.
Another limitation, particularly for archaeological data, is that .four assumptions about the
data or conditions must be met for the test to be valid: (a) that one variable is continuous
and the other is dichotomous; (b) the two datasets have equal variance; (c) the two datasets
are normally distributed; (d) the observations are independent (except if running a paired
t-test).
In archaeological ceramic analysis, t-tests are most often used to compare macro-
scopic data, vessel morphology, or context (see Abramiuk, 2012). For example, !-tests
can be used to understand the distribution of artifacts across a landscape. However, the
limitations and assumptions required for valid t-tests seriously reduce their utility for
archaeological data.

Chi-Square Test (or Chi-Squared Test)

1he chi-square test (;r') is any statistical hypothesis test in which the test statistic follows a
chi-square distribution if the null hypothesis is true. Chi-square tests are used to determine
whether the difference between expected and observed frequencies for one or more vari-
ables is statistically significant. 1he most commonly used chi-square test in archaeology is
the Pearson's chi-square test, also known as the chi-square goodness-of-fit test or the chi-
square test for independence. The Pearson's chi-square test is able to evaluate large popula-
tions of unpaired data in order to determine the probability or likelihood that the observed
difference between populations arose by chance (Drennan, 1996).
Like the t-test, chi-square tests use a null hypothesis of "no difference'' between datasets
(observed and expected), which is accepted or rejected on the basis of the p-value for the
desired level of significance. Also like the t-test, chi-square tests do not provide informa-
tion about the strength of the relationship between expected and observed frequencies or
the substantive significance of the relationship in the population. (Van Pool and Leonard
72 GULSEBNEM BISHOP

(2011) discuss the difference between statistical significance and substantive significance.)
Additionally, chi-square tests are sensitive to sample size, the calculated chi-square is
directly proportional to the sample size regardless of the strength of the relationship between
variables, and small expected frequencies in one or more of the cells in the dataset. These last
two limitations are critical for archaeological datasets because the sensitivity of chi~square
to sample size may make a weak relationship appear statistically significant in a large dataset
and/or impact the validity of chi-square tests where one or more cells are less than five.

CoNcLusiON

In this chapter we tried to present an overall view of statistical data types, tests, and tools
that can be used to describe and analyze archaeological ceramic data. Ceramic data can be
numerical or non-numerical, discrete or continuous, quantitative or qualitative. By under-
standing our data, its strengths and limitations, we can develop a well-defined research
question and sample population in order to describe that data and derive and predict mean-
ingful outcomes. Tables and bar and pie charts can be used to describe and predict outcomes
for non-numeric or qualitative data, and histograms, stem and leaf plots, and distribution
analysis can describe and predict outcomes for quantitative data. Complex data can be
described and modeled and outcomes predicted using multi-response permutation pro-
cedure (MRPP), kernel density estimation (KDE), principal components analysis (PCA),
!-tests, and chi-square tests.

REFERENCES

Abramiuk, M. (2012). The Foundations of Cognitive Archaeology (Cambridge, MA: MIT Press).
Baxter, M. J. and Beardab, C. C. (1995). "Graphical Presentation of Results from Principle
Component Analysis:' In: Huggett, J. and Ryan, N. (eds), Computer Applications and
Quantitative Methods in Archaeology 1994. BAR International Series 6oo. (Oxford: BAR
International Series), 63-67.
Baxter, M. J. and Beardah, C. C. (1997). "Some Archaeological Applications of Kernel Density
Estimates:' Journal ofArchaeological Science 24: 347-354-
Drennan, R. D. (1996). Statistics for Archaeologists: A Common Sense Approach (New York:
Springer).
Mielke, P. W. (1984). "Meteorological Applications of Permutation Techniques Based on
Distance Functions:' In: Krishnaiah P.R. and Sen, P. K. (eds), Handbook of Statistics, vol. 4
(Amsterdam: North-Holland), 813-830.
Shennan, S. (1997). Quantifying Archaeology (Edinburgh: Edinburgh University Press).
VanPool, T. L. and Leonard, R. D. (zon). Quantitative Analysis in Archaeology (Oxford: John
Wiley and Sons).
Wallace Matheson, P. M. and Wallace, M. B. (1982). "Some Rhodian Amphora Capacities:'
Hesperia: The Journal of the American School of Classical Studies at Athens 51(3): 293-320
Wand, M.P. and Jones, M. C. (1995). KernelSmoothing(London: Chapman & Hall/CRC).
 ·~~···----------------

CHAPTER 6

RECYCLING DATA
Working with Published and Unpublished
Ceramic Compositional Data

MATTHEW T. BOULANGER

INTRODUCTION

THE Oxford English Dictionary defines "recycle" as the process of returning material to a pre·
vious stage in a cyclic process. In this sense, nearly all scientific pursuits involve recycling
data: analyses generate data from which knowledge is produced, and that knowledge is used
to formulate new analyses that in turn generate new data. Knowledge and data are entwined,
each requiring the other to produce and sustain itself (Carraway, 2011). But as scientists
interested in the formulation of knowledge we often lose sight of the importance of data,
focusing instead on the resultant knowledge and neglecting the primary datasets used to
produce that knowledge. This problem has been, and in some cases continues to be, endemic
across scientific disciplines (e.g. Curry, 2011; Hanson et al., 2011).
This chapter focuses on the fundamental nature of data recycling with respect to the anal·
ysis of archaeological ceramics. Though archaeological ceramic analysis is a small player in
the Big Data movement, archaeology as a discipline is beginning to recognize that it suf-
fers from many of the same problems of poor data-management practices being discussed
by scientists as varied as ecologists, particle physicists, and paleontologists (e.g. Curry, 2on;
Brewer et al., 2012; Uhen et al.} 2013). Here, I focus specifically on one form of archaeologi-
cal ceramic data: geochemical data generated to facilitate estimating or determining prov-
enance, or geological origin of ceramic raw materials. Despite this focus, nearly all of the
details of this discussion are applicable to other forms of ceramic data, be they quantitative
or qualitative.
Until relatively recently most ceramic·compositional data were generated by a limited
number of individuals operating in specialized laboratories. Decreases in cost and physi-
cal size of analytical instruments, as well as the increased commercial availability of such
instruments have resulted in the decentralization of data·generation capabilities (Shackley,
2010; Frahm and Doonan, 2013). Although I believe this shift to be positive, a historical per·
spective on the use of these technologies is necessary. In the past, specialized laboratories
74 MATTHEW T. BOULANGER
1
carried-and lived up to-the obligations of interlaboratory communication, collabora-
tion, insurance of mutually interchangeable data, standardization to allow reuse (both inter-
nally and externally), and maintenance of databases (Harbottle, 1982b). Reuse of data in
this environment was typically small scale and easily accomplished: the individual players
knew each other, knew what data were being generated, and knew each others' procedures
so as to ensure mutual intelligibility. Regardless of its "potential to make very real changes in
our discipline'' (Shackley, 2010: 18), the currently increasing widespread adoption of instru-
mentation capable of generating compositional data has the very real potential of leading
to what Speakman and Shackley (2013: 1435) refer to as silo science-a situation in which
"each researchers' data is self-contained, independent, and cannot be verified externally:'
Silo science, as they mean it, is highly problematic for archaeology in general, and ceramic
compositional analysis in particular, because data are generated without regard for preci-
sion, accuracy, or interobserver compatibility. As long as the data appear to be internally
consistent with previous analyses on the same instrument, they are good enough. Under this
perspective, the archaeological knowledge (i.e. from where a piece of obsidian came, or what
compositional groups are made from pottery) is the goal, and chemical analyses are simply a
means to get there. '!be problem, though, is that the data used to generate this knowledge can
be neither replicated nor evaluated. At best, this results in additional time and effort to re-
analyze the same or similar specimens. At worst, it means that the resultant knowledge can
be neither confirmed nor refuted, and any evaluation of these data necessarily boils down to
argument from authority or opinion.

AN HISTORICAL PERSPECTIVE ON
THE RECYCLING OF DATA

Analyses of archaeological ceramics have, in many ways, always rested upon a foundation
of data recycling. Consider the case of the University of Michigan's Ceramic Repository for
the Eastern United States established by the National Research Council in the late 1920s
and directed by Carl E. Guthe (Lyon, 1996; O'Brien and Lyman, 2001). james B. Griffin,
one of the first graduate students to assist Guthe with the repository, was charged with
bringing "some semblance of order into the heterogeneous prehistoric pottery material
in the Midwest and in the eastern United States ... by the study of material already out of
the ground in Museums and private collections" (Griffin, 1976: 21, emphasis added; see also
O'Brien and Lyman, 1998: no-ns). Individuals wishing to draw upon data housed in the
repository could travel to the university or correspond with Guthe and/or Griffin. They
could incorporate existing data into their own research as well as contribute new data to the
repository. 1he goal of the repository was to provide a central hub for data storage and data
dissemination.
As successful as the Ceramic Repository and similar institutions were, their use was
restricted by the need to travel to a specific location. This situation slowly began to change
in the late 196os, when computers made it possible to store and to analyze data digitally.
However, computing centers were generally available only at large universities and
government-funded national laboratories. Storage media-punch-cards and magnetic
F
RECYCLING DATA 75

tape~ required physical delivery, and neither media was amenable to easy exchange across
long distances. Even if they had been, the end user would need to have the correct hardware
to read them and knowledge of the correct sequence of control commands to access them.
Nonetheless, the advent of digital data-storage set the stage for fundamental changes in how
data could be stored, accessed, and reused.
Concomitant with the development of digital computers was the development and refine-
ment of physicochemical techniques aimed at the compositional analysis of archaeologi-
cal pottery, driven in large part by nuclear research facilities throughout the Western world
(see reviews by Sayre, 1963; Harbottle, 1976; Wilson, 1978; Harbottle, 1982a; Bishop and
Blackman, 2002; Beaudry-Corbett, 2003; Speakman and Glascock, 2007). Nearly all com-
positional analyses performed after the mid-196os have been directed at identifying the raw
material provenance of archaeological material (Sayre et al., 1957; Emeleus and Simpson,
1960; Richards and Hartley, 1960; Sayre, 1963; Perlman and Asaro, 1969; Perlman et al., 1972;
Harbottle, 1976; ).
Many data were produced between 196o and 1980, and most of these data were generated
at a handful of laboratories specializing in bulk compositional analysis. In 1982, Harbottle
suggested that until the mid-1970s most compositional studies of archaeological ceramics
were "isolated, 'self-contained' usually even within the laboratory concerned" (Harbottle,
1982b: 68). Pottery analyses were usually undertaken at the level of individual projects or
sites. Rigorous comparisons to databases-even within the same laboratory-were rarely
undertaken except at the coarsest levels. There was little concern with ensuring long~term
data preservation. I suspect that this isolation of data was, at least partially, the result of
three factors. First, comparisons of raw data were often performed, at least initially, by hand.
Second, laboratories were focused primarily on the novelty of methodology. And, third, not
many data existed. Regardless of cause, this is precisely the situation described thirty years
later by Speakman and Shackley (2013) as "silo science:'
By the mid-1970s, this "isolation'' of data was effectively ending. Sayre (1975) intro-
duced a series of computer programs for multivariate compositional-data analysis; thus it
was possible to analyze large data matrices without resorting to a slide rule or pocket cal-
culator. Harbottle (1982b) estimated that data existed for upwards of 5o,ooo archaeological
specimens worldwide; thus comparative data were available for many regions of the world.
And, most importantly, nearly every laboratory producing ceramic-compositional data had
established routine protocols involving the analyses of standard reference materials, and the
mutual exchange of these standards with other laboratories. Over time, nearly all major labo-
ratories converged on the use of internally developed standard materials (e.g. Perlman-Asaro
Standard Pottery) (Yellin et al., 1978; Asaro and Adan-Bayewitz, 2007; Yellin, 2007), interna-
tionally available standard reference materials (Blaclanan and Bishop, 2007; Glascock et al.,
2007; Harbottle and Holmes, 2007 ), and intercalibration among laboratories (Yellin et al.,
1978; Ferreira et al., 1980; Yeh and Harbottle, 1986; Djingova et al., 1990; Tomlinson, 2002).
All of these factors, as well as the newly available microcomputer, crystallized in the early
1980s, and archaeologists and ceramic analysts began addressing the need to establish one
or more repositories to preserve and provide access to data being generated across the world
(e.g. Matson, 1982a: 25-26, 1982b; Sayre, 1982). The Smithsonian Archaeometric Research
Collections and Records (SARCAR) initiative (Bishop et al., 1983) was created as a poten-
tial solution for the accumulation-but general lack of rigorous integration and long-term
preservation-of ceramic data in archaeometric laboratories.
76 MATTHEW T. BOULANGER

Like the University of Michigan's Ceramic Repository, SARCAR was planned as a physi-
cal repository to which researchers could travel to access data. In part, this was because of
limitations in data-storage technologies at that time. Large-capacity data storage was only
available on magnetic media, and this was not only difficult to transport, it was (relative to
later technologies) fragile both physically and in terms of its ability to retain data. Subsets
of data could be sent to colleagues on 8 in., 5.25 in., or 3-5 in. diskettes; but again, these mag-
netic media were not particularly robust. Moreover, with capacities of 500 kilobytes, 8oo
kilobytes, and 1.44 megabytes respectively, none was capable of holding a very large data-
set. Interlaboratory data exchanges typically involved printing tabular data at the source
and subsequent transcription of these data at the destination (e.g. Tomlinson, 1997; Hein
et al., 2001; French et al., zooS). Despite the difficulty of transferring and digitizing stacks
of printed paper and the fragility of magnetic storage media, direct exchange and reuse of
ceramic data showed a marked increase during the 1980s and early 1990s (e.g. jones, 1986;
Knapp and Cherry, 1994).
In 1995, after several years of increased Internet commercialization, the National Science
Foundation Network (NSFNet) transitioned into what became the backbone of today's
World Wide Web (WWW). The effect of the WWW on the reuse of archaeological data was
profound because it provided the ability for researchers to have near-instantaneous access
to data generated at other laboratories, regardless of the size of a database. In the mid-1990s,
Hector Neff, then at the Archaeometry Laboratory at the University of Missouri Research
Reactor (MURR), established a Web page containing datasets from published studies on the
Internet.' To the best of my knowledge, this was the first effort to provide a single source
of compositional data for archaeological ceramic analyses, in open-access format, on the
WWW. In the years since, the sophistication and scope of online data distributions have
changed dramatically, moving away from individuals and individual laboratories toward
large data warehouses. The ceraDAT database (<http://www.ims.demokritos.gr/ceradat/
ceradat_home.php>) developed by Hein and Kilikoglou (2011) is intended to provide a
central repository for compositional data on archaeological ceramics from the Aegean and
eastern Mediterranean. No similar database exists for the Americas. However, the Digital
Archaeological Record (tDAR) (<http://core.tdar.org>) (Kintigh and Altschul, 2010;
McManamon et al., 2010) is an online repository for all archaeological data and can serve as
a distribution hub for compositional data (e.g. Boulanger, 2013). Unlike earlier repositories
(e.g. the Michigan Ceramic Repository and SARCAR) these tools provide researchers with
direct access to raw data at any time from nearly anywhere with access to the Internet.

RECYCLING DATA IN THE TWENTY-FIRST CENTURY

Kintigh et al. (2014: 879) argue that "the greatest payoff [in archaeological knowledge during
the twenty-first century] will derive from exploiting the explosion in systematically collected
archaeological data that has occurred since the mid-2oth century:' I agree, and the current
push to implement policies and infrastructure for long-term data-management practices
should provide benefits to archaeology in the future. An historical perspective suggests that
recycling of ceramic analysis data has been a major objective throughout most of the twen-
tieth century; yet what is fundamentally different in the twenty-first century is the almost
 RECYCLING DATA 77

limitless capacity to store data, and the ability for individuals to access those data instan-
taneously from nearly anywhere (e.g. Snow et al., zoo6). Development of computer tech-
nologies for storing, analyzing, and sharing ceramic-compositional data has the potential to
greatly increase the scale of data recycling. Adoption both of ethical obligations (e.g. prin-
ciples six and seven of the Society for American Archaeology's Principles of Archaeological
Ethics, <http://www.saa.org/ AbouttheSociety/PrinciplesofArchaeologicalEthics/tabid/
203/Default.aspx>) and funding mandates (e.g. the National Science Foundation Data
Management Plan Requirements adopted in 2011, <http://www.nsf.gov/bfa/dias/policy/
dmp.jsp>) regarding data management and data sharing provide incentives and motivations
for current researchers to ensure that their data are reusable over the long term. However,
these programmatic statements do not address the large body of data generated during the
latter half of the twentieth century that remains inaccessible-and largely unusable-in its
current forms (Snow, 2010 ).
Data must be transitioned into formats that are usable with modern technologies. If
Harbottle's estimation that so,ooo archaeological specimens were analyzed by 1982 is cor-
rect, all of these data were generated prior to the introduction of 3-5 in. floppy disks, MS-
DOS, and the IBM Personal Computer. Nearly all of the laboratories that produced these
data have now dosed, and have been dosed for over a decade (Figure 6.1). Interlaboratory
data standardization must be established: that is, it must be demonstrated that legacy data
are directly compatible with newly generated data. This may not be a problem for those labo-
ratories that, while in operation, established such standardizations. Yet not all laboratories
did so. Moreover, laboratory practices change over time, and intimate knowledge of these
changes was often retained only by those individuals working within the laboratory. '!bese

Brookhaven.. · ·· f.o-o<----------------------;
Berkeley· ·
Mithigan~<H><------------------------i

Smithsonian/NIST· ·
MURR··
SLOWPOKE (Toronto)f«>-~--------------1
ITN, Portugal··
Hebrew U n i v . ; . o . < > + - - - - - - - - - - - - -
Oemokritos- ·
Univ. Manchester·· . - - - - - - - - - - - - - - <
Univ. Sofia.·>+----------<
British M u s e u m r . - - - - - - - - - - - - - - - ;
Budapest ·
Bonn ·
TexasASM· ·
SLOWPOKE (Quebec)· ·
Argentina·
IPf.N, Peru ·
McMaster·
H Formal laboratory/Institute operating
· · · Reactor opera(ing. occasional archaeom. res~arch Oregon State,__ __
500 archaeological specimens analyzed by NM

1950 1960 1970 1980 1990 2000 2010

FIGURE 6.1 Timeline of a selection of former and current nuclear archaeometry laborato-
ries, and estimates of the total numbers of archaeological specimens analyzed.
Data compiled primarily from vol. 49(2) ofA.rchaeometry.
-------··-····

78 MATTHEW T. BOULANGER

data must also be made available in a manner that ensures their perpetual availability, and
this may require current researchers to reconsider long-held beliefs about ownership of
data and intellectual property. I address each of these points in the following section, using
my work on the ceramic-compositional database of the former archaeometry program at
Lawrence Berkeley Laboratory to provide specific examples and direction.

The Lawrence Berkeley Laboratory Archaeometry Program

Archaeometric research began during the mid-196os at Lawrence Berkeley Laboratory
(LBL) in the research group of Isadore Perlman, comprising himself, Frank Asaro, and
Helen V Michel. By 1967, Perlman and Asaro (1967) had developed a method involving neu-
tron activation (NAA) and high-purity germanium detectors, and, shortly thereafter, they
modified this method to include the use of an in-house multi-element reference material,
Perlman-Asaro Standard Pottery (Perlman and Asaro, 1969), to ensure consistently pre-
cise elemental determinations during each assay. Perlman took early retirement from LBL
in 1972, and in 1973 accepted dual positions in archaeology and chemistry at the Hebrew
University of)erusalem where he, with joseph Yellin, began developing an NAA archaeome-
try laboratory (Yellin, 2007 ). Asaro remained at LBL and directed the archaeometry program
from 1972 onwards. Although he officially retired in 1991, Asaro continued archaeometric
research at LBL until his death in 2014-
Between 1967 and 1989, the Berkeley archaeometry program analyzed over w,ooo
archaeological specimens, most of which were assayed during the 1970s. Generation of
compositional data at LBL involved the use of three different computer data-storage media
and extensive use of paper records. Powdered archaeological specimens were prepared for
irradiation, and descriptive and contextual data for each specimen were handwritten on
loose-leaf paper stored in D-ring binders. IBM punch cards were prepared listing specimen
identification number, weight, thickness, irradiation and decay times, counting times, and
other pertinent information. These cards were fed into the LBL mainframe and used to pro-
cess spectral data, stored on magnetic tape, from the five gamma-ray counts performed on
each specimen. Processing of the spectral data resulted in the generation of elemental abun-
dance data, which were printed out and quality checked by hand. After the data were quality
checked, various statistical tests were performed both by hand and on the LBL mainframe,
and compositional groups were formed. Once analyses were completed, data were stored
digitally on magnetic-tape cartridges in LBLs mass storage system. Printed copies of elemen-
tal abundances were also retained.
Irradiation of specimens at the laboratory ended in 1989 with the decommissioning of
the Berkeley reactor (Asaro and Adan-Bayewitz, 2007). Shortly before this time the LBL
group began sending specimens to either the Reed Research Reactor or MURR for irradia-
tion. After irradiation offsite, specimens were shipped back to LBL for counting. In 1990
and 1991 considerable effort was made to copy the LBL archaeometry database from obso-
lete mass storage cartridges to more than fifteen individual 3.5 in. floppy disks. Funding
was scarce and computing infrastructure at LBL had changed dramatically by this time.
Much of the effort to copy these data was personally funded by Helen Michel (F. Asaro,
pers. comm., 2006).
 RECYCLING DATA 79

The Lawrence Berkeley Laboratory Archaeometry Archives

In 2006, Asaro transferred a large collection of materials from the LBL program to the
Archaeometry Laboratory at MURR (Asaro and Adan-Bayewitz, 2007). These archives
consist of surplus specimens and powders, more than s,ooo pages of handwritten records,
twenty volumes of12 in. x 18 in. dot-matrix printouts of elemental abundances, and a COM
microfilm archive of channel counts for (presumably) every gamma-ray count conducted
at the laboratory. These documents represent the largest single archive of archaeological
(and some geological) specimens irradiated and analyzed at LBL from 1967 until decommis-
sioning of the LBL reactor in 1989. Although the laboratory performed gamma-ray counts
on specimens irradiated elsewhere, these data are not present in the archive. The massive
amount of compositional data in the LBL archive, and the presence of detailed descriptive
data for nearly all of the analyzed specimens, provide significant research potential.
Despite the effort to retrieve the elemental abundance data from antiquated magnetic tape
during the early 1990s, the 3·5 in. floppy disks retained by the laboratory were found to be
empty. Moreover, none of the handwritten descriptive and contextual information for ana-
lyzed specimens had ever been digitized. Thus, the only record of data produced at LBL was
in printed form. Digitization of these data required the line-by-line transcription of more
than thirty elemental abundance calculations for each specimen in addition to all identi-
fication numbers, descriptions, and archaeological contexts. Fidelity in transcription was
ensured through third-party examination of each entry afterwards. Nearly three years of
labor performed sporadically between various other obligations was required to transcribe
all of the data.'
At some point in the digitization process it became apparent that many more specimens
had been analyzed at LBL than those for which elemental abundance data were present.
Once all of these records had been digitized I estimated that the archives sent to MURR con-
tained less than half (roughly 40%) of the estimated 1o,ooo specimens analyzed (Boulanger
and Glascock, 2009). Between 2009 and 2013 I was able to locate an additional So% of these
missing data within the records of former LBL collaborators and in published sources
(Boulanger, 2013). In some cases, these were fortuitous discoveries. Michal Artzy completed
her PhD dissertation research through LBL in the early 1970s and was hired there as a post-
doctoral researcher. Before leaving LBL in the late 1970s, Artzy printed a large amount of
elemental data from the LBL mainframe with the intention of continuing her research. More
than thirty years later, she provided copies of these printouts for the digitization effort. lu
other cases, the discoveries were disheartening. One well-meaning colleague stated that he
had been holding on to several binders ofLBL data printed in the early 1970s. But, after hear-
ing that MURR had received the archives of the LBL program, he had assumed them to be
redundant and subsequently discarded them. Whether they were indeed redundant may
never be known. If they were not, it is likely that these data can never be recovered.
In 20n, a preliminary digitized l.BL database containing all the data provided by
Asaro was uploaded to tDAR to ensure long-term open access to these data. In 2014, an
update (including all of the data acquired between 2010 and 2013) was made to these files
(Boulanger, 2014). In addition to making the digital versions of these archives available, all
the original paper records were transferred to the University of Missouri Anthropology
Museum Support Center for long-term curation. Because nearly all the original
80 MATTHEW T. BOULANGER

collaborators with the LBL program are either retired or deceased, questions concerning
ownership or intellectual property rights of these data are vague at best. Respecting the
collaborative agreements that resulted in the generation of these data, it was decided to
include the names oflaboratory analysts (i.e. Perlman, Asaro, and Michel) as well as those
of collaborating archaeologists as the "authors" of these data as listed on tDAR. Thus, any
use or citation of these data will explicitly acknowledge the contributions of the individu-
als involved.

LOOKING BACKWARD AND LOOKING fORWARD

Ceramic provenance studies have historically been situated on the fringes of the social and
natural sciences (Dunnell, 1993; Killick and Young, 1997 ), yet our data are explicitly archae-
ological. Recycling data has been, and will continue to be, a fundamental aspect of archaeo-
logical ceramic analysis. In some cases, much work may be required before extant data can
be incorporated into current and future projects (Kintigh, 2006; Snow, 2010). However,
we should not shy away from this task. From an ethical standpoint, many of these data
were generated with some form of public funds, and thus researchers have an obligation
to ensure that these data are usable by future generations of scientists. From an economical
perspective, reusing existing data is an efficient way ofincreasing sample size and the signif-
icance of research at minimal cost-consider that to day's costs of reproducing the entirety
of the LBL database would be somewhere between US$300,ooo and $I,ooo,ooo, and doing
so would require at least three years of full-time exclusive work! Perhaps most significant,
though, is the fact that the preservation and reuse of data encourages-and allows-a cul-
ture of replication, reproducibility, and standardization, which serves to decrease waste of
resources and ultimately improve the quality and accuracy of archaeological knowledge
(Ioannidis, 2014).
In the United States, the scope and scale of regulatory compliance archaeology (cul-
tural resource management) began growing exponentially in the 196os. Much of this work
focused on saving artifacts and archaeological data from proximate destruction by bull-
dozers, hydroelectric projects, and highway construction. Yet standards and guidelines for
curating those artifacts and data were not established until decades later, when management
of archaeological collections had reached a tipping point at which collections and data were
being lost (Bawaya, 2007). Ceramic compositional data are reaching an analogous tipping
point. I estimate that today, compositional data have been generated for well over 300,000
individual archaeological specimens by NAA alone, and yet no formal guidelines (e.g. Geboy
and Engle, 2011) exist to assure the quality or long-term usability of these data. Moreover, no
dedicated repository exists in which these data may be stored. Exacerbating this problem
is the fact that data-storage technologies are changing at hyperexponential rates; media on
which data were stored as recently as ten years ago are nearly obsolete today. Failure to keep
pace with these changes has led to a massive backlog oflegacy data. Unless these issues are
addressed, this situation will only worsen as more people generate more data. Working to
preserve legacy databases allows us to better recognize deficiencies in current practices and,
perhaps most importantly, to identify how best we may ensure that our own data are usable
by future generations of scientists.
 RECYCLING DATA 81

NOTES

1. An archived version of this page from 1999 is available on the Internet Archive: <https:/ I
web.archive.org/web/ 19991128144604/http:/ /web.missouri.edu/- reahn/ archdata.htm>
(last accessed May 5, 2016). The current version of this page is available via the MURR
Archaeometry Laboratory website: <http:/ /archaeometry.missourLedu/ datasets/ datasets.
html> (last accessed May 5, 2016).
2. The project would likely have taken less time if dedicated external funding was avail-
able, but many granting agencies (e.g. the National Historical Publications and Records
Commission) are prohibited from supporting projects involving the digitization of feder-
ally funded programs. Because LBL was supported by the US Atomic Energy Commission,
the US Energy Research and Development Administration, and the US Department of
Energy, digitization of records from the laboratory is ineligible for nearly all federal grant-
ing programs.

REFERENCES

Asaro, F. and Adan-Bayewitz, D. (2007). "The History of the Lawrence Berkeley National
Laboratory Instrumental Neutron Activation Analysis Programme for Archaeological and
Geological Materials." Archaeometry 49: 201-214.
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F

PART III

FOUNDATIONAL
CONCEPTS
 CHAPTER 7

CERAMIC RAW MATERIALS

GIUSEPPE MONTANA

INTRODUCTION

RAw materials are the essential substances for the manufacturing of any secondary good. In
ancient times, natural resources were the only available raw materials, preliminarily trans-
formed, modified, or purified, or used directly without significant modification. The ceramic
raw materials, being basically sandy and/or silty days, are, in effect, comprised within the
wider category of"geomaterials:' Geomaterials include all the materials of geological origin,
such as rock, sediment, or soil, which could be advantageously utilized for the manufacture
of artifacts in their natural state or after man-made processing. Consequently, a geomaterial
by itself is somehow associated to a specific manufacturing procedure in order to be con-
verted into a finished artifact.
"Raw material" is used to refer to the substance(s) from which archaeological ceramics
are manufactured because the term "clay" is problematic for several reasons. The term "clay;'
in fact, can refer to a natural incoherent (or weakly coherent) fine-grained material deriv-
ing from the in-situ alteration of some types of rocks, or deposited during an erosion cycle
(sediment). It can also be used as a descriptive term for small-size particles (less than 0.004
or o.ooz mm depending on the adopted classifKation) in the granulometric study of sedi-
mentary rocks or soils. Clayey materials primarily contain "day minerals;' which are mainly
originated by the weathering of feldspars and by low temperature hydrothermal alteration of
various crystalline rocks. Clay minerals are hydrous silicate minerals belonging to the group
of phyllosilicates, and they are distinguished by a "sheetlike structure" with interlayer spaces
along the crystallographic c-axis. They are essentially composed of Si, Al, Mg, 0 and H,O,
frequently with appreciable amount of Fe and K. A major characteristic of clayey materials
is the developing of plasticity when mixed with a suitable amount of water and hardening
when air dried and properly fired.
The manufacture of ceramic artifacts from a clay-based paste, known from the Neolithic,
can be considered without doubt one of the most significant advances in human techno-
logical development. Any ceramic object represents the result of a well-structured produc-
tion chain which starts with the localization and the exploitation of a suitable raw material
and ends with the artisanship and craftsmanship of the potter. All these subsequent opera-
tions of shaping, drying, and firing will lead to a good finished product having specific
88 GIUSEPPE MONTANA

morphological and functional characteristics, showing very different mechanical properties

with respect to the original raw material.
Selection and preparation of raw materials are important aspects of pottery making, but
at the heart of this process is pyrotechnology. At temperatures around 6oo°C, evaporation of
the structural water in the clay minerals triggers their collapse, and subsequent mixing with
water fails to render it pliable. In case of the calcite-bearing or calcareous clays and raw mate-
rials, at temperatures around 850-900°C (temperatures typically reached even in antiquity),
when the decarbonation of calcium carbonate is largely completed and the CO, is driven
off, new crystalline phases (anhydrous calcium aluminosilicates) become stable and grow
up. The hardening reaction induced by the presence of carbonates in the paste thus occurs
by means of high· T and low-P conditions. Mineralogical and structural transformations at
high-Tare essentially influenced by composition of the raw clay, its grain-size distribution,
kiln temperature, and kiln atmosphere (oxidizing or reducing). As stated by Cultrone and
co-workers (2001) concerning high-temperature Ca and Mg silicate formation in carbonate·
rich materials (gehlenite, wollastonite, diopside, and anorthite), combined mass transport
(viscous flow) and reaction-diffusion processes are involved. The development of reaction
textures in consequence of the marked disequilibrium originated by the artificially gener-
ated pyrometamorphism could have some implications for understanding ancient ceramic
technologies and discriminating raw clays sources.
Over the last fifty years the importance of integrating typological classifications of archae-
ological ceramics with quantitative compositional data has increased. As stated by Tite
(zooS): "the primary aim of the application of the physical sciences to the study of ancient
ceramics is to contribute to the reconstruction of their life-cycle from production through
distribution to use, and then to help in the interpretation of this reconstructed life-cycle in
terms of the behavior of the people involved:' Since the publication of the pioneering text by
Shepard (1956), the conventional analytical techniques strictly belonging to the field of min-
eralogy and petrography have been widely and productively applied to the study of ceramic
artifacts, supplying essential information concerning their composition and production or
manufacture technology. Determining mineralogical and chemical resemblances between
ceramic pastes could facilitate the identification of specific productive centers. Within a
particular territorial and/or chronological context, these analytical studies may assist the
reconstruction of the multifaceted empirical knowledge linked to the whole ceramic manu~
facturing process. The development of a well-established production standard is somehow
related to the familiarity of the manufacturer with local geomaterials and pyrotechnical
expertise. Therefore, experimental data should always be integrated into studies pertain·
ing to archaeological ceramics. Several analytical methods applied to ceramic artifacts
might help to answer some major questions of the archaeologist, confirming or rejecting
his hypotheses, which generally have socioeconomic and/or historical implications. In gen-
eral, the analytical procedures belonging to mineralogy, petrography, and geochemistry are
considered to be very important tools for the studies of ceramic and related clayey raw mate-
rials. Distribution or "provenance studies" are intended to establish, on the basis of thin-sec-
tion petrography and/or chemical composition, whether pottery was locally produced or
imported. Provenance studies of archaeological ceramics are based on the assumption that
pottery from specific locations exhibits compositions at least distinguishable from pottery
produced elsewhere. This is because every raw clays source area should be characterized by
definite compositional markers. 'The classification of a ceramic paste and its assignment to
 CERAMIC RA\V MATERIALS 89

a production center can be established more easily vvhen ceramic sherds, kiln wasters (if
available), and raw material are studied in combination and put side by side in terms of min-
eralogical and chemical composition, and critical textural aspects (i.e. packing and size dis-
tribution of aplastic grains) are considered and compared. To identify with a satisfactory
level of accuracy the source of the clayey raw materials used in a given production center
requires an "integrated approach" in which field geology, mineralogy, petrography, and
chemistry are uniformly concerned (Figure 7.1).
In any case, a good knowledge of the compositional and technological properties of the
clayey raw materials available in that particular territory may be a fruitful approach for a
more accurate determination of ceramic provenance. It should be considered, however, that
in the case of the study of specific kiln sites or wider regional ceramic production and circu-
lation it is important to establish the degree of compositional (mineralogy and chemistry)
and/or textural variability in the clayey raw materials of the area. Certainly, this will help
in understanding the intraproduction variability which is an important factor for the cor-
rect interpretation of the ceramic analytical data. It is thus not surprising that the study of
ceramic raw materials has been increasingly regarded in archaeometric ceramic research, in
both archaeological and ethnographic case studies, as the best starting point for identifying
local paste recipes for pottery diachronically produced in any historical period.
The subsequent interpretation of the ceramic "production chain" involves the consider-
ation of further questions relating, for example, to the extent of technological specialization
with the choices made in the selection of raw materials in a specific region, as well as mixing
or tempering procedures and firing skills with reference to a given class of ceramic objects. It
is a significant achievement to be able to identify whether a single clay or a mixture of clayey
materials was consciously used to create a ceramic paste with the specific compositional and

ClAY DEPOSITS
(POTENTIAL RAW MATERIALS CERAMIC PRODUCTION)

INTEGRATED PRODUCTION CENTERS

APPROACH • C!RCUIATION{TRADE

PROVENANCE
~ o!MPORTS

~~~·~W~~~l~M~A~NU~~~cr~U~RE~S;;.;;~
END-USE REQUIREMENTS

~~~"""''
o TEMPERING
o MIXING
• FIRING CONDITIONS

~MI~~~lOGICAl
(OXIDISING/REDUCING)
~
ACHIEVEMENT OF A
AND REPRODUCIBLE STANDARD
TEXTURAL MARKERS). QUALITY

ARCHAEOLOGICAL
CERAMIC

FIGURE 7.1 "Integrated approach" for characterizing and sourcing ceramic raw materials.
90 GIUSEPPE MONTANA

textural characteristics to produce, after drying and firing, finished objects with the looked-
for desired qualities and performance characteristics.
Once the "compositional reference groups" have been established, the model of exchange
and trade for a given archaeological! chronological context may be very likely resolved, and
the questions of where the ceramics were produced and/or where they were distributed and
used will be answered clearly.

MINERALOGICAL AND CHEMICAL

CHARACTERISTIC§

The raw materials for manufacturing pottery essentially include: (a) clays or clayey materi-
als, the dominant or matrix material, and (b) temper, that is to say sand size grains (o.o6-
z mm) which can be arbitrarily added to the ceramic paste by the potter in order to control
physical and mechanical properties or other desired characteristics in the finished products.
Supplementary inorganic natural materials are necessary to impart a slip or a glaze, while the
manufacture of bricks and tiles often requires organic additives (e.g. straw). As mentioned
in the Introduction to this chapter, the term "clay" has three different connotations: (r) fine-
grained and ordinarily loose geological material that develops plasticity when mixed with
water; (z) a grain-size classification for the smallest particles (less than o.ooz mm) found in
geological sediments; (3) the group of hydrous allumosilicate minerals named "day miner-
als;' produced (by weathering or pedogenesis) from preexisting minerals and mostly char-
acterized by a sheet-like crystalline structure. Clay minerals are ubiquitous in continental
fluvial and lacustrine deposits, soils, weathering environments of silicate rocks, and marine
sediments. Clay deposits are found for the most part on or near the surface of the Earth.
In a straightforward categorization concerning the origin of clay deposits it may be recog-
nized: "primary clays" which are formed in situ by the weathering of bedrocks characterized
by high-alumina minerals such as feldspars (e.g. granite, arkoses, etc.); "secondary clays"
mainly formed by means of fluvial transport and deposition of clay minerals and day-sized
particles produced by eroding pre-existing rocks and soils within a complete sedimentary
cycle (Figure 7.2). The majority of natural clays are composed of heterogeneous mineral
mixtures that can be roughly subdivided into clay and non-clay minerals, including poorly
crystalline (low-range ordered or more simply amorphous) inorganic phases. Sporadically
a single clay mineral may be predominant (e.g. kaolinite deposits). Accordingly, clays are
ordinarily composed of mixtures of clay minerals and day-sized or coarser crystals of other
minerals such as quartz, feldspars, micas (muscovite and biotite), carbonate (chiefly calcite
and dolomite), iron oxides, hydroxides (e.g. hematite and goethite), and a variety of parent
bedrock fragments (lithoclasts).
All the clay minerals belong to the family of "phyllosilicates" (from Greek <jlUAAOv, leaf)
which are distinguished by a composite layered structure leading to a silicon:oxygen ratio
of 2:5 giving a flaking appearance. The most characteristic property of several clay minerals
is the ability to adsorb water between the layers, resulting in strong repulsive forces and clay
expansion. From the structural point of view, clay minerals consist of stacked tetrahedral
and octahedral layers, which are kept together by cations, respectively coordinated by Si or
 CERAMIC RAW MATERIALS 91

FIGURE 7.2 Examples of primary and secondary clays: (a) kaolinite deposits in the crater
of Mount Gibele at the volcanic island ofPantelleria (Italy); (b) outcrop of Upper Miocene
marine clays in southern Sicily.
92 GIUSEPPE MONTA~A

Al (tetrahedral layer) and by Al, Mg, Fe'\ Fe'' (octahedral layer). They are classifred first
into "layer types;' differentiated by the number of tetrahedral and octahedral sheets that have
combined, and then into "groups;' based on the type of isomorphic cation substitution that
has occurred. Therefore, in the simplest way, clay minerals can be distinguished: (a) two-
layer or 1:1 sheet silicate structures, consisting of an octahedral layer linked to a tetrahedral
layer, or (b) three-layer or 2:1 sheet silicate structures, consisting of an octahedral layer sand-
wiched between two tetrahedral layers. The composite layers are stacked along the crystal-
line c-axis and linked by cations and/or water molecules placed in the interlayer spaces.
Sheet silicates ordinarily exhibit a special form of polymorphism (the same chemical com-
position but diverse structural framework), defined as "polytypism;' which constitutes dif-
ferences in the stacking of the tetrahedral and octahedral layers. The most common clay
minerals belong to: (r) kaolinite and serpentine group (e.g. kaolinite, dickite, nacrite, halloy-
site, chrysotile, lizardite, antigorite); (2) illite-mica group (e.g. pyrophyllite, talc, illite, mus-
covite, biotite, phengite, glauconite, celadonite); (3) smectite group (e.g. montmorillonite,
beidellite, nontronite, saponite, hectorite); (4) chlorite group (e.g. clinochlore, chamosite,
nimite, pennantite ).
The kaolinite group is the most common of clay minerals with two-layer 1:1 crystal-
line structure (tetrahedral and octahedral combined layers). The general formula is
Al 4Si 40w(OH) 8 and kaolinite, dickite, and nacrite are the principal polytypes. Halloysite is
distinguished by the presence of one water layer in the interlayer structural space. The identi-
fication ofpolytypes, accomplished by means ofX-raypowder diffraction (XRPD) methods,
enable identification of the formation conditions of the deposit. The three principal miner-
als in the "serpentine group;' chrysotile, antigorite, and lizardite, have very similar chemical
compositions, the general formula incorporating all three members being X6Si4 0;o(OH) 8
(where X= Mg, Fe'+, Ni, Zn, Mn), but significantly different structures which attempt to
minimize the mismatch between sheets ofSiO 4 tetrahedra and the octahedral sheets.
The mica group is composed of 47 different mineral species which are all characterized
by 2:1 tetrahedral-octahedral-tetrahedral sheet structure with interlayer cations and little
or no exchangeable water. The most abundant minerals of the mica group are muscovite
KAl,(AlSi 30w)(OH), and biotite K(Fe,Mg) 3AlSi,OwCOH),. Both muscovite and biotite are
usually characterized by tabular crystals with prominent basal planes, and they are very
common minerals in igneous (e.g. granite pegmatite, granodiorite), metamorphic (e.g. slate,
phyllite, schist, gneiss) and sedimentary clastic rocks. The name "illite" is a general term for
the clay mineral constituent of argillaceous sediments belonging to the mica group, having
2:1 composite layer structure. In the illite structure the substitution of Si4" by Al'" produces
a net negative charge of about 0-7-1.0 per formula unit, which is equilibrated by the entry of
K+ in the interlayer space, where water molecules may also be present. A general formula of
illite could therefore be K(Al,Mg,Fe),(Si,Al) 4 0w(OH),. Glauconite is the Fe-rich illite, while
celadonite is relatively more Mg-rich.
Up to sixteen minerals belong to the so-called smectite group, a family of swelling 2:1
phyllosilicates (expandable along the crystallographic c-axis) having residual surface charge
because of the isomorphous substitution in the octahedral layer (Mg2+, Fe+, Mn2+ may sub-
stitute AP") and/or in the tetrahedral layer (AP+ and sporadically Fe'+ may substitute Si4 +).
These substitutions lead to net negative charges in the clay structure which must be satisfied
by the presence of charge-balancing cations within the interlayer. Monovalent cations such
as Na+ cause more expansion than divalent cations such as Ca2+. Smectites are referred to as
 CERAMIC RAW MATERIALS 93

"swelling" clay minerals because they may take up a notable amount of water in the inter-
layer space of their structure. The most frequent mineral in this group is montmorillonite,
with a general chemical formula (Ca,Na)(Al,Mg,Fe) 4 (Si,Al) 8 0,0 (0H) 4 .nH,O. Other com·
mon smectite group minerals are beidellite, nontronite (dioctahedral), Mg·rich saponite,
and U-rich hectorite (trioctahedral). Montmorillonite is able to absorb in a stepwise manner
up to four monomolecular sheets of water producing a maximum swelling along the crys·
tallographic c-axis of around 10 A which in turn leads to a complete basal (om) d-spacing
of around 20 A (thickness variation by almost 100%). Each adsorbed water layer separates
the composite T-0· T sheets by almost 3 A, which is the approximate diameter of a water
molecule.
The chlorite group is composed of twelve phyllosilicate minerals characterized by a
structure consisting of T-0· T layers regularly alternating with a brucite-like octahedral
layer of closely packed hydroxyls. The chlorites are primarily found in weakly metamor·
phased materials deriving from the alteration of pyroxenes, amphiboles, and micas. They
vary greatly in chemical composition owing to substantial cation substitution in both the
octahedral and tetrahedral sites. Thus, a rather complicated general formula may be stated:
A,-.T 4 2, 8, (where A ~ Al, Fe'+, Fe3+, Li, Mg, Mn, or Ni; T ~ Al, Fe3+, Si; Z ~ 0 and OH). The
most common species in the chlorite group are clinochlore (Mg, Fe'+) 5Al(Al,Si,Owl(OH) 8
and chamosite (Fe'+, Mg) 5Al(Al,Si30, 0 )(0H) 8•
Major and trace elements in clay-sized sediments are mostly dependent upon the litho!·
ogy of parent geomaterials and the complex of processes responsible for their formation.
Clay materials vary greatly in their chemical composition. Some of them contain much iron
(i.e. red clays), while others are rich in calcium carbonate (i.e. calcareous clays). Predictably,
the chemical composition of clays is basically controlled by the relative abundances of clay
minerals as well as non-clay minerals. These latter are mostly representative of the silt- and
sand-sized detritic fractions (respectively o.oo2-o.o6 mm and o.o6-z.o mm). Indeed it fol·
lows that a wide range of variation of the concentration of major elements may occur. In
Table 7.1 the chemical composition of the "average terrigenous marine clay" (after Clarke,
1924) is reported together with those of some Italian and Greek clays, which have been here
considered as representative examples of deposits traditionally used as ceramic raw material
in the Mediterranean area. It is possible to highlight some remarkable differences in the bulk
chemistry between the various clayey materials concerning especially the most abundant
oxides (i.e. SiO,, Al,0 3, Fe,03, CaO).
In general, clay materials for ceramic manufacture are characterized by the predominance
ofSiO, (generally between 50% and 65%) that can be correlated to the abundance of detritic
quartz grains (naturally present in the clay material) and other silicate minerals (e.g. feld·
spars, mica) or rock fragments (e.g. granite, gneiss, sandstone), which, on the whole, com·
pose the coarser granulometric fractions (silt and sand), in addition to the SiO, content of
the clay minerals composing the finer groundmass.
Another relevant compositional differentiation between the various ceramic raw mate-
rials is the amount of calcium oxide. In fact, according to the classification made by Tite
and Maniatis (1975), the "calcareous clay" (CC) with a concentration ofCaO greater than 5%
weight can be distinguished from the "non-calcareous clay" (NCC) having CaO concentra·
lion lower than 5% weight. Of course, the CaO abundance is strictly associated with the pres·
ence of calcite, often due to the presence of calcareous microfauna (particularly in marine
clays) and/or to detritic sand-sized fragments oflimestone.
Table 7.1 Chemical composition of the "average terrigenous marine clay" [after Clarke, 1924) and of some representative Italian and
Greek clays
Description of clay deposits Reference Na 20 MgO Al 20 3 Si0 2 P,o, K,o CaO Ti0 2 MnO Fe20 3
---
Quaternary marine clay (Ischia, Italy) n = 2 Montana, 2010 1,75 3,09 15,71 56,63 0,19 2,75 14,73 0,71 0,11 5,46

Lower Pleistocene marine clay (Palermo, Italy) n = 9 Montana et al., 2011 0,75 2,95 17,45 57,22 0,13 1,77 12,43 0,93 O,Q2 6,38

Middle Pliocene marine clay (Benevento, lta!y) Grifa et al., 2009 1,02 3,36 14,96 57,67 0,14 2,43 14,15 0,69 0,07 5,51

Quaternary alluvial clay (Paola, Italy) n ~ 4 Gliozzo et al., 2008 2,01 3,86 19,30 60,00 2,49 2,49 4,89 1,03 0,15 7,40

Quaternary terraced fluvial deposits (Foggia, Italy) n ~ 16 Gliozzo et al., 2005 0,68 2,13 13,26 54,79 0,23 2,60 21,55 0,59 0,13 3,99

Miocene-Pleistocene basinal sediments De Bonis et al.,2013 0,67 3,81 14,75 54,94 0,13 2,85 15,50 0,74 0,12 6,48
(Campania region, Italy) n ~ 22

From Upper Cretaceous to Quaternary basinal sediments De Bonis et al., 2013 1,29 3,10 19,96 61,88 0,15 3,00 1,85 0,93 0,09 7,75
(Campania region, Italy) n ~ 7

Neogene marine clay deposits {Crete, Greece) n = 24 Hein et al., 2004b 0,89 7,20 13,31 53,82 0,20 2,34 14,24 0,89 0,09 7,03

Quaternary red clayey alluviums (Crete, Greece) n = 18 He in et al., 2004a 0,61 . 2,21 22,09 59,99 0,17 2,80 1,69 1,24 0,15 9,06

Average Marine Terrigenous Clay Clarke, 1924 1,15 2,38 18,89 62,60 0,23 2,47 2,24 1,39 0,13 8,09

Normalized value vs. LO.I.

n =number of samples analyzed belonging to the same geological context and considered for calculating the average values
 CERAMIC RAW MATERIALS 95
-----
The concentration of Al 2 0.v as '"''ell as those ofK 2 0 and Na 20, in general, can be positively
correlated to the relative abundance of clay minerals and/or to the quantity of monominer-
alic granules of feldspars and mica in the coarser granulometric fractions. The bulk concen-
tration of Fe,0 3 is controlled by the abundance of colloidal particles of poorly crystalline
iron oxides/hydroxides in the clay materials. It is usually greater in the sedimentary depos-
its where particles with diameter less than o.oo2 mm are on the whole predominant on silt
and sand. MgO content is often associated with the presence of dolomite or Mg-bearing
silicates in the sand fraction, while TiO, content is related to the presence of rutile and leu-
coxene among the accessory heavy mineral and also to the abundance of 2:1 clay minerals.
Both MnO and P ,0 5 are normally not abundantly concentrated in clays and are respectively
linked to the presence of manganese oxides (e.g. pyrolusite) and calcium phosphate (apatite).
Concerning trace elements, the chemical composition of primary and secondary clays is
even more closely correlated than major elements to the parent geomaterial from which they
have developed by weathering or to the pre-existing rocks or soils eroded and involved in the
sedimentary cycle. For example, alluvial clay deposits in a territory characterized by basic
volcanic rock outcrops are very likely richer in trace elements, such as Cu, Zn, Ni, Cr, and
light rare earth elements LREE (La and Ce), that can be used as geochemical "markers" for a
basic environment. Another example: during the weathering process vanadium is incorpo-
rated in the structure of clay minerals by replacement of aluminum in tetrahedral or octahe-
dral positions. Therefore, somewhat higher vanadium concentrations should characterize
clay deposits where the day-sized particles are relatively more abundant than the silt ones.
The concentration of Co is apparently positively correlated to the content of Fe in the clays
because of their positive association in the geochemical cycle in general. High values of Ba
can be associated to the content of feldspar minerals of the clay material (the geochemical
affinity between K and Ba is well known), while a relatively higher Rb concentration could
reflect the greater weights of the finest fractions (clay and silt) in the clay deposit and/or an
abundance of mica flakes. Strontium is more often positively correlated to Ca concentration
thus acting as marker of sedimentary marine calcite-rich clays. Clay deposits of the upper
Tortonian age in Sicily underlying the Messinian evaporitic sequence, particularly) are char-
acterized by more than 1,ooo ppm of Sr.
Mineralogical and chemical composition of a given clay raw material significantly influ-
ence its suitability for producing pottery, bricks, or tiles. For example, iron-ricb and "cal-
careous clays" may be used in the manufacture of red colored and porous ceramic after
firing at 850-950°C with oxidizing kiln atmosphere. Clays naturally containing volcanic
minerals and rock fragments or artificially tempered with them are, theoretically, more
suitable for producing purposely designed cooking ware, fired also at relatively lower tem-
peratures (generally within 750-85o°C). In fact, the presence of volcanic temper produces
a ceramic paste more effectively resistant to thermal shock than quartz temper, which suf-
fers the alpha-beta phase transition at 573°C that produces a rapid volume change (around
5%). The expansion and contraction of quartz grains due to repeated cooking cycles may
produce defects in the ceramic object, such as veining, causing it to break more readily and
thus limiting its usefulness. For comparable reasons, clay deposits full of swelling clay min-
erals (smectites) are seldom used "pure''; however, they are often mixed with poorly plastic
clays in order to improve their performances. Smectite-rich clays profusely tempered with
coarse sand are also attested to have been used locally in the Mediterranean area for pro-
ducing bricks and/or tiles.
96 GIUSEPPE MONTANA

RELEVANT PHYSICAL PROPERTIES

The common characteristic of all clay materials, plasticity when mixed with water, derives chiefly
from the sheet-like structure of clay minerals and from their minute crystal size. As highlighted
above, clay minerals, particularly those belonging to the smectite group (e.g. montmorillonite),
are capable of changing their volume in one dimension by absorption or desorption ofwater. The
volume change process is termed "swelling'> if water molecules enter into the crystal structure or
interlayer space, and "shrinkage" if water is released after dehydration. Moreover, owing to the
ionic substitutions at tetrahedral and octahedral level, the surface of any individual clay particle
(also indicated as "micelle") is typically negatively charged, leading to the attraction/absorption
of cations and water molecules. According to Van Olphen (1963), a structure of water molecules
can be built up around the micelle particle, giving rise to a "double diffuse layd' A relatively ele-
vated concentration of high valence cations will support a thin "diffuse layer:' Conversely, low cat-
ion concentration of the aqueous solution or low valence cations will produce a thicker "diffuse
layer:' As a direct consequence, when high valence cations (typically Ca>+ followed by Mg,. and
AJ3+) are concentrated in the "diffuse layer;' clay particles can approach each other closely with-
out repulsion because the Van der Waals forces of attraction exceed the repulsive forces. These
"attractive" forces lead to the formation of clay particle aggregates which are inclined to precip-
itate-a phenomenon named "flocculation:' When clay particles are dispersed in seawater the
same phenomenon can be observed owing to the high cation concentration of seawater.
Important for our discussion of ceramic raw materials and their properties is that clay materi H

als predisposed to flocculation often produce an excessively porous paste which will likely result
in unwanted cracking and fracturing of the ceramic artifacts during drying and firing. Worral
(1982) explains how the deflocculation of a clay with adsorbed ca++ can be accomplished by
replacing this cation with Na+. For this reason, in modern industrial ceramic production defloc-
culants (e.g. sodium metasilicate, sodium hexametaphosphate, sodium pyrophosphate), with
the ability to sequester Ca,. and alter the pH of water, are habitually used in order to provide
pastes with satisfactory properties for casting and molding. Owing to the presence of a low-
valence cation (Na'), clay particles are prevented from aggregating and a more dispersed solu-
tion/mixture is obtained. An interesting solution for overcoming the problem of flocculation,
attested in several ancient Sicilian ceramic workshops and still used by some contemporary pot-
ters, involves the addition ofNaCl to freshwater during the preparation of clay paste (or even the
direct use of seawater), in order to avoid flocculation of the locally available calcium-rich clay
materials (CaO concentration up to 20-25% weight) (Montana, 2on) (Figure n).
Another physical property of days relevant for their use as ceramic raw materials is their
particle-size distribution. One of the most common procedures for determining the particle-
size distribution of a geomaterial involves separating the loose materials into a coarse (par-
ticles of between 2 and o.o6 mm) and a fme (particles< o.o6 mm) fraction using distilled
water dispersion in a settling cylinder according to Stokes' Law. The fine fraction suspension
may be further separated into silt (o.o6-o.oo2 mm) and clay ( < 0.002 mm) via centrifuga-
tion at zooo rpm and 4000 rpm, respectively.
Particle-size distribution has important implications for both technological performance
of the raw materials and their archaeometric identification (provenance). Grain size is an
important consideration in the selection of raw materials and the preparation of a ceramic
paste because the particle-size distribution of the paste affects the performance characteristics
FIGURE 7·3 Brick and roof tile makers in western Sicily, traditionally using NaCI as
a deflocculating agent: (a) and (b) Spina's Furnace at Gela (Caltanissetta); (c) Martorelli's
Furnace at Racalmuto (Agrigento ).
98 CTTUSEPPE MONTANA

of the object during manufacture and, ultimately, its intended use. There are three impor~
tant ranges of particle sizes each with a distinct role: the "texture fraction' composed by very
coarse sand grains (1-2 mm) primarily used to give strength to structural clay objects: the
"filler fraction;' composed for the most part of medium and fine sand grains (0.1-0.5 mm),
used to control excessive shrinkage and cracking of the ceramic objects during drying and
firing; and the "plastic fraction;' grain sizes below o.o6 mm, composed of both silt and clay
particles, the latter being solely responsible for working and shaping the ceramic paste.
In the manufacture of thin-walled fine ware using the potter's wheel, the "plastic frac-
tion' should predominate in order to facilitate the fluid movement of the paste. A ceramic
raw material appropriate for the manufacture of coarse wares for daily use (e.g. bowls, cups,
jars, basins, jugs) might be composed of: o-10% in the texture fraction, 5-30% in the filler
fraction, and 70-90% in the plastic fraction. It is important to remember that many natural
clay deposits contain a sand fraction (o.o6-2 mm) between 10-15 weight % and a signifi-
cant part of the fine fraction (up to 85-90 weight%) is composed of coarse silt grains (o.o2-
o.o6 mm), which act as part of the filler fraction. The relative amount of clay-sized particles
(< 0.002 mm) is variable in natural clay deposits, ranging between 35-60 weight%.
As a result of their clay minerals content, ceramic raw materials possess some distinguish~
ing characteristics. For example, colloidal clay mineral particles when mixed with water
can easily slide over each other, giving rise to the so-called "plasticity" of clayey materi-
als. Plasticity, according to Grim (1953), can be defined as the property of moistened fine-
grained earths to be deformed under the application of pressure, with the deformed shape
being retained when the deforming pressure is removed. Plasticity is acknowledged to be
largely dependent upon water content, grain-size distribution, and the relative abundance of
swelling-type clay minerals in the material.
Estimation of the plasticity of a ceramic raw material can be determined by means of the
empirical measurement of the ':Atterberg limits;' according to the standard normative CEN
ISO/TS 17892-12:2004, using a "Casagrande apparatus:' Atterberg limits, that is to say the
plastic limit (Wp) and the liquid limit (Wl), define the increasing water content boundar-
ies between non-plastic, plastic, and viscous fluid states. The plasticity index (Ip = Wl-Wp)
defines the complete range of water content in which the clay material can be worked in the
plastic state. The Atterberg limits of a clay material therefore represent its water content at
critical stages of fine-grained sediment behavior and as such are mainly used in geotechni-
cal engineering to provide empirical information regarding the reaction of soils to water.
However, they have also been applied in the characterization of raw materials used in ceramic
production, in order to evaluate material workability when plastic (Marsigli and Dendi, 1997).
Slightly to moderately plastic days exhibit values of the plasticity index (Ip) lower than 18%,
while highly plastic clays are characterized by a plasticity index generally greater than 22%.

ExPERIMENTAL TES1'ING: WHY AND How

The compositional and textural characterization of clay raw materials has been increasingly
recognized as a successful approach for identifying centers of ceramic production when car-
ried out in parallel with the study of ceramic artifacts from the archaeological excavation
of a site or sites in a particular region. Nevertheless, fundamental questions generally arise
concerning the interrelation between raw materials composition and their selection crite'ria,
 CERAMIC RAW MATERIALS 99
----------
which may depend both on natural diversity and/or accessibility (vicinity to the production
site) of available raw materials. At the same time, it is well known that there are inherent
limitations in the raw materials themselves, related to their mineralogical and technologi-
cal properties (e.g. grain size distribution, plasticity, linear shrinkage after drying and fir-
ing), which also affect their suitability for ceramic manufacture. Therefore, a compositional
comparison between potential ceramic raw materials and the ceramic artifacts themselves
should always be undertaken with an appropriate level of care.
A detailed study of textural, compositional, and technological properties of local clay
deposits, which were potentially employed as raw materials for ceramic production in antiq-
uity, can be illuminating for archaeological!archaeometric case studies interested in under-
standing regional ceramic production and circulation. The outcomes of such a study include,
but are not limited to: (I) construction of a database oflocal ceramic raw materials, highlight-
ing the important technological aspects of each deposit relevant for ceramic manufacture
and differentiated in terms of typological classes (forms), end use, and chronological con-
texts; (2) identification of pertinent markers for distinguishing local ceramic products from
imports, by means of cross-correlation of compositional and textural data; (3) determination
of regional production centers based on a comparison with local raw clays; and (4) construe~
tion of a prototype model of Territory Information System (TIS), which is considered to be
a critical instrument for categorizing the so-called ceramic "reference groups" within the
most important archaeological contexts in the studied area. Analysis of raw clays and clayey
materials in order to evaluate their suitability for ceramic production will commonly include
granulometric analysis, chemical analysis such as X-ray fluorescence spectrometry (XRF),
inductively coupled plasma-optical emission spectrometry (ICP-OES), inductively coupled
plasma-mass spectrometry (ICP-MS), instrumental neutron activation analysis (INAA),
mineralogical analysis, X-ray diffraction (XRD), petrography/petrographic microscopy, and
empirical tests for determining key properties, such as plasticity.
Investigating random variation of compositional and textural properties of natural clays
facilitates the constitutive modeling of the behavior of ceramic raw materials. Clay minerals
characterization (type and quantity) and measurement of grain-size distribution will allow
a comparative evaluation of the features influencing performance and failure of a ceramic
raw material. After separation of the sediment fraction smaller than o.oo2 mm, the semi-
quantitative composition of the clay minerals may be obtained by XRD analyses of the mate-
rial. Moreover, experimental firings performed on test-pieces (clay briquettes) at various
final temperatures may be carried out. Briquettes can be manufactured specifically starting
from the collected clays (adding an appropriate amount of water until obtaining a workable
paste at the plastic state) with the help of a wooden mold. These empirical experiments allow
the researcher to simulate the ceramic end-products obtainable from a given raw material
both in its natural state and according to various paste preparation protocols involving arti-
ficial mixing and tempering of raw materials. Linear shrinkage and color changes after fir-
ing of different raw clays can be directly measured and comparatively evaluated (Plate 1).
Experimental test-pieces fired at higher temperature might also be used for obtaining "thin
sections" for the petrographic study under the polarizing microscope. The "microscopic
fabrics" of the raw clays (hypothetical ceramic raw material), fired at their natural state or
after mixing and/or tempering experiments, could be profitably compared to the analogous
results showed by the archaeological ceramic artifacts in order to individuate the clay source
and appreciate any possible "receipt" modification attributable to specific end-use require-
ments or diachronic technological evolution.
100 GIUSEPPE MONTANA

REFERENCES

CEN ISO/TS 17892-12:2004. Geotechnical Investigation and Testing-Laboratory Testing of

Soil-Part 12: Determination of Atterberg Limits.
Clarke, F. W (1924). "The Data of GeochemistrY:' US Geological Survey Bulletin 770
(Washington): 785.
Cultrone, G., Rodriguez-Navarro, C., Sebastian, E., Cazalla, 0., and De La Torre, M. ). (2001).
"Carbonate and Silicate Phase Reactions during Ceramic Firing:' European Journal of
Mineralogy 13(3): 621-634.
De Bonis, A., Grifa, C., Cultrone, G., De Vita, P., Langella, A., and Morra, V (2013). "Raw
Materials for Archaeological Pottery from the Campania Region of Italy: A Petrophysical
Characterization:' Geoarchaeology: An International Journal28: 478-503.
Gliozzo, E., Fortina, C., Memmi Turbanti, 1., Turchiano, M., and Volpe, G. (zoos) "Cooking
and Painted Ware from San Giusto (Lucera, Foggia): The Production Cycle, from the Supply
of Raw Materials to the Commercialization of ProductS:' Archaeometry 47(1): 13-29.
Gliozzo, E., Vivacqua, P., and Memmi Turbanti, I. (2oo8). "Integrating Archaeology,
Archaeometry and Geology: Local Production Technology and Imports at Paola" (Cosenza,
Southern Italy). Journal ofArchaeological Science 35:1074-1089.
Grifa, C., Cultrone, G., Langella, A., Marcurio, M., De Bonis, A., Sebastian, E., Morra, V (2009).
"Ceramic Replicas ofArchaeological Artefacts in Benevento Area (Italy): Petrophysical Changes
Induced by Different Proportions of Clays and Temper:' Applied Clay Science 46: 231-240.
Grim, R. E. (1953). Clay Mineralogy (New York: McGraw-Hill Book Co).
Hein A., Day P.M., Cau Ontiveros, M.A., and Kilikoglou, V. (2004a). "Red Clays from Central
and Eastern Crete: Geochemical and Mineralogical Properties in View of Provenance
Studies on Ancient Ceramics." Applied Clay Science 24: 245-255.
Hein, A., Day, P.M., Quinn P. S., and Kilikoglou, V. (2004b). "The Geochemical Diversity of
Neogene Clay Deposits in Crete and Its Implications for Provenance Studies of Minoan
Pottery:' Archaeometry 46(3): 357-384.
Marsigli, M. and Dondi, M. (1997). "Plasticita delle argille italiane per laterizi e previsione del
loro comportamento in foggiatura." L'industria dei laterizi, Gruppo editoriale Faenza Editrice
(Faenza, Italy) 46:214-222.
Montana, G. (zow). La prima serie di analisi mineralogiche sulle anfore di Ischia. In: Olcese, G.,
Le Anfore greco italiche di Ischia: archeologia ed archeometria (Roma, Edizioni Quasar),
199-202.
Montana, G. (ed) (2011). Le ''argille ceramiche" della Sicilia occidentale e centrale. (Enna: Ilion
Books).
Montana, G., Cau Ontiveros, M.A., Polito A. M., and Azzaro, E. (2011). "Characterisation of
Clayey Raw Materials for Ceramic Manufacture in Ancient Sicily:' Applied Clay Science
53(3): 476-488.
Shepard, A. 0. (1956). Ceramics for the Archaeologist (Washington, D.C.: Carnegie InstitLition
ofWashington).
Tite, M.S. (2oo8). «Ceramic Production, Provenance and Use-a Review:' Archaeometryso: 216-231.
Tite, M.S. and Maniatis, Y. (1975). "Scanning Electron Microscopy of Fired Calcareous Clays:'
Transactions and Journal of the British Ceramic Society 74: 19-22.
Van Olphen, H. (1963). An Introduction to Clay Colloidal Chemistry (New York: Wiley).
Worral, W. E. (1982). Ceramic Raw Materials. The Institute of Ceramics Series (Oxford:
Pergamon Press).
F

CHAPTER 8

CERAMIC MANUFACTURE
The chaine opera to ire Approach

VALENTINE ROUX

INTRODUCTION

THE term chaine operatoire was coined almost fifty years ago by Leroi~Gourhan while seek-
ing to characterize techniques: "Techniques are at the same time gestures and tools, orga-
nized in sequence by a true syntax which gives the operational series both their stability and
their flexibility" (Leroi-Gourhan, 1964: 164). Rooted in French cultural ethnography which
promoted the cultural dimension of material culture (Mauss, 1947; Magel, 1953; Haudricourt,
1987), the study of technical facts according to this concept gave birth to numerous studies
in the domain of the anthropology of techniques under the leadership ofR. Creswell, whose
team was gathered around the journal Techniques & Culture. The definition of the chaine
operatoire used to be largely debated by both anthropologists and prehistorians (Karlin et al.,
1986; Balfet, 1991). Nowadays, depending on authors, it describes the whole manufacturing
process-defined as a series of operations that transform raw material into finished product,
either consumption object or tool (Creswell, 1976: 13)-or part of the manufacturing pro-
cess, which is then decomposed into several chaines operatoires (Lemonnier, 1983).
In archaeology, the worldwide success of the chaine operatoire owes mainly to the
results obtained in the 198os and early 1990s by studies in the anthropology of techniques
and ethnoarchaeology (e.g. Balfet, 1981; Creswell, 1983, 1996; Arnold, 1985; Longacre, 1991;
Gallay, 1992; Gosselain, 1992; Dietler and Herbich, 1994; Lemonnier, 1992, 1993; Latour and
Lemonnier, 1994; Sigaut, 1994). Although each of these studies focused on a different culture
area, their conclusions can be distilled into a universal observation or general trend: there
is a strong correlation between technological behaviors and social groups. Individuals tend
to do as their group does, thus maintaining the diversity of cultural traits within their social
group and making visible their social borders. Applied to archaeological assemblages, this
correlation opened new avenues of research since it enabled researchers to view objects from
a different perspective, as part of a social and technological process and therefore as signifi-
cant of the social groups behind them.
This chapter first addresses the cogency of the social dimension of the techniques since it
represents the cornerstone of the technological approach. Description of the main features
102 VALENTlNE ROUX

of the ceramic chaines operata ires follows, completed by the procedure for highlighting diag-
nostic attributes. The methodology for classifying archaeological assemblage according to
the chaine operatoire approach is then precised. We conclude by mentioning the different
domains of interpretation rendered possible by the analysis of ancient chaines operatoires.

THE CHAINE OPERATOIRE

AND ITS SOCIAL DIMENSION

Clarifying the link between chaines operatoires and social groups requires explaining why
it is that techniques have an identity dimension. Explanation is to be found in the learn-
ing and transmission processes studied in the fields of experimental psychology and social
anthropology. The results of these studies indicate that the mastery of technical practices
corresponds to a process of inheritance which occurs both at the individual (the learning
process) and collective (the transmission process) level according toboth "bio-behavioral"
and "anthropologicaf' rules.
At the individual level, it has been demonstrated that learning involves a tutor and a
model (Reed and Bril, 1996; Bril, 2002a, 2002b ). When the individual explores the task to be
learned, he does it through the observation of a model which corresponds to the tutor's way
of doing it. The tutor's role is to educate the learner's attention and to orient his exploratory
activities toward the model and intended outcome to be achieved. This guidance not only
facilitates the learning process, it also participates directly in the reproduction of the task.
This guidance is the key to cultural transmission. At the end of the learning process, the
learned skills are literally "embodied" (Dobres, 2000; Gosselain, 2000; Ingold, 2001): (a) the
learner has progressively acquired the perceptual-motor and cognitive skills necessary, pro-
posed and demonstrated by the tutor, for making objects, but only these skills; (b) in the
course of the apprenticeship, the learner has built up specific mental representations about
the way to make objects. As a consequence, it will be difficult for the learner to perceive and
manufacture objects in a different way than the one he/she learned, by virtue of the "bio-
behavioral rules" which require a subject to learn not by innovating but by reproducing a
model, therefore acting as true "fixing agent" of the cultural model.
At the collective level, transmission occurs within groups made up of individuals
linked by social ties. These ties determine the social perimeter into which ways of doing
are transmitted, and by the same token, the boundaries beyond which there are other net-
works with other ways of doing (e.g. Mahias, 1993; Kramer, 1997; Stark, 1998; Bowser, 2000;
Livingstone-Smith, 2000; Gosselain, 2002, 2008; Degoy, 2008). The "anthropological" rules
which determine the transmission network of skills are the same as those that maintain the
cohesion of the group and facilitate its reproduction. The nature and structure of the groups
within which a "way of doing" is transmitted are highly variable. They can correspond to
a band, a clan, a faction, a caste, a subcaste, a lineage, a professional community, an ethnic
group, an ethno-linguistic group, a population, or a gender (exclusive transmission of a
"way of doing" among women or men). In addition, the nature and structure of a group
can change over time and the social boundaries be redefined. Thus a "way of doing" can be
used at a timet by a small social group, and at a time I+I by a larger social group, the social
 CERAMIC MANUFACTURE 103

boundary delimited by the transmission network having evolved in the course of time.
Moreover, the same community can include several transmission networks depending on
the type of objects. For example, the manufacture of culinary pots may be the responsibility
of women at the household level of production, whereas storage jars may be the responsi-
bility of a few specialized men at the regional level of production. As a result, the historical
dynamics at work will vary depending on types of objects, creating phenomena of arrhyth-
mia (Perles, 2013).
But whatever the social boundaries, learning and transmission processes explain that
technical traditions overlap with them: technology is always transmitted through tutors
selected within one's social group. The immediate archaeological implications are: (a) the
chaines operatoires are inherited ways of doing, that is technical traditions transmitted
through successive generations; (b) the distribution of technical traditions indicate the
social perimeters into which they have been learned and transmitted; (c) changes within
technical traditions are the expression of culture histories and the factors affecting them
(Shennan, 2013); (d) technical traditions situated in space and time can be powerful chrono-
cultural markers, in particular when stylistic features are not significant (Roux et al., 2011;
Ard, 2013); and (e) the combined study of technical processes and objects is necessary for an
anthropological understanding of archaeological assemblages.

DESCRIBING THE CERAMIC

CHAINE OPERATOIRE

Discussion of the ceramic chaines operatoires involves two levels of description. The first
describes the main actions which organize the successive transformations of the raw mate-
rial into a finished product. They are: collecting and preparing the raw materials, fashioning,
finishing, surface treatment, decoration, and firing. The order of these actions is universal
given the properties of the material and the objective sought (making vessels). The second
level describes the chaines operatoires involved in each of these actions. It is at this level that
technological behaviors or activities are highly variable. This diversity is determined by both
cultural and functional factors.
Preparing the raw material into a ceramic paste includes: drying, pounding, sorting,
hydrating, adding temper, and wedging. Each of these behaviors is dictated by the potter's
natural and cultural environment, the inherent properties of the raw material, in terms of
its qualities for making the desired finished products, the modifications of the raw material
necessary to achieve the sought-after qualities of the finished products, and the potter's cul-
tural tradition.
The chaine opera to ire related to the fashioning stage includes a series of operations which
transform the clay paste into a hollow form and can be described in terms of technique,
methods, gestures, and tools. Some important definitions are given below.
Method: orderly set of functional operations undertaken to obtain the desired shape,
starting from the raw material. It comprises phases, stages, and operations, each of which
can be achieved through different techniques. There are three main forming phases: fash-
ioning of the body (lower part, upper part), of the orifice (neck and rim), and of the base.
104 VALENTINE ROUX

The fashioning of the body can be divided into two stages; the forming of the rough out and
of the preform.

Roughout: hollow form which does not present the final geometrical characteristics of the con-
tainer. A roughout is obtained by thinning operations.
Preform: container with its final geometrical characteristics but whose surface has not
been (or will not be) subjected to finishing techniques. A preform is obtained by shaping a
roughout.

Technique: physical modalities according to which clay is fashioned. These modalities can
be described on the basis of the following parameters:

(a) the source of energy (muscular energy vs. rotative kinetic energy);
(b) the clay mass onto which the pressures are exerted (homogeneous vs. heterogeneous);
(c) the type of force (pressurevs. percussion);
(d) the type of pressure (discontinuous vs. continuous);
(e) the degree of hygrometry of the clay paste (humid vs.leather hard vs. dry)

The two main families of fashioning techniques are distinguished by the source of energy
involved: techniques not using rotative kinetic energy (RKE) and those that do. There are
eight roughing-out techniques that do not use RKE. They are further differentiated as tech-
niques which act on assembled elements (the coiling technique by pinching, crushing, and
drawing, and the slab technique) and those that act on a clay mass (modeling by pinching
and drawing, hammering, and molding). There are seven preforming techniques which do
not use RKE. 1hey are distributed between those that act on wet clay (scraping, preform·
ing with continuous pressures, beating) and those that act on leather hard day (shaving,
"repoussage;' paddling, hammering). The roughing-out technique that uses RKE is wheel
throwing. There are four preforming techniques that rely on RKE: wheel throwing, wheel
coiling, wheel molding, and turning (shaving leather hard clay paste with RKE). In total,
there are nine roughing-out and eleven preforming techniques which describe the ceramic
fashioning process. These techniques are implemented according to methods, gestures,
and tools whose description accounts for the diversity of the fashioning chaines opera to ires
(Figure 8.1).
The fmishing techniques are achieved after the preforming stage and can act on wet
(smoothing) or leather hard clay (brushing, smoothing on leather hard clay). Surface
treatments transform the superficial state of the vessel and involve either rubbing the ves-
sel (softening, burnishing/polishing, shining), or coating it (slips, glazes, organic materi-
als, graphite, silica, carbon). 1he three types of decorative techniques are distinguished
by dimensionality: low relief or one-dimensional decoration (painting); negative relief or
recessed decor (impressed-rolled, simple, pivoting, embossed; paddled; incised-simple,
pivoting, scratching, carving; or excised-excised, pierced); and two-dimensional or high-
reliefdecors (applied elements or modeling).
Firing is the final step in the manufacturing sequence. It is a major one since it is at this
stage that the vessels are gaining their final physicochemical properties. The latter depend
not only on the clay properties, but also on the firing parameters which include temperature,
heating rate, time of exposure, and firing atmosphere. The firing techniques are distributed
 CERAMIC MANUFACTURE lOS

ROUGHING OUT
I
With~ut RKE With RKE
I
on assembled elements on a clay mass on a day mass

I
o
I
Coils
pinching
II Slabs I ( ModLng
• pinching
(I Mol~ling II Ham~ering I I Wheel Lowing I
• crushing • drawing
• drawing
l
PREFO~MING

With~ut RKE Witi RKE

1
Wet day Leather hfrd clay Wet clay Leather hard clay
I
I
Pressure
I
Percussion Press\ure Perculsion
I
Pressure
I
Pressure
~Contin~ous))
scrapmg 1
Beating !J"Repou~sage"l/1
shavmg
Paddin.g ~II Whe~l J
hammenng throwmg
I w~_eel I Wh~el ]I
co!lmg moldmg
Turning I
I I
j
FINISHING

FIGURE 8.1 Classification chart of roughing out and preforming techniques.

between two main families: those where the vessels are in contact with the fuel (open firings,
walled firings) and those where they are not (kilns).

IDENTIFYING THE CERAMIC CHAINE OPERATOIRE

The technological reading of the clay pastes implies a comparison between (a) the final
structural state of the clay material, characterized by petrofabrics, and (b) its initial struc-
tural state (the raw material), characterized by petrofacies, in order thereafter to unravel the
technical process of transformation of the raw material (pounding, hydrating, adding tem-
per, wedging, forming, firing). The interpretation of the initial structural state calls upon
general reference data of geological facies and local paleogeographic data as well as physics
of materials and experimental data in order to understand the structural transformations of
the clay paste (Raux in coiL with Courty, 2016).
The identification of the manufacturing process is a difficult exercise in the sense that each
gesture produces features which can obliterate the previous features and that surface features
are polysemic: not only the same surface features can be obtained by different techniques, but

u
 106 VALENTINE ROUX

FIGURE 8.2 Diagnostic features taken into account for reconstructing an Early Bronze Age chaine
operatoire from the site of Tell Arqa (Lebanon): (a) print on external base indicating a clay disk laid on a
basalt support;(b) concentric over-thicknesses related to a coil laid on the clay disk; (c) view of the coil
laid on the clay disk; (d) digital thinning prints at the junction base/body; (e, f) bumpy wall and fissures
indicating discontinuous pressures on assembled elements; (g) oblique fissure indicating oblique junc-
tion of coils; (h) internal wail showing that the neck was made after the body and finished with a rotary
movement; (i) external wall combed after fashioning the neck, while humid; (j) crisscross humid comb-
ing; (k) digital depressions indicating the hand support against the internal wail while combing; (1) regu-
larizing the junction bottom/body when leather hard and while the pot was drying upside down.
 CERAMIC MANUFACTURE 107

also the same technique can produce different surface features. This explains why ceramic
chafne optiratoire analysis has taken a longer time to develop than lithic technology, whereas
its basis was elaborated as soon as the 1960s (Franken, 1970, 1978; Rye and Evans, 1976; Van
der Leeuw, 1977; Rye, 1977> 1981). Since the 1990s research has been conducted, calling upon
both ethnographic and experimental data and considering both surface features and micro-
fabrics (e.g. Pierret and Moran, 1996; Livingstone-Smith eta!., 2005) (Figure 8.2). The prin-
ciple is the one of "controlled analogY:' Attributes considered to be significant indicators of
particular techniques are those whose formation has been explained and the univocal char-
acter of which has been demonstrated. For this purpose, experiments are carried out accord~
ing to a protocol where only one parameter varies at a time. It is then possible to unravel the
mechanisms explaining the fornlation of the attributes and to assess their diagnostic value.
As a general rule, given the often polysemic character of the attributes, it is important to com-
bine different scales of observation, from the naked eye down to the microscope (Roux and
Courty, 1998). It is also important to combine different analytical tools (e.g. thin-section,
X-ray analysis; Pierret eta!., 1996; Berg, zooS).

CLASSIFYING CERAMIC ASSEMBLAGES ACCORDING

TO THE CONCEPT OF THE CHAINE OPERATOIRE

Highlighting the ancient ceramic traditions constituent of archaeological assemblages

requires not only deciphering the manufacturing process involved in the making of the
ceramics, but also classifying the assemblages according to the chaine operatoire approach.
This is an original procedure implying a hierarchical classification including three successive
sortings:

(I) The first sorting is by technical groups: they are defined by the manufacturing pro-
cess as expressed by both the micro fabrics and the surface features present on the
inner and outer walls of the vessels (sherds or full vessels).
(2) ·!he second sorting is by technopetrographic groups; that is, by petrographic group
within each technical group: it is done by reference to the classification of the petro-
facies present on the site. Once the catalogue of these petrofacies is achieved, the
sherds belonging to each technical groups are examined in order to identify the class
of petrofacies they belong to and to characterize their petrofabrics in terms of tech-
nological transformation undergone by the raw material. It is at this stage that the
modalities for preparing the clay paste are studied and the ensemble of the chaine
operatoire restituted, from the collection of the raw material to the firing.
(3) The third sorting is bytechnomorphological and stylistic groups, that is by morpho-
logical and stylistic types within each technopetrographic group. It is at this stage
that the functional categories of vessels made according to each technopetrographic
group are characterized.

These successive and embedded sortings are meant to characterize the different chaines
operatoires present in the assemblage (the technopetrographic groups) and to link them to
108 VALENTINE ROUX

the intention of the potter (the finished products). Results can be visualized with the help
of technostylistic trees of a dendrogram type (Figure 8.3). They offer a synoptic view of the
different chaines operatoires present in the assemblage and the finished products they are
implemented for. They also allow us to discuss the nature of the technostylistic variability
of the assemblage, whether functional or cultural, whether simple or complex in terms of
sociological composition.
The functional variability of the chaines operatoires can be established when the function
of the vessels determines the variability of the chaines operatoires. When it does not, this is
cultural by default. As an example, when a technopetrographic group is associated with a
unique type of pot (e.g. cooking pot) and when this function explains the differences in the
chatnes opiratoires of these vessels and others in the assemblage, then we are in a situation
where the variability can be interpreted in functional terms, as opposed to variability created
by social or cultural borders.
The sociological complexity underlying the variability of an assemblage can be established
depending on its technopetrographic homogeneity or heterogeneity (Roux and Courty,

MOLDED COILED

j
Scraped
l
Smoothed Scraped Smoothed Slipped
outside outside outside outside outside

GROUP PETRO-A GROUP PETRO-B

Paddled Not paddled Burnished Not
burnished
GROUP PETRO-A !-"Gtiour-riTiio:c-!
·----~-----------·

FIGURE 8.3 Example oftechnostylistic trees. '!he tree on the left gathers molded ceramics
made up with same clay materials. The preforming techniques vary depending on function
of ceramics (functional variability). The tree on the right gathers coiled ceramics whose pre-
forming and finishing techniques co-vary with clay sources and relate to different functional
categories (functional variability). Now the molding and the coiling techniques apply to the
same functional categories, signaling therefore two technical traditions corresponding to
two sociological groups.
 CERAMIC MANUFACTURE 109

2 oo7). Homogeneous assemblages are characterized by homogeneous technopetrographic

groups with either low or high sociocultural variability. Homogeneous assemblages with a
low sociocultural variability are characterized by only one technical tradition and the use
oflocal clay sources and describe sites occupied by a homogeneous social group, which is a
single group sharing the same way of doing. At the regional scale, the juxtaposition of sim-
ple homogeneous assemblages expresses the sociological mosaic of a region. Homogeneous
assemblages with a high sociocultural variability are characterized by a few technological
traditions and the use of one or several clay sources located in the neighborhoods of the
site. They reveal sites with multiple social components whose sociological interpretation will
depend on the petrographic, quantitative, and contextual data (e.g. urban, port, colonized,
economic exploitation sites).
Heterogeneous assemblages are made up of n technological traditions characterized by
heterogeneous petrographic groups with either low or strong variability revealing a wide
variety of clay sources distributed in the region (low variability) or even beyond in the
macro-region (strong variability). Heterogeneous assemblages signal the presence of con-
sumers originating from a wide regional area. The functional interpretation of the site will
depend on petrographic, quantitative, and contextual data (consumer sites importing ves-
sels from different places, marketplaces, gathering place including aggregation, pilgrimage,
ceremonial sites, etc.).

INTERPRETING THE CHAINES OPERATOIRES

Once the functional and sociological variability of ceramic assemblages is characterized,

each chaine operatoire can be studied from a socioeconomic, historical, and evolutionary
perspective.
On the synchronic axis, issues relate to the production, distribution, and circulation of
ceramic vessels. They can be dealt with at the scale of the site, but it is at the macro-regional
scale that an overview of the spatial distribution of technical traditions will emerge, ben-
efiting indispensably from the comparative perspectives of multiple site analysis. Issues for
modalities of production are restricted to homogeneous assemblages (those occupied by
single or multiple groups of producers); issues for modalities of distribution and circula-
tion of objects apply to both homogeneous and heterogeneous ones (those occupied by con-
sumers exclusively). Distribution (direct or indirect) relates to the acquisition of the vessels
within both social and economic frameworks. Circulation relates to the movement of the
vessels in the course of their use by consumers. Modalities of distribution and circulation
can be understood using two elementary mechanisms: first, that potters have an inherited
way of doing, and manufacture vessels in response to a demand from all or part of their
social group; and secondly, that the movement of containers combined with ways of doing,
quantities, and morpho-functional types generates, at the regional scale, spatial distribution
specific to the cultural components in operation (Gallay, 2007). The operation of these two
mechanisms gives rise to three main zones or interaction Spheres: central, peripheral, and
remote. The first one designates both production and distribution zone of a particular ware
or class of vessel. The latter two designate regions or social spheres into which ceramics are
distributed or have circulated along with their consumers. The distinction can be made on
110 VALENTINE ROtJX

the basis of the quantities of vessels, their form or type, and the recurrence of their presence
l
I
through time. Non-recurrent anecdotal quantities of exogenous ceramic traditions and/or
technologies indicate the circulation of containers.
On the diachronic axis, the chaine operatoire approach addresses the evolution of tradi-
tions and technologies over time, and by the same token the history of the social groups,
by virtue of the transmission mechanisms that allow for an anthropological link between
vessels. Both the chaines operatoires and the finished product are considered, given that
the dynamics of historical change may affect them differently depending upon their nature
and context of production. These differential dynamics are the privileged witness of endog-
enous or exogenous evolutionary phenomena in relationship with both the producers and
consumers.
In concrete terms, the issue is first to identify patterns of cultural descent in the chaine
opiratoire in order to establish whether there is filiation between the ceramic assemblages
(Haudricourt, 1987; Creswell, 1996; Manem, 2008). When traditions are linked by inherited
technical gestures, there is historical continuity. On the other hand, when traditions are not
linked by inherited technical gestures, it indicates that social groups are not interconnected,
and therefore there is potential for the emergence/expansion of new groups and/or the dis-
appearance of previous groups (Raux, 2013).
The next issue is to approach the historical dynamics behind the emergence of new tech-
nical facts. The complexity of "innovation" leads us to believe that it is not possible to order
the different factors at work and, therefore, that the dynamic approach is probably most
appropriate (Raux, 2003). Secondly, the issue is to examine the evolutionary forces underly-
ing the historical dynamics. They are two categories of forces: those underlying the order
of development of techniques in relationship with "the technical trend" ("Ia tendance;' thus
named by Leroi-Gourhan, 1964), and those specifying the conditions for change. The former
explains the way techniques evolved, with a general trend toward lower energy expenditure
(Simondon, 1958; Leroi-Gourhan, 1964; Boeda, 2013). The latter relate to the context in which
historical scenarios occur. For example, social mutations have been shown to be determi-
nant for technological leaps; the diffusion of a technique has been shown to depend on the
sociological structure of the potters, either homogeneous or heterogeneous (Creswell, 1993,
1996; Roux, 2010, 2013). Both categories of forces represent huge areas of research within
evolutionary archaeology.

CONCLUSION

Although the chaine operatoire approach is now more than fifty years old, its operational
dimensions have not finished surprising us yet. Not only does this approach enable us to
identify ancient technical traditions and technosystems, it also enables us to follow the
history of social groups by identifying patterns of cultural descent through the transmis-
sion of technical gestures. The huge heuristic character of the chaine operatoire lies in its
inherited character, which makes it both a social and a transmissional indicator. Its episte-
mological strength is its grounding in empirical data. Its ambition joins with evolutionary
archaeology in seeking to highlight the general forces behind changes (Shennan, 2013). This
 CERAMIC MANUFACTURE 111

qualitative approach, resulting in a measure of the phenomena under study, has thus a rich
future ahead.

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Methodology and History in Anthropology (Oxford: Berghahn Books), 346-360.
Sigaut, F. (1994). "Technology:' In: Companion Encyclopedia of Anthropology. Humanity,
Culture and Social Life (London: Routledge), 420-459.
Simon don, G. (1958). Du mode d'existence des objets techniques (Paris: Aubier).
Stark, M. T. (ed) (1998). The Archaeology of Social Boundaries (Washington, D.C.: Smithsonian
Institution Press).
Vander Leeuw, S. (1977). "Towards a Study of the Economics of Pottery Making:' In: Ex Horreo
(Amsterdam: University of Amsterdam), 68-76.
 CHAPTER 9
·········································································································
THE ORGANIZATION OF
POTTERY PRODUCTION
Toward a Relational Approach

KIM DUISTERMAAT

INTRODUCTION

THE organization of ancient pottery production has been a topic of interest in ceramic
archaeology for decades, 1 because organization and production are seen as sources of infor-
mation on the economy and sociopolitical processes in society (Schortman and Urban,
2004; Costin, 2005). However, besides viewing organization as a proxy for larger-scale eco-
nomics or politics, it is equally interesting to study organization on its own merits (Kohring,
2012b). How people organize themselves in order to make pottery concerns the relations
between the people who make pottery, the relationships between potters and pottery users,
and tbe dynamics of power and authority between potters and others. How did people coop-
erate and communicate, and how did they control material, human, and spatial resources)
as well as the products? And how is the organization of pottery production related to the
organization of other activities? Archaeologists try to approach these questions by searching
for links between the material and the social aspects of pottery production. We usually try to
identify material correlates for predefined social structures, often based on ethnographical
examples. In this chapter I argue that these strategies have a tendency to limit our view on
the diversity of ancient organizational practice, because their top-down perspective restricts
the possibilities for identifying new, previously unknown ways of organizing. On the con-
trary, I advocate the development of a bottom-up, relational approach, building on several
recent developments in the study of technology and organization. Such an approach will
enable us to think outside the predefined boxes of types, modes, and parameters of produc-
tion, in order to access the large variety of ways in which people organized pottery produc-
tion in the past.
This chapter will first discuss several traditional archaeological approaches to the orga-
nization of pottery production, including ceramic ecology and typological approaches. My
main focus is on what I see as a major issue: tbese approaches struggle to bridge the ana-
lytical divide between the material remains and the social structures (organization) they are
 THE ORGANIZATION OF POTTERY PRODUCTION 115

trying to identify. I do not present a complete chronological or historical overview: many

of these approaches were developed in roughly the same period, have mutually influenced
each other, and are still influencing the work of many pottery specialists today. I will proceed
to discuss a number of approaches that focus on technology and human-thing relations,
including social constructivist approaches, behavioral archaeology, and approaches influ-
enced by actor-network theory. The latter see "the social" not as a structure or framework
that has left material traces; rather, the social is understood as an effect that comes about
through the interaction of people, artifacts, materials, and animals. These perspectives do
away with the gap between material and social. Not all of these "sociotechnical" approaches
have yet been applied to the study of pottery production organization, but they jointly
provide important tools and principles for future work. In the section entitled "Towards a
Relational View of the Organization of Pottery Production'', I present some preliminary sug-
gestions for a relational approach, using an archaeological case study as an illustration.

CERAMIC EcoLOGY

Which variables, which people, things, materials, circumstances, institutions, and events,
influence how pottery was produced in a specific case? At least since the work of Frederick
Matson (1965) it has been clear that ceramic production should not be studied in isolation.
Production is too strongly interlinked with consumption, distribution, and other processes
in society to do so. We should study the organization of production as part of a larger whole,
including the artisans and their social identities and roles, their technologies and the means
of production, the objects themselves and their functions and meanings, the mechanisms
for distribution, and the consumers (Costin, 2005: 1038-1039). That all these components
together influence, and are influenced by, production has been central to pottery studies for
a long time, especially since the articulation and spread of ceramic ecology, later combined
with general systems theory (a historical review can be found in Kolb, 1989; see also Matson,
1965; Rice, 1984, 1987, 1996: 184-185; Van der Leeuw and Pritchard, 1984; Arnold, 1985; Pool,
1992; Pool and Bey, 2007: 17-20 ), and the "Leiden School" approach to pottery study (Loney,
2000; Van As, 2004). "Holistic ceramic ecology" presented a model in which the "pottery
production system" is influenced by the physical, biological, human, and cultural environ-
ment, and by the economic, social, religious, and psychological subsystems (Kolb, 1989 ). The
ceramic ecological approach explicitly aimed to focus on the relations between all "subsys-
tems" and their constituent parts in the model. The aim to understand the relations between
the environment, materials, social and economic factors, and the production and use of pot~
tery, resulted in a boost in archaeometric, ceramic ethnoarchaeological, and experimental
research. The approach encouraged archaeologists to work together with other disciplines,
and to look at the total picture rather than one aspect of production only. This approach has
in many different ways shaped archaeological ceramic research, and is still very much a vis-
ible influence in recent work (Pool and Bey, 2007: 19).
Critics have accused the model of"techno-environmental determinism'' and of not focus-
ing enough on understanding the exact nature of the relationships between the variables
(Gosselain, 1998; )ones, 2004; Pool and Bey, 2007: 18; Arnold, 2oo8). The model groups
social, economic, religious, and environmental factors in just as many subsystems, and
116 KIM DUISTERMAAT

keeps them apart from each other and from the pottery production subsystem. Although it
acknowledges links between each of them, they are kept as separate analytical entities, form-
ing a "frame" or "context'' for pottery production. This creates an inferential gap between
the data on the pottery and its manufacture, and the social, economic, or religious "frame"
in which these data are supposedly set. We have to manage a jump from one system to the
other, from the pots at hand to the "larger" context, but it is not clear how to do so. Moreover,
in the ceramic ecological approach, materials, objects, and humans have rather passive roles
to play. Human behavior is seen as an "adaptation" to the environmental, cultural, social, or
economic context. Material properties and principles are often seen as main drivers behind
technical choices, leaving "the sociar' in the background.

TYPOLOGICAL APPROACHES

Between the 1970s and the 1990s, many archaeologists used modes or types of production
organization to describe and classify the organization of craft production. Viewing organiza-
tion as part of the socioeconomic context or of political economy, they explicitly aimed to
focus on the social, economic, and political factors relevant to production. In pottery stud~
ies, the most often-used typologies include those of David Peacock (1982), Elizabeth Brumfiel
and Timothy Earle (1987), and Sander Vander Leeuw (1977). Over the past two decades, cri-
tique on typological approaches has been fterce (e.g. Costin, 1991, 2004, 2005, 2007; Pool,
1992; Mills and Crown, 1995; Feinman, 1999; Clark, 2007a; Neupert, 2007; Pool and Bey, 2007;
Shimada and Wagner, 2007; Arnold, 2012). A production type is a label that obscures the
complex, continuously moving, multifaceted, and multilayered reality behind it. Types are
limiting and prescriptive rather than helping us to understand. Many scholars of craft pro-
duction have now abandoned their use; however, some current archaeological studies of pot-
tery production still rely heavily on these classifications. Perhaps this is because of a tendency
to search for simple ways to approach the enormous complexity of pottery production (Rice,
1996: 191; see also Costin, 1991, for a claim that identifying production organization is rela-
tively easy). Unfortunately, the typological approach is still advocated in introductory texts
(Tite, 2oo8; Orton and Hughes, 2013) and even in work that otherwise seems to have moved
away from traditional typological thinking (e.g. Vander Leeuw, 2008: table 12.2).
As in the ceramic ecology approach, a fundamental problem of the typological approach
is that production types are based on supposedly universal links between variables. 1bese
models assume agreement between a limited number of organizational variables, such as
output, intensity of production, economic dependence on the craft, density of production
debris, spatial extent of the distribution of the products, and the size, elaboration, and con-
text of production locations (Feinman, 1999). However, many of these links are assumed to
exist, mostly based on ethnoarchaeological case studies, but most links have not actually
been studied very well. Furthermore, the material correlates of these variables are mostly
assumed, rather than studied. Even those relations between variables and archaeological
evidence that have been studied in more detail, through ethnoarchaeology, experimental
archaeology, or archaeometry, are not universal (such as the causal links between organiza-
tional variables and "standardization"; for recent critical discussions see Berg, 2004; Gandon
et al., 2014; Hilditch, 2014; Kotsonas, 2014; Roux, 2003b). Production types based on these
 THE ORGANIZATION OF POTTERY PRODUCTION 117

links thus have limited relevance for real~life cases. However, our aim in studying pottery
production should not be to discuss the universality of the links assumed in the model, or
the validity of the types of production. Our aim should also not be to classify our case in
one or the other type. Rather, we should try to understand how-in our particular historical
case-pottery production was organized and why in that manner, which links were there,
and why.
A related problem is that these typologies also more or less explicitly assume relations
between types of production and processes on a larger scale, such as the emergence of social
complexity or state formation. Archaeologists tend to classify their case in a production type
as a stepping stone to approach larger social processes, connecting those modes of produc-
tion that are perceived to be more complex to increasing sociopolitical complexity (David
and Kramer, 2001: 304). Related to this is the obsession with the concept of "specializa-
tion" as a cause or indicator of social complexity and political power (perhaps most dearly
voiced in Rice, 1981; for more reading on the problematic concept of specialization see also
Schortman and Urban, 2004; Hruby and Flad, 2007; Menon, 2008; Day et al., 2010; Baysal,
2013). This fascination with "specialization'' is rooted in eighteenth-century political econ-
omy and nineteenth-century cultural evolutionism, and is shaped by our owrt experiences
with capitalism (Clark, 2007a; Arnold, 2008).1hese theories sketch a unilinear evolution of
human organization from egalitarian to capitalist, and frame organization in terms of costs,
economics, and efficiency. This has historically defined the ways we understand the relations
between specialization and human organization (Patterson, 2005; Kienlin, 2012), and the
ways we understand the relations between technology and society in general (Dobres and
Hoffman, 1994; Rice, 1996: 180; Arnold, 2008: 2-3; Dobres, 2010: 105). However, we should
question whether neoclassical economic theory applies to past societies, or whether these
models are limiting our views on the past (Clark, 2007a; Bay sal, 2013).
More recently, it has been suggested that increasing sociopolitical complexity can better
be characterized by a growing variety of simultaneously existing forms of production orga-
nization, not by the emergence of complex forms of organizations per se (Sinopoli, 2003: 21;
Costin, 2004). Notwithstanding this nuance, it is unclear exactly how a type of organization
such as "household production" (a label that covers a wide variety of cases and definitions),
or a parameter such as «division of labor;' connects to specific forms of sociopolitical orga-
nization; the precise links between them are not clearly defined. We should question, not
assume, the nature of relations between organizational practices, political power, and social
inequality (Schortman and Urban, 2004; Day et al., 2010 ).

Cathy Costin and Christopher Pool's Characterizational

Approaches: Typologies in Disguise
In an attempt to overcome the drawbacks of rigid and prescriptive typologies, Cathy Costin
(1991) suggested that we should describe production organization with the help of four
parameters, which are not static but can each independently vary between extremes across a
sliding scale. Originally these parameters were: context (the nature of elite control over pro-
duction), concentration (the relative geographical concentration), scale (the size and con-
stitution of production units), and intensity of production (the degree to which production
118 KIM DUISTERMAAT

is part-time or full-time). At almost the same time, Christopher Pool (1992; Pool and Bey,
2007) similarly proposed to study the "dimensions of variation" in production, consump- I
tion, and distribution. These included scale, intensity, size of production and consumption
units, segregation of activities, location of production and consumption, the variability of
products, and the range and direction of distribution. How these approaches differ is dis-
cussed in Mills and Crown (1995) and Pool and Bey (2007). Originally, Costin (1991) again
proposed a typology, channeling the almost infinite number of possible combinations of the
four parameters into eight types of production, ranging from "individual specialization'' to
"retainer workshop:' 'There were several critiques on this approach: first, many aspects of
the parameters (such as the amount of time spent on production, or the amount of income
raised by production) are difficult to operationalize in the archaeological record (Sinopoli,
2003; 17; Shimada and Wagner, zoo7; Menon, zooS; Kelly, zoo9). Second, the focus is very
much on the extremes of a parameter, but if a specific case sits somewhere in between it is
difficult to position it in the model (Kelly, zoo9). Moreover, the approach focuses mostly
on the division oflabor and sociopolitical centralization, and on artificial dichotomies such
as prestige vs. utilitarian. And it neglects issues such as the value of things, time, and skill
(Clark, zoo7a; Shimada and Wagner, 2007; Day et al., zow ).
Again, each parameter conflates several aspects that are not necessarily causally related,
thus reintroducing the problem with the assumed links between variables in the typologi-
cal approaches mentioned above. For example, in Costin's model, the parameter "context''
includes not only the relation of potters to authorities, but also makes statements on the types
of product (utilitarian or luxury), on the principles driving production (such as efficiency),
on the nature of demand, on the quality of the products, and on the access to products
(whether controlled by elites or not). In "scale;' the number of workers and the principles
of their recruitment (kin-based or not) are conflated, although they are in reality not neces-
sarily related. It is clear that in order to understand how these various aspects are related in a
specific case, we must study them separately rather than conflate them in parameters (Pool
and Bey, 2007; Arnold, 2008). In her later publications Costin (2001, 2005) seems to aban-
don the eight types, stating that her approach of parameters varying along axes "eschews
typology" (Costin, zoos). Furthermore, over the years Costin (zo01, 2005, zoo7) redefined
the four parameters that are important for understanding production organization: they are
now called the degree of elite control, the spatial organization of production units, the size
of production units, and the relative amount of part-time or full-time production (Costin,
2007; Pool and Bey, 2007; Arnold, zooS). Additional important variables are listed as well,
including the types of production loci, the social relations of production, the composition
of the work-group, specialization, and the relations between producers and consumers
(Costin, zoos).
Costin's approach had a large impact in the field of pottery studies. Among the effects were
a much more focused consideration of the various variables at play, and a clear realization
that most variables are relative rather than absolute and thus can best be studied in compari-
son to other data. Many of the parameters are still found to be useful. Nevertheless, Costin's
approach, too, is limiting our vision to the specific nature of the links between all variables
involved in the organization of pottery production in a particular case. Both typological and
characterizational approaches decide beforehand which variables are most likely to be linked
together and how, which variables are most interesting to look at, and which predefined
sociocultural forms they may represent. This is overly reductive (Olsen et al., zo12; 184).
r
THE ORGANIZATION OF POTTERY PRODUCTION 119

A Focus ON TECHNOLOGY
AND HUMAN- THING RELATIONS

The time has come to develop new strategies for studying the organization of pottery pro-
duction in archaeology, to move beyond a search for the material traces of predefined forms
of organization. Without disregarding the enormous wealth of information and useful con-
cepts resulting from the approaches discussed above, I think a relational approach can be
built from elements that are core issues in the approaches discussed below, all dealing with
the study of technology and human-thing relations. It is time to consider "organization"
as what has to be explained (the explanandum), rather than as a predefined category that
explains the patterns in our data (the explanans; Latour, 2005). We should adopt a bottom-up
approach that meticulously studies the data at hand on their own merit. Further, we should
carefully study which relations exist between our data in our specific case, without relying
from the outset on assumed, but non-universal, links. If our material conforms to such links,
fine; if it does not, even better: we will have brought out new information. Moreover, we
should take an holistic perspective and focus on the materials, spaces, the potter, the pots, the
users, and the function or use of the vessels. A future strategy should be applicable in cases
where direct evidence for production is missing, and it should be useful for all kinds of soci-
eties. I think elements from approaches such as social construction of technology (SCOT),
cultural technology, behavioral archaeology, holistic approaches, symmetrical archaeology,
and entanglement can all contribute to the development of such a strategy, even if they have
their roots in different theoretical or disciplinary backgrounds (for short introductions see
Hodder, 2012b). In this section, I briefly discuss their principles and those elements I think
are useful, before presenting a brief case study as an illustration.

The Social Construction of Technology

Social constructivist approaches were developed in sociology from the 198os onwards.
1bey reject explanations that attribute changes in technological practice only to their inter-
nal technical aspects, or to "black-box" mechanisms such as "efficiency;' "market forces;'
"adaptation:' or "progress" (Loney, 2000; Killick, 2004). For example, science, technology
and society (STS) studies or social construction oftechnology (SCOT) studies (Bijker, 2010;
Bijker et al., 2012[1987]) focus on how the choice for a particular technology is closely inter-
woven with the beliefs, social structure, and historical choices of various groups of people.
Technology is socially constructed (Bijker, 2010). In the words of Dobres and Hoffman
(1994: 247): "the relation between technology and society can be described as a 'seamless
web' [... ] that dialectically weaves together social relations, politics, economics, belief sys-
tems, ideology, artifact physics, skill, and knowledge:' One of the notions in this approach
that is useful for my purposes here is the idea of"relevant social groups" (Bijker, 2010 ). SCOT
acknowledges that an artifact, or technology, is heterogeneous: there is not one "real" artifact
but there are many forms of it. This pluriformity exists because different social groups attri-
bute different values and meanings to an artifact. In order to understand the social construc-
tion of technology, we have to identify these social groups and their view on the technology
120 KIM DUISTERM.A.AT

under study (Bijker, 2010 ), Social constructivist approaches have been criticized for privi-
leging humans over things, artifacts, and technology, and for lacking adequate understand-
ings of materials and technological processes (Killick, 2004). SCOT is rarely explicitly
quoted as a source of inspiration for pottery studies (however, see Jeffra, 2oua; Murphy and
Poblome, 2012).

Cultural Technology and chaine operatoire

A social constructivist perspective that has become widely adopted in archaeology in gen-
eral, and in archaeological pottery studies in particular, is that of technological choices or
cultural technology (Lemonnier, 1992, 1993, 2012; Pfaffenberger, 1992; Dobres and Hoffman,
1994; Dobres, 2000, 2010). This approach claims that most components of a technique-the
choice of materials, the energies transforming materials, the choice of tools, the specific ges-
tures, and the knowledge and skills involved-are determined by social factors (Lemonnier,
1992, 2012). Techniques are never only ways to make things in a utilitar~an sense; techniques
are also ways to fulfil social, political, religious, and symbolic needs (Gosselain, 2011). One
of the most important analytical tools offered by this approach is the use of the chaine opera-
loire, or operational sequence, as a methodology to study social factors in technological
choices (for a detailed discussion see Roux, 2011; Roux, Chapter 8, this volume). Another
important idea is that technological choices in one technique may be paralleled in other
techniques, together forming a technological system (Lemonnier, 1992, 2012). Pottery mak-
ing and other crafts can share pervasive beliefs and practices, gestures, technical knowledge,
or resources (such as clay or fuel). Relations between crafts may also concern the existence
of similar objects in other media (Knappett et al., 2010 ), the shared use of space, a similar
consumer group, or other crafts and activities carried out by potters during the day or year.
Ideally then, pottery should not be studied in isolation from other crafts (Sinopoli, 1998,
2003; Sillar, 2000; Sillar and Tite, 2000; Killick, 2004; Sofaer, 2006; Brysbaert, 2007; Shimada
and Wagner, 2007; Michelaki, 2008; Brysbaert and Vetters, 2010; DeMarrais, 2013; Goldstein
and Shimada, 2013).
In ceramic studies the popularity of the chaine operaloire approach has resulted in an
increased focus on topics such as the social identity of potters, communities of practice,
mobility and interaction of potters, skill, apprenticeship and learning strategies, and techno-
logical innovation and change (some recent examples are Gosselain, 1998,2000, 2011; Roux,
2003, 2011; Berg, 2007; Michelaki, 2008; Brysbaert and Vetters, 2010; )eifra, 2011a; Kohring,
2012a; Sofaer and Budden, 2012; Abell, 2014; Hilditch, 2014). These are all crucially impor-
tant topics for understanding the organization of production. However> there seems to be
less interest in studying organization. 1bis is perhaps because in practice the chaine opera~
loire approach as applied in archaeological pottery studies is mostly limited to the study of
the producers and the production stage of ceramics: the preparation of raw materials, and
the shaping, decoration, and firing stages, including the used tools, firing installations, and
spaces (Sillar, 2ooo; Skibo and Schiffer, 2008; Hodder, 2012a). However, the organization
of pottery production is influenced not only by decisions made during the production of
pots, but also by considerations related to their distribution and use. After production, pots
become tools (Braun, 1983), components of other techniques such as storage, food prepa-
ration, transport, and burial, and therefore pots become part of the technological choices
F
i

THE ORGANIZATION OF POTTERY PRODUCTION 121

of users in their activities. Since all techniques can be studied with the chaine opiratoire
approach, the method may be applied to the study of the whole life-cycle of a pot or an
assemblage, from raw material selection, production, distribution, use, breakage, repair, and
reuse, to discard, and to identify the social groups involved in these processes (Lemonnier,
1993, 2012; Naji and Douny, 2009; Knappett, 2012).

Behavioral Archaeology
One of the more vocal advocates of the need to focus on the interaction between people
and things is behavioral archaeology. Developed since the 1970s by Michael Schiffer and
colleagues, behavioral archaeology claims that it is impossible to directly observe "social
processes:' such as organization, since these are theoretical constructs. We can only study
behavior, since behavior is composed of people-object interactions which leave traces
(Schiffer et al., 2001; Schiffer, 2007, 2011; Skibo and Schiffer, 2008; LaMotta, 2012).
Behavioral approaches try to achieve a full understanding of a particular technology by
studying, in minute detail, several core aspects. Well known is the focus on cultural deposi-
tion processes and site formation processes, a topic much neglected in other approaches to
pottery production. Other core components of the approach are the behavioral chain and
the life history (of objects or of technologies; Hollenback and Schiffer, 2010 ); activities and
interactions; technical choices; and performance characteristics and compromises (Skibo
and Schiffer, 2008; Hollenback and Schiffer, 2010). Behavioral approaches promote an inte-
grated study of the complete life history of a technology or artifact, from procurement, pro-
duction, use, reuse, and repair, to discard and deposition. Each link in this behavioral chain
is an activity, an interaction between people and things. Behavioral chain analysis specifies
all components of these interactions, such as the location, frequency, other artifacts, external
influences, techno-communities, and cadena. The concept of cadena is used to indicate all
social groups interacting with the artifact during its behavioral chain.
A cadena can be homogeneous, when all members appreciate the same performance char-
acteristics of an object, or heterogeneous, including many different (and sometimes conflict-
ing) demands on performance characteristics. The cadena and all activities in a behavioral
chain provide input to the technical choices an artisan will make during production, as an
artisan weighs the effects of his choices on the various performance characteristics and
demands (Walker and Schiffer, 2oo6; Schiffer, 2007; Skibo and Schiffer, 2008). The concept
of cadena is comparable to the "relevant social groups" in the SCOT approach, but later
publications suggest that a cadena not only includes people but may also contain objects
and materials, treating people and things as socially equivalent or symmetrical (Walker
and Schiffer, 2006; Schiffer, 2007; Skibo and Schiffer, 2008; Hollenback and Schiffer, 2010; a
cadena also resembles the "entanglements" of Hodder, 2012a; see also below).
Behavioral approaches see technical choice as a (conscious or unconscious) decision
based on the (utilitarian, symbolic, ritual, etc.) use of the pot, while the technological choice
of the cultural technology approach concerns the (conscious or unconscious) adoption of a
practice based on the experiences and background of the potter (such as social identity, com-
munity of practice, and learning patterns). Technical and technological choice are thus two
complementary sides of the process of making things, which both may offer useful insights
in the organization of production. For Schiffer's views on the differences and similarities
l22 KIM DUISTERMAAT

between concepts of behavioral archaeology and cultural technology, such as behavioral

chain vs. chaine operatoire, technical choices vs. technological choices, and techno-commu-
nities vs. communities of practice, see Schiffer (zoo7) and Skibo and Schiffer (zooS).
One of behavioral archaeology's main attractions for the study of the organization of pot-
tery production is the focus on the people involved in all stages in the life of an artifact, which
all may influence production, production decisions, and social relations during production.
Behavioral archaeology moreover offers a practical methodology to study these processes. It
actively advocates an integrated use of archaeology, ethnoarchaeology, experimental archae-
ology, and archaeometry.
Behavioral approaches have been said to be overly utilitarian and functionalist
(Gosselain, 1998) or materially determinist (Hodder, 2012a: z29), emphasizing fhings over
people (Webmoor, 2007). Although in principle they claim not to favor utilitarian, material-
based, or functional perspectives over "non-utilitarian" social or ritual explanations (Skibo
and Schiffer, 2008: 25; Hollenback and Schiffer, zow: 318-319; Schiffer, 2011), in practice the
approach is often understood as such. This is not in the least owing to the insistence that we
have to identify utilitarian performance characteristics first, before thinking about possible
non-utilitarian characteristics (as advocated in Skibo and Schiffer, zooS: 26; contra Dobres,
zooo, 2010). Olsen et al. (zo1z: 186) furthermore object to the fact that behavioral archae-
ology puts the relational properties of things (performance characteristics) second to their
"intrinsic" properties. Others point out that behavioral approaches do not pay enough atten-
tion to the deep history of the involvements of people and things (Webmoor, 2007; Hodder,
2o12a), and portray artisans as "engineers'' doing tests and solving technical problems
(David and Kramer, zoo>: 141). An additional problem, in my view, is behavioral archaeol-
ogy's focus and reliance on predefined universal or nomothetic principles and assumptions
about the relations between material traces and social processes. For behavioral archaeol-
ogy they are not only the ultimate aim of our efforts but also an indispensable tool needed
to bridge the gap between the archaeological record and our interpretation of it (as, e.g., in
Schiffer eta!., zoo1; Walker and Schiffer, zoo6; Schiffer, zo11). However, these principles and
laws are obscuring our view of the actual associations between people and things (Gosselain,
1998; see also below).

Holistic Approaches to the Organization of Craft Production

An approach specifically developed to study the organization of craft production, and com-
bining methods and insights from ceramic ecology, behavioral archaeology, chaine opera-
loire, and constructivist perspectives, is the "holistic" approach developed by Izumi Shimada
(Shimada and Wagner, 2007; Shimada and Craig, 2013). This ambitious approach explicitly
looks at the whole craft production process, from raw material acquisition to product use
and recycling, including both the material-technological and the social-ideological com-
ponents of a craft production system, while trying to avoid modern preconceptions and
analytical distinctions (Shimada and Wagner, 2007). It has four major components: (1) a
regional, multi-site, and diachronic scope to clarify the environmental, historical, and social
contexts of craft production and the distribution and use of its products; (z) the study of
production sites, aimed at understanding the complete production process; (3) close inter-
disciplinary cooperation between complementary specialists; and (4) the integration of
 THE ORGANIZATION OF POTTERY PRODUCTION 123

archaeometry, experimentation, and ethnoarchaeology (Shimada and Wagner, 2007). The

focus in the holistic approach is very much on the detailed study of direct evidence for pro-
duction, although in principle this approach can be applied as well to assemblages that lack
such evidence.
Recent studies adopting an holistic approach to pottery production organization (includ-
ing study of the environment, production, production locations, distribution, function, and
use), whether or not explicitly following Shimadas framework, are Day et al. (zoo6, 2010),
Duistermaat (zooS), Gagne (2012) and Greene (2013). Such holistic studies have been suc-
cessful in bringing out the nuances and complexities of the (organizational) relations
between all actors involved in craft production. They also clearly show that the study of craft
production is far from an easy matter, and ideally involves a long-term commitment of an
interdisciplinary team.

The Ontological Turn

Understanding the relationship between the social and the material, and developing the-
ory and method to bridge the gap and understand the one by studying the other, has been
a long-standing issue in archaeology (Olsen, 2003, 2010; Hicks, 2010 ); many would per-
haps say that this is what archaeology is all about. A major transdisciplinary ontological
turn that has been taking shape since the 1980s promotes a radically different perspec-
tive: the dualism between social and material, between humans and things, is not a given,
but a construct of modernist thinking that we should let go of (Olsen, 2003; Walker and
Schiffer, 2oo6; Witmore, 2007; Hicks, 2010; Watts, 2013). This perspective is strongly influ-
enced by actor-network theory (ANT), a sociological approach originating in STS stud-
ies and developed since the 1980s (Law, 1992; Latour, zoos). In archaeology, approaches
influenced by ANT that are relevant for my argument here include symmetrical archaeol-
ogy (Shanks, 1998; Olsen, 2003, 2007, 2012, 2013; Webmoor, 2007: Olsen et al., 2012) and
entanglement (Hodder, zon, 2012a). Symmetrical concepts and ideas are also influencing
behavioral archaeology (Walker and Schiffer, zoo6; Schiffer, 2007; Skibo and Schiffer, 2008;
Hollenback and Schiffer, 2010 ).
ANT -inspired approaches share an understanding of the social not as a category separate
from the material, as a larger context or framework behind the material world. The "social"
or "society" is not something written in or embodied by things; rather, things are an insepa-
rable part of its constitution (Shanks, 1998; Olsen, 2010 ). "1be social" is an interactive effect,
emerging during the mutual interaction between humans, nature, things, animals, and so
on. People, society, technology, and material culture are continuously coproducing each
other, rather than one being embedded in the larger context or framework of the other. In
order to see the effect we call "organizing:' we have to reassemble the associations and inter~
actions between all these actants, while treating people and things symmetrically, without
any a priori ontological or analytical distinction between the two.
In this perspective there is no gap to bridge between the social and the material
(Webmoor, 2007: 572); rather, the "materials of past (and present) societies are not seen as an
epiphenomenal outcome ofhistorical and social processes [... ] but actually as constituent-
even explanatory-parts of these very processes" (Olsen, 2010). The lack of living people as
a source of information in archaeology, as opposed to ethnography, is not seen as hindering
124 KIM DUISTERMAAT

or complicating the study of "the social" through material remains: "We uphold a material-
ist outlook-you do not have to talk to people to find out how they conceive of the world,
because something of the way people operate, work, and do is wrapped up in their achieve-
ments. People are so involved with the world of material goods that we can put to one side
the old split between mind and matter, beliefs and the material world that may leave traces
for the archaeologist to work upon" (Olsen et al., 2012: 167). This is not only relevant for
archaeology: students of contemporary organizations increasingly turn to study materials
and technology, irrespective of the fact that they can directly observe and interview orga-
nizational members (Orlikowski and Scott, zooS; Orlikowski, 2010; Leonardi et al., zo1z;
Carlile et al., 2013; Humphries and Smith, 2014). In this respect, organizational research is
now starting to look at "things" using concepts and methods that have been used and devel-
oped in archaeology for decades.
Bruno Latour proposes that "reassembling the social" is best done by looking at situa-
tions of innovation, at the places where things are made (such as an artisan's workshop),
at situations of breakdown and failure, and through looking at the history of technology
(Latour, zoos). This, and the focus of ANT on technology, power, and organization, makes
this approach especially interesting for those studying the organization of pottery produc-
tion. However, there are as yet few pottery studies adopting ANT-inspired or symmetrical
approaches (examples are Watts, zooS (cited in Watts, 2013); Jervis, 2011, 2013; Stockhammer,
2012; Van Oyen, 2013).

TOWARDS A RELATIONAL VIEW OF

THE ORGANIZATION OF POTTERY PRODUCTION

The approaches mentioned in the previous paragraph relate to, and differ from, each other in
complex ways (Coupaye and Douny, 2009; Hicks, 2010; Hodder, zoua; Ingold, 2012). A dis-
cussion of their compatibility or comparability falls beyond the scope of this chapter. In this
section I propose these approaches may be combined to study pottery production organi-
zation. Examples of other strategies combining elements of these approaches are Hilditch
(zooS) and Jeffra (zona).

Tracing Entanglements
As Latour (zoos) suggested, "the social" (such as organizational practices) can be reassem-
bled by empirically following, tracing, the numerous interactions between all human and
non-human "actants:· Similar strategies are employed by symmetrical archaeology using the
term "rearticulation" (Olsen et al., 2012: 176) or entanglement (Hodder, zo12a). Interactions
between these actants lead to the formation of actor-networks (Law, 1992; Latour, zoos),
assemblages (Shanks, 199S; Alberti et al., 2013; Fowler, 2013), or entanglements (Hodder,
2012a; see Fowler, 2013, for a more elaborate discussion of the differences and similarities
between these concepts). Organization should be understood as a process, as emerging from
such entanglements. There exist no such entities as "household production" or "attached
 THE ORGANIZATION OF POTTERY PRODUCTION 125

production" which are out there and can be discovered, or which can be used to explain
archaeological data. Rather, we have to explain how organization becomes, how it is a con-
tinuously emerging effect of the entangled and enmeshed relations and interactions of het-
erogeneous actants, including people, objects, tools, materials, spaces, and forces (Law, 199z;
Hernes, zooS; jervis, zon; Humphries and Smith, zo14).
In the case of pottery production, the actants are many, and may include anorganic mate-
rials (day, water, rocks, metal), plants (as fuel, organic temper, resins, rope and textiles,
wood), people (potters, users, authorities, children, middlemen; including their skills, needs,
demands, and identities), animals (transport animals, cattle and sheep providing dung for
fuel and temper, bone tools, and hair as tools and temper), technologies (clay extraction,
paste preparation, shaping, decorating, firing, transporting, cooking, storage, distribution,
burial), architecture, places, and spaces (fields, mountains, the workshop and its location
and layout, roads, places where pots are used), concepts, interests, feelings, and opinions
(efficiency, aesthetics, magic, value, gender, norms), forces, energies, processes, and reac-
tions (gravity, pressure, speed, oxidation, weight, temperature, time, decomposition). Each
of these actants can, in their turn, be seen as entanglements, networks of relations. For exam-
ple, a "potter" is a complex meshwork of interactions and associations between a human
being, day, tools, technology, knowledge, skills, other people's opinions about "potters;' the
community, and more. Recurrent interactions between all these may lead to a stable state
that presents itself in daily life as a single entity, recognized as a "potter" (Law, 199z; Hernes,
zooS; Michelaki, zooS; Orlikowski and Scott, zooS; Budden and Sofaer, zoo9; jervis, zon;
Fowler, zo13). One of the more challenging aspects of a research project is to determine
which entanglements we decide to see-for analytical purposes-as such a black-boxed
entity, and which entanglements we aim to "untangle" by following the interactions between
all the actants involved (Latour, zoos; Hernes, zooS: 7-8). This depends on our research
questions.
Research questions should avoid a top-down approach, avoid trying to fit archaeo-
logical evidence in (and searching for evidence of) a priori existing analytical distinctions
(Shimada and Wagner, zoo7), meta-narratives, frameworks, concepts, and models, such
as "the emergence of complex societies;' "craft specialization;' or "modes of production''
(Olsen et al., 201z: 175-176, 190). This does not mean that larger-scale questions are irrel-
evant. I am also not claiming that variables that are thought to influence craft organization,
such as task divisions, specialization, or intensity of production (cf. Costin, 2005; Van der
Leeuw, zoo8: figures 1z.z-1z.8) are irrelevant. Rather, I suggest that we should not let these
constructs lead our way, determining from the start which associations are worth tracing.
I propose that it is important to question, rather than assume, the existence and specific
nature of these variables and the relations between them in each particular case, and to also
actively search for any associations that do not fit these a priori frameworks. We have to
adopt a bottom-up approach (Fahlander, z013; Mimisson and Magnusson, 2014), focusing
on practice and process, and systematically following the "networks of empirical, statisti-
cal, metaphorical, narrative, conceptual, causal and systemic association'' in our data (Olsen
et al., zo12: 176), while using our creativity and trying to think beyond our usual assump-
tions. Such a relational approach will also enable us to see how organization and complexity
is apparent on any scale, and how we can approach larger-scale issues through the detailed
study of materials on the micro-level (Day et al., zoo6; Kohring, 2on, 201zb; Mimisson and
MagnUsson, 2014).
126 K1M DUISTERMAAT

I propose four interlinked and overlapping strategies to study the organization of pottery
production (Hodder, zorza: 204-227; Humphries and Smith, 2014). First, it is important to
attend to the material properties of the actants involved in pottery production, and to what
they do: how they constrain, afford, or influence (organizational) practices. Secondly, using
the chafne ophatoire approach> we can map the sequences, activities, and entanglements of
pottery production and its organization, identifying all actants and establishing what they
do. Thirdly, the chaine operatoire approach may be used to follow the biography or life-his-
tory of our material. Last, we can trace the spatial aspects of these entanglements, including
the location of materials and production> users and use activities, and the distribution and
circulation of pottery. We can also trace the various temporal dimensions of the entangle-
ments at various timescales (Hodder, 201za). These approaches may be combined to bring
the relevant social groups or cadena into view. All strategies are interlinked) and have no
particular order or sequence (and most probably will be performed simultaneously). They
provide different lenses one can use to look at the same material, to bring different aspects
of it into focus. Together, they can be used to map entanglements and situate them in space
and time.
I will briefly describe these strategies in more detail below, each time using a Middle
Assyrian "carinated bowl" from Tell Sabi Abyad, Syria (c.1zoo BC), as an example of an actant
under study (all information is based on Duistermaat, zooS).' I chose this particular shape
because it has become almost iconic for the supposedly standardized, centralized, state-con-
trolled mass production of pottery in the Middle Assyrian period, a view which I find overly
simplifying and unhelpful for understanding Middle Assyrian craft production. Moreover,
my choice for a vessel instead of a find from the pottery workshop we also excavated at Sabi
Abyad, will hopefully show that many useful insights can be gained in the absence of direct
evidence for production. I chose to draw "tanglegrams" (Hodder, zmza) as a visual sup-
port of my point, but this actually may not be the most practical solution. Of course, trac-
ing entanglements should not be limited to one bowl, but should include the whole ceramic
assemblage (Roux, zon; Van Oyen, 2013). It should also include tools, spaces, materials,
texts, images, and any other actants involved in the organization of pottery production, as
much as are available.

First Strategy: Tracing Material Properties

A first step in tracing entanglements involves tracing materials, and studying how the physi-
cal properties of materials affect the organization of production (Jones, 2004), what these
materials do, and what happens to them during their life (Ingold, 2012). We can look at mate-
rials from at least three perspectives. The first perspective concerns the physical nature and
properties of the materials involved in the actant under study, and their interrelations or
entanglements with other materials and actants both within the object itself and outside it
(Figure 9.1). Our bowl was made of calcareous clays with vegetal inclusions. Possibly, ani-
mal dung was used as temper material. If we focus on tracing the entanglements of dung,
this opens up a range of connections to other actants and processes, such as animals, the
plants they ate, agriculture, procurement of amounts of dung, drying times and places for
dung cakes, seasonal activities, and the use of dung in other activities (e.g. as fuel, or as a
component of plaster; cf. Sillar, 2000; Goldstein and Shimada, 2013). Of course, detailed
 THE ORGANIZATION OF POTTERY PRODUCTION 127

potting
cooking smithing
hearths, kilns

seas~
fields

I \ IIdung as fuel /
building

dung in plaster - - architecture

excrements
smell
fertility

plan\ ~-~

increase workability
sheep smell decrease plasticity
reduce weight
sheep herding increase porosity
rough vessel surface

/ brackish water?
pits and bins ~-~···-··0"-Salt supply?
farming \

fields ~soils -r--'----..;~ ~

wadi ~ /calcareou\ay houses

river
dust

building
writing
not very plastic
high shrinkage
dust and dirt
risk of lime spa !ling
soil, land
fertility

FIGURE 9.1 Entanglements of the materials used to make a carinated bowl.

understandings of materials will also provide information on the spatial dimensions

of entanglements, for example when establishing the geographical source of materials.
Secondly, we can study what materials do: how they interact together and how their interac-
tion results in constraints and a:ffordances for action of other actants, affecting the material
engagement between material and potter (Malafouris, 2008), the chaine operatoire, and the
organization of work.
Materials do not have intrinsic properties that are waiting to be brought out by people;
rather, these properties and affordances are the result of the interaction between actants in
specific situations (Knappett, 2004; Hodder, 2012a; Jones and Alberti, 2013: 24) and have
functional as well as representational aspects (Gosselain, 2011). In our case of dung temper,
these interactions may result in specific technologies for mixing clay and dung, the smell of
the clay body, effects of the dung temper on increased workability of the otherwise rather
128 KIM DUISTERMAAT

short clay body, effects of vegetal inclusions on coping with shrinking problems, and the
behavior of the clay body during firing and its relation to kiln technology and firing skill. A
third perspective focuses on what happens to materials during activities after their produc-
1
tion: how they perform and affect use, but also how they change, decay, and disintegrate dur-
ing their life-history. In our case most of the dung will have burnt out during the firing stage.
However, the dung-containing fabric of the bowl will have particular qualities including
fabric porosity and vessel weight. Together with size and shape, this fabric will have effects
on, for example, tensile strength and mechanical shock resistance of the bowl, breakage pat-
terns and frequency, or the resistance to hot contents. This particular fabric will also change
during its lifetime; for example, as a result of its interaction with acid contents. Apart from
the functional consequences of material properties, these properties also constrain or afford
social practices (Jones, 2004). In our case (although this has not been studied yet), we may,
for example, wonder whether any material properties of dung, such as its smell, may relate to
cultural connotations of dung (Sillar, 2000 ): if these were negative, perhaps we can link them
to the choice of dung-free fabrics for drinking goblets, the preference of the high elite for
glass and metal drinking vessels, or the low social status of the potters and their profession.
The entanglements of the calcareous clay and other components of the fabric can be traced
in similar ways.
A second aspect of material properties is form; the specific size and shape of our ves-
sel. Again, form is a bundle of connections among processes, uses, techniques, and per-
formances (Olsen et al., 2012: 191). We are dealing with a small bowl with a flat base, a
simple rounded rim, and a flaring, lightly carinated wall. The bowl is somewhat slanted
to one side and the base is cracked. The surface is left untreated and undecorated.
Comparisons with similar bowls show that ours belongs to the middle one of three
loosely defined size groups. Form and material affect interactions between actants in
specific situations, resulting in particular constraints and affordances (Knappett, 2004;
Gosden, 2005; Hodder, 2012a). For example, our bowl affords the holding and taking out
of food, drink, and other materials, it fits in a hand, the carinalion and surface prevent
slipping and facilitate grip, it can easily tip over, it can be stacked (but the irregular slant
prevents a high stack), it is lightweight, it is not very watertight, it fits the mouth oflarge
jars as a lid, it can hold c.o.3liters, it is not particularly beautiful, and it is very recogniz-
able (and regarded as an archaeological "type-fossil" for the Middle Assyrian period).
This specific form is closely tied to the way in which it was made, and to the ways it
was expected to perform during use. It is also closely related to bowls made in the same
shape, but from bronze. Bronze bowls were expensive and rare. Still, these bowls shared
the shape of our everyday pottery bowl, which was found in huge quantities in a large
variety of contexts. This suggests that the carinated shape is not only recognizable for us
archaeologists but carried meaning for its users as well. Meaning and value may also be
accessed through its quick and rather careless shaping and finishing, and through their
relative uniformity.

Second Strategy: Tracing chaines operatoires

Using the second lens to look at our bowl, the aim is to study in detail its chaine operatoire
and forming techniques, using a variety of low-tech and high-tech methods of analysis
 THE ORGANIZATION OF POTTERY PRODUCTION 129

(e.g. Smogorzewska, 2007; Bouzakis et al., 2011; Berg, 2013), in order to trace the entangle~
ments of the production process. A close mapping of all sequences and activities related to
the making of our bowl will enable us to identify the actants related to each step ofproduction
(such as the potter, assistants, the clay and other ingredients, tools and firing installations,
and spaces). We can study how materials and their properties affect the chaine operatoire,
and what happens to them during the work Questions are provoked about the kind and
size of spaces and tools needed, and about access to materials and spaces. A thorough study
of the chaine opiratoire and traces on the vessels (such as fingerprints, mistakes and correc~
tions, or differences in skill levels) provides information on the probable number of people at
work, on task segmentation, repetition and serial work, and on the possible involvement of
children or trainees (Crown, 2007; joy, 2009; Sofaer and Budden, 2012). Moreover, through
this approach, we can come closer to gestures, kuowledge, and skills. These are important
aspects when addressing questions about the intensity of production or the output per pot-
ter, the relative skill level of the potter, or the amount of time spent on production (Roux,
2003a, 2003b; Crown, 2007). We can focus on the potter's social identity and status, and on
communities of practice. The chaine opiratoire approach also helps to assess time, including
issues such as seasonality and the involvement of people in other activities, time-flow of the
work, and the minimum amount of time needed to complete the work. This is crucial infor-
mation if we want to estimate the intensity and output of production. The chaine operata ire
opens up possibilities for comparisons with other crafts and activities using similar tech-
nologies, gestures, tools, spaces, or materials, producing similar products, or dealing with
similar user groups (Sofaer, 2006; Brysbaert and Vetters, 2010 ). Regarding our interest in the
organization of production, we may want to pay special attention to those parts of the chaine
operatoire that involve communication between people involved in production, and com-
munication and cooperation with other human actors (such as neighbors, users, suppliers
of materials, or authorities). We should also consider how techniques, tools, infrastructure,
and spaces afford organizational practices.
Figure 9.2 presents a basic chaine operatoire for our carinated bowl. In order to keep the
image readable, I have listed the various materials, places, and activities that are part of the
entanglement in separate boxes rather than in a tanglegram. Also, in order to focus on orga-
nizational practices, I have marked those steps that are likely to have involved task divisions
or the help of assistants, as well as those steps that likely involved communication and coop-
eration with people outside the workshop (see also Sofaer and Budden, 2012). It appears that
our bowl was made by a skilled potter and at least one assistant, who were able to throw ves-
sels from the cone using the rather short local clay, and fire them with modest firing losses.
Communication and cooperation with others was mostly needed for the acquisition of raw
materials and tools, and perhaps for kiln building. Despite skill levels, or perhaps we should
say enabled by them, our potter was focusing on output and speed, and less on quality and
aesthetics. Among the interesting and unexpected entanglements of our bowl in produc-
tion are the frequent links to scribes. In one phase of the site, the pottery production takes
place in the courtyard of a scribe's house (identified by texts found there). Furthermore,
cuneiform writing and seal impressions occur sporadically on our type of bowls, and unfired
waste fragments from pottery production are found in recurrent association with unfired
cuneiform tablets and clay sealing fragments. These entanglements show that the coopera-
tion and social relations between potters and scribes may have gone beyond the sharing of
raw materials.
130 KIM DUISTERMAAT

MATERIALS
day (clay digging )QO (fetching water )0 ( collecting sheep drug ~
water
dung
digging tools ( crushing ) ( crushing )
baskets
water skins or jars ( take out large particles
grinding tools
stick to stir liquid clay I mixing day, water and dung
lubricant
potter's wheel SPACES _l days- weeks
stik to spain the whet! field ( restg)
bowl of water river
thread sheep pen
kiln ( kneadir.g store unused clay) hours
mixing pit or place

shapin~to cone~
fuel
kneading place
gypsum
bitumen place to put ready cones Q(
basalt wheel emplacement
thread drying space/shade 0( put cone on the wheel)
reeds firing location
wind direction storage space
wood workshop ( spin the wheel )
sunshime
rainfall
house I miniutes
temprature scribe's house ( throw a bowl from the cone --
seasons aboandoned space/IUim '~
It:(
ACTIVITIES farming grinding
( use thread to cut )
'•
'K
potting
assisting
bnsketmaking
grinding tool making
cooking
( plate bowl aside ---- J '"
kiln building writing
sheep herding s~al us~ 0( move bowl to dring split~

I d.,,
0 I ( collect{make bricks
I
r*J recycle damaged bowls
0)( coll~ct da0
(prepare plaster build kiln mov~ bowl to kiln )
0 ll fetch water )-=1"
Q( collect fuel
~ "'''' ""'') hours

0( move bowl to storage 0

FIGURE 9.2 Chaine operatoire for a Middle Assyrian carinated bowl with a flat base. Gray
circles indicate likely situations where communication with "outsiders" is necessary. Open
circles indicate likely moments of task division and the presence of assistants.

Third Strategy: Tracing Biographies

The "biography" approach has enjoyed some popularity in the past decades (Hicks, 2010).
Some studies focus on the meaning or significance of objects to people (as in Kopytoff, 1986;
Gosden and Marshall, 1999), some on the technical and functional changes of objects dur-
ing their use-life (as in behavioral chain analysis, see above; see also Pefia, 2007). Others call
for more attention to the literary techniques of biography writing (Burstrom, 2014), discuss
the long-term life-history or evolution of a particular technology (Roux, 2010, 2013; Laneri,
2011), or investigate the extension of an object's life-history into the present (Shanks, 1998;
Holtorf, 2002).
I do not intend to sketch a linear or chronological life-course for our bowl, starting
with production, through use, maintenance, and reuse, and ending with discard. Of
course, all these stages in the "life" of our bowl are important to consider, but the sequen-
tial aspect (was it first used during meals, and later as a lid, or the other way around?) is
M$A

THE ORGANIZATION OF POTTERY PRODUCTION 131

often hard to reconstruct. My focus is mostly on the relations between objects and people
during the post-production part of the bowl's life-cycle: these relations determine the
use, value, and meaning of our vessels and directly influence production (Clark, 2007a).
We will follow the bowl as it gathers entanglements of heterogeneous actors (Shanks,
1998). 1be purpose is to consider "the range of interactions between people and objects
and [to explore] how multiple forms of agency emerge through them" (Jervis, 2013: 219).
Recurrent associations with other pottery vessels, with other objects and materials, with
places, and with people create durability in the social assemblages in which our bowl
was a participant (Jervis, 2011, 2013; Zedei\o, 2013). Therefore, I will adopt a "relational"
perspective and attempt to map the heterogeneous events and actions that our bowl
(and similar bowls) was participating in (Joy, 2009), in order to understand the vari-
ety of activities and actants. These different activities, interactions, and resulting social
assemblages (or cadenas) may have affected the organization of pottery production in
different ways (Walker and Schiffer, 2006). The mapping ofinteractions is based on traces
of use and repair and residues of contents (Skibo, 2013), specific find contexts, and the
appearance of this particular shape in other materials, contemporary images, and texts.
The same approach should, of course, also be applied to any available direct evidence for
production, including spaces (e.g. Papadopoulos and Sakellarakis, 2013, using computer
simulation to study the affordances of a room identified as a pottery workshop), architec-
tural features, and tools (studying tool manufacture, acquisition, and style, e.g. Gosselain,
2010; Ramon and Bell, 2013), use-wear on potter's tools (e.g. Torchy and Gassin, 2010;
Van Gijn and Lammers-Keijsers, 2010), and tool provenance (e.g. Murphy and Poblome,
2012; Fiaccavento, 2013: 85). It is crucial to link these studies to the chaine operatoire stud-
ies of the pottery assemblage.
The resulting tanglegram (Hodder, 2012a) in Figure 9-3 presents several instances of our
bowl's "cumulative" biography. Our bowl has now become a tool in other technologies, such
as cooking, food preparation, storage, and burial. The entanglements of each of these tech-
nologies can be traced again by using the chaine operatoire approach, following the courses
of action resulting from these associations (Sillar, 2000; Jervis, 2013); Figure 9-3 shows
only the very start of such entanglements (cf. also figure 3-5 in Hodder, 2012a). As Figure
9-3 shows, our bowl was a multipurpose bowl mainly used for the presentation and con-
sumption of food and drink. As such, the bowl played a role in re-enacting and maintaining
social relations, traditions, and feelings of "home;' through specific ways of sharing meals.
Perhaps these ways were similar to the modern Middle Eastern "mezzeh;' where multiple
small bowls containing different kinds of food are placed in the middle of a group of people,
rather than each person having their individual plate. The connections with "brewing" raise
questions about connections between potting and brewing, especially in the light of a con-
temporary text from the site suggesting that the brewer was on occasion in a position to
order the potter to produce vessels (Wiggermann, 2008). Perhaps this lead can be followed
further by attempting a better identification of the vegetal fibers in the pottery fabric. Did the
potters indeed use animal dung as temper, or did they use the waste of the brewing process,
so that the brewer was not only a user but also a supplier to the potter? Our bowl had addi-
tional roles in craft production, storage, and ritual activities such as burial. Comparisons of
this tanglegram with that of other types of small bowls reveals that other small bowls were
never used in burials, nor as lamps or jar lids, although they do afford such uses. This, com-
bined with the rather rare occurrence of maintenance and repair of carinated bowls, raises
132 KIM DUISTERMAAT

cooking
/ \ everybody
kitchen / "'

ft ~ ~ites
storage vessels, sac:souse

I I
/als vybanquets

0 0 ..
baskets, etc short-term dry storage food serving/ )

open v~socoop
. , dnnkmg /
bronze drinking bowls
b .
strame~ O ~ beer - - rewmg

/""'" gypsum -
processmg 0 ...._
water
potting
~men ::.~
~ingtool
0 jar lid
Q-
/
storage
grain
largej:S- beer
b · 1 ·f~t
0
wick
'--- 'II una 91 burial jar
oil --""'-..... 01 amp 0 ---.
darkn~~ 0 offering ~ iff' r;ual

li~ng oen;iller ogarb.ag·e· 0- te~;~:rl~

\I /o .· .. ·.
built environment
I
building

FIGURE 9·3 Entanglement of the life-history of carinated bowls, from production

until deposit in the archaeological record. The size of the circles indicates the relative
importance of this use. Gray circles indicate secondary uses after fragmentation beyond
repair.

questions about the values and meanings our bowl had for the community living at the site.
The use of specific vessels in burials and during shared meals touches on the creation of iden-
tity and community, issues that were of special importance in a settlement that was founded
by Assyrians in "hostile" territory, as part of a hegemonic strategy to incorporate the region
into the Assyrian empire. The variety of our bowl's biography also illustrates its multiplicity,
and this opens up ways to investigate the composition of the various "relevant social groups"
interacting with our bowL As these groups are directly contingent on decisions concern-
ing design and technology, they are of interest for the study of the organization of pottery
production.
dfi-

THE ORGANIZATION OF POTTERY PRODUCTION 133

Fourth Strategy: Locating Entanglements in Space and Time

Tracing the spatial dimensions of the entanglements of materials, production, and biog-
raphy will enable us to access issues of source, distribution, circulation, and deposition of
materials and objects (Hodder, 2012a; Jervis, 2013). We can look at source areas of materi-
als and tools, helping to plot the location of production regionally, and bringing people-
landscape interactions into focus (Druc, 2013; Michelaki et al., 2015). At different scales, we
can study the spatial dimensions of the chaine operatoire, the specific layout of the workshop,
and the location of production in relation to the site (Stissi, 2012). Also important is the dis-
tribution of vessels after production: were they exchanged locally or further away, through
which mechanisms, and which actants are involved? Each use also has its own spatial dimen-
sions. At our site, we were fortunate to find the production locations where our pottery was
made, including workshop areas, drying areas, and kilns. We were able to study the spatial
organization of production activities in detail, both in the workshop as well as in relation to
the rest of the site. But even if that is not the case, careful plotting of spatial dimensions may
yield interesting understandings on the movement of materials, tools, products, and people.
Again, we should study these processes through the whole life-cycle of the actants involved
in production. One example of the spatial dimensions of our bowl is its regional distribution.
Sabi Abyad was a fortified estate founded in order to incorporate the region into the Assyrian
empire, and to exploit its agricultural resources. Texts suggest that there were numerous
settlements in the close surroundings of our site, housing local non-Assyrian inhabitants
who were dependent on the Assyrian administration. However, our typical carinated bowl
was only sporadically found at such sites. This raises questions on how dependent the local
population really was, and on the apparent lack of active attempts to ''Assyrianize" the local
population by encouraging the use of''Assyrian" vessels. Moreover, if pottery was not distrib-
uted among dependents, this informs us about the relatively small size of the user group for
whom our potter produced, putting doubts on the idea that production was a full-time affair
(Duistermaat, 2015).
Locating entanglements in time can also be done on several scales (Gosden, 2005;
Hodder, 2012a). On one scale, there is "operational" time: the time and sequence that builds
up each activity that is part of making or using our pottery vessels. There is often a specific
order for doing things, and there are constraints and demands on time in each sequence.
One can think of drying time needed before firing a vessel, or of the need to finish an opera-
tion before the wheel loses momentum. Moreover, certain cooking or storage techniques
require vessels to be in use for considerable durations of time, while other uses result in
quick fragmentation. The temporal perspective also brings in concerns of seasonality, and
the simultaneous involvements in other tasks and crafts. On a second scale, we can con-
sider the life-history of artifacts. This does not only concern the various uses an artifact
had, but also the recycling, inheriting, or purposeful destruction or deposition of artifacts.
Assemblages are never homogeneous in age: some pots will be brand new, while others will
have been used and reused for decades. This is not only relevant for chronological purposes,
but also directly impinges on production organization, affecting aspects such as replacement
needs and rates, and output volumes. On a third scale, we can look at the historical develop-
ments and changes of techniques and organization. The very important and currently much
studied concept of innovation and technological change is crucial in this respect. Historical
134 KIM DUISTERMAAT

patterns-in the form of knowledge and experience-may constrain the adoption of new
practices. For example, the use of a certain technique or production organization can com~
plicate the adoption of a new one (Arnold et al., 2007; Vander Leeuw, zoo8; )effra, zona), or
a certain layout of a building may dictate future locations of walls (Hodder, zo12a).

Analyzing Entanglements and Reassembling Organization

Despite the hard work of tracing the innumerable entanglements of all possible actants we
have at our disposal, one could argue (as do jones and Alberti, 2013: 27) that this does not
immediately bring forth an understanding of organizational practice. Nevertheless, in the
process of doing so, we have gained an amazingly detailed understanding of our pottery, its
production, and related materials and people. In itself, this is already much more than we
ever could have learned from classifying our case based on a limited number of predefined
criteria, as in typological approaches.
We have now identified the relevant actants (including people and non-humans) and
traced their relations. But the relations between the actants should not simply be lines. It is
more productive to view these relations as actions expressed with verbs, such as "use;' "pro-
duce;' "depend on:' To understand organizational practices, we should look at what these
actants do: what are the actions they perform together and on each other, and how do they
affect organizational practices? Which actants are "mediators:' influencing and consolidat-
ing roles, relationships, communication, control mechanisms, decisions, and power, and
how do they do so (Latour, zoos: 37-42)? We should also look for patterns, recurrent actions,
and routines (Olsen et al., 2012). Partly, these questions can be tackled through archaeom-
etry or experimental archaeology.
For Latour, the clue to reassembling the social lies in the process of writing (Latour,
2005: 121-140; see also BurstrOm, 2014). He sees the writing process as crucial, because the
social will appear only through a well-written account. He defines a good account as a narra-
tive in which every participant is a mediator, is doing something. The quality of an account is
measured according to the number of actors the scholar is able to treat as mediators, without
taking the shortcuts provided by concepts such as, for example, "efficiency:·
I think it is also interesting to see if we can approach the relations between actants in a
more formal way. Any tracing of actants will quickly result in a large and varied collection of
heterogeneous connections between heterogeneous actants, which need to be analyzed for
significant relational patterns. Would it be possible to approach these entanglements with
techniques from the quickly growing field of network analysis and computer applications
in archaeology (Knappett, zon; Hodder and Mol, 2015)? Organization studies adopt such a
formal approach with the concept of"narrative network" (Pentland and Feldman, 2007) or
"action network'' (Pentland et al., 2010 ), in order to visualize and analyze these patterns and
routines to understand organizational practices. In a narrative network, each action between
actants is a "narrative fragment" (e.g. "the potter forms a vessel on the wheel"). Fragments
are linked together in coherent sequences (narratives), much like a chaine operatoire (e.g.
"potter waits for assistant to place clay on wheel-potter forms vessel on the wheel-potter
cuts vessel from wheel head and puts it aside"). A narrative is different from the perspec-
tive of each of the multiple actants (humans and non-humans alike). All narratives together,
and the links between them, form the narrative network which characterizes that particular
p l

THE ORGANIZATION OF POTTERY PRODUCTION 135

organizational routine (e.g. "throwing a vessel on the wheel"). 'The narrative network can be
visualized in a graphical image. Analysis of the network, and comparisons with networks
for similar situations elsewhere in place or time, can yield information on which actants
and actions affect organizational change the most (Pentland and Feldman, 2007; Hayes
et aL, 2011; Pentland et al., 2012). Narrative networks and organizational routines can also be
analyzed and compared through a variety of statistics for network analysis (Pentland et al.,
2010), and through agent-based simulation (Gao et al., 2014). Of course, this approach can-
not be transferred from organizational studies to archaeology as is, but I think it is worth-
while to explore the possibilities it offers for the analysis of archaeological material.
As yet, archaeological applications of computer techniques in the study of craft produc-
tion organization are rare: Brysbaert et al. (2012) discuss how process mining techniques
can be used to analyze chaines operatoires, and perhaps ontological datasets will be key in
exploiting the strength of computers to search for meaningful patterns in our entanglements
(Hong et al., 2013). An example of the application of agent-based simulation to the organiza-
tion of salt mining in Hallstatt can be found in Kowarik et al. (2012); while Rouse and Weeks
(2011) use agent-based modeling to study production specialization in Bronze Age Arabia.
This is not the place to present a full discussion of network approaches and related com-
puter techniques, nor of their compatibility with the approaches discussed in this chapter.
Useful introductions are published elsewhere: for discussions of formal network analysis in
archaeology, see Brughmans (2010, 2013, 2014), Knappett (2011, 2013), Ostborn and Gerding
(2014), Peeples and Roberts (2013); for introductions to complexity theory and modeling,
see Bentley and Maschner (2007), Kohler (2012), Kohler and Vander Leeuw (2007); for
introductions to simulation and agent-based modeling, see Barton (2014) and Lake (2013).

CoNcLusioNs

In this chapter I have discussed two major traditions in the study of pottery production orga-
nization: ceramic ecology and typological approaches. Despite their major contributions to
our understanding of pottery production, there are two important shortcomings. First of
all, there is an analytical gap between pottery production and the larger social or economic
"context:' It is often not clear how a certain type of production is linked to these larger-scale
concepts. The nature of the relations between organizational practices, power, and social
inequality should be the subject of our inquiries, not part of the typological label used as
explanation. Secondly, typologies link variables such as output, intensity, economic depen-
dence, or labor divisions, while these links should be questioned in each particular case.
These issues, as well as the more recent development of approaches focusing on technol-
ogy and people-thing relations, suggest that the time has come to develop new strategies to
study the organization of pottery production. I suggest that such strategies can be built from
elements offered by SCOT, cultural technology, behavioral archaeology, holistic approaches,
symmetrical archaeology, and entanglement perspectives. I provided brief summaries of
each of these different approaches.
An approach to the organization of pottery production should view organization as a
process, emerging from the specific interactions between peOple, materials, objects, ani-
mals, and so on. It should study organizational processes first on their own merits, rather
l36 KIM DUISTERMAAT

than as a proxy for the larger sociopolitical or economic context or complexity. We should
follow the evidence: organization should be explained from the relations emerging from
our data, not used as a label to explain our data. We should adopt an empirical, bottom-
up perspective, focusing on relations and actions. We should incorporate the multitude
of factors influencing organizational processes in an holistic perspective, and allow for
active roles of people, materials, and things in a symmetrical manner. This will result in
an acknowledgment of the unique historical quality of each case, and in an appreciation
of variation in organizational practices rather than a search for universal principles. The
approach should ideally also cover the study of relations with related crafts and containers
in other media, breaking down traditional boundaries between material categories in field
projects.
As a limited illustration of these points, I proposed to study the organization of pottery
production applying the concept of entanglement through four related strategies, focusing
on materials, chaines opiratoires, biographies, and placements in space and time. These strat-
egies can be used to trace the entanglements of all vessels, tools, materials, spaces, and so on,
relevant to the organization of pottery production, while keeping an open view on relations
that do not fit our traditional concepts. They will also yield information on the relevant social
groups or cadenas involved, and how they relate to production decisions. A careful analysis
of this multitude of relations will allow us to "reassemble" organizational practices. I used the
example of a small bowl to illustrate each strategy. The analysis of these entanglements can
take the form of carefully written narratives. I also suggested that it would be worth explor-
ing the possibilities offered by formal network analysis and computing technology. All this
will only be possible by fully integrating archaeology, experimental archaeology, and archae-
ometry, and by enlisting the expertise of different specialists, something that is increasingly
done (Pollard and Bray, zoo7). Tracing entanglements and analyzing their patterns will be a
laborious, time-consuming project, but I am positive that our analytical methods and tech-
niques are capable of making such a project both feasible and worthwhile.
A new strategy does not need to discard all previous insights, but can build on them.
Through mapping entanglements of materials, chaine operatoires, and life-histories, and by
placing them in space and time> many of the variables important for understanding organi-
zational practices (e.g. those listed by Costin, zoos) will come into view. However, by care-
fully tracing entanglements, we can approach each variable independently, without any
preconceived typologies, predefined links between variables, or a priori assumptions on
organization. Tracing entanglements is a way to systematically and consciously explore rela-
lions and associations in our data, without following only those paths prescribed by models.
This may yield new and unexpected understandings and avenues for research. The results
of such a study will not yield a cover-alllabel to characterize production organization, but
rather a detailed and animated narrative. This will not render cross-cultural comparisons
impossible, only more laborious. In any case, I think it is an illusion to think that specific
cases grouped under the typological label of, for example, "individual workshop organiza-
tion" or "attached production" have more in common or are better comparable than cases
described in detailed narratives.
In conclusion, the time is right to develop new approaches to the study of pottery pro-
duction organization. A broad variety of theoretical perspectives and practical methods
are being developed, including those that promote a radically new perspective on people,
things, technology, and their mutual relations. Analytical techniques and methods, both in
 THE ORGANIZATION OF POTTERY PRODUCTION 137

archaeometry and in computer science, have reached unprecedented levels of precision and
strength, and have opened up a wide range of possibilities for studying pottery. I am confi-
dent that these developments will contribute to exciting new approaches and discoveries in
the field of craft organization.

NoTES

r. I do not use the phrase "craft specialization" here. The use of the word "specialization''
where actually"organization'' is meant, even in basic textbooks (Orton and Hughes, 2013),
has caused a lot of confusion and discussion and should be avoided (Clark, 2007a, 2007b
vs. Costin, 2007; Hendon, 2007; Smith, 2004: 82-83). Organization and specialization are
different processes with different causes and dynamics (Neupert, 2007).
2. I used a typology based on vessel shape. However, for the approach proposed here a typol-
ogy based on forming techniques and fabric, rather than shape, would have been more
useful (Jeffra, 2onb; Roux, 2011). For more reading on categories and typologies, see
Fowler (2013), jervis (2011), Lucas (2012), Shanks (1998), Van Oyen (2013), and Zedeiio
(2013).

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 CHAPTERlO
l
PROVENANCE STUDIES
Productions and Compositional Groups

YONA WAKSMAN
IN MEMORIAM MAURICE PICON

INITIAL DEFINITIONS AND PRINCIPLES

"PROVENANCE studies" is the common expression used by archaeological scientists to des-

ignate analytical investigations, that aim at identifying the place of manufacture of archae-
ological artifacts, or the location of the raw materials sources used to manufacture them.
Such investigations are not new as, according to Harbottle (1976), they were introduced by
Fouque (1879), who studied ceramics found in Santorin petrographically in order to distin-
guish local artifacts from imports. They have been carried out by many researchers since
(e.g. Catling et aL, 1963; Shepard, 1963; Perlman and Asaro, 1969; )ones, 1986; Peacock and
Williams, 1986; Picon, 1993; Mannoni, 1994; Schneider, 2ooo; Speakman and Glascock,
2007; see also Tite, Chapter 2, this volume, for further history of research). In spite of its
widespread use and general acceptance, the term "provenance studies" may be ambiguous, if
not misleading (Hunt, 2012). Therefore, we would like to begin by defining our terminology
before addressing some of the issues related to "provenance studies:''
This chapter mainly deals with ceramics considered representative for a given produc-
tion, which is part of the output of a workshop or group of related workshops.' A produc-
tion may include different types of wares and last for variable periods of time, but it always
corresponds to similar clayey material or ceramic paste. The characteristics of the paste are
those of the final product; they integrate both those of the raw materials and their potential
changes due to processing by the potters, subsequent changes being considered indepen-
dently. A single pottery workshop may manufacture several different productions corre-
sponding, for instance, to different functional categories, such as table and cooking wares,
the latter having technical constraints requiring a more careful selection of raw materials
(Picon, 1995; Tite et aL, 2001). Conversely, it may be difficult to distinguish within an "area
of uncertainty" the output of several workshops working in the same technical tradition,
exploiting raw materials within the same geological formation presenting similar geochemi-
cal and mineralogical features, sometimes over long distances (Picon, 1993).
The place of manufacture of an artifact is defined as its origin, and the location where
it was recovered archaeologically as its provenance. Provenance studies, as defined here,
 PROVENANCE STUDIES 149
~~~~~~~-~~~-~ ~-~---~~~-

designate the procedures and reasoning that aim at attributing archaeological ceramics to
their origin, and by extension to a predefined production, based on petrographic or chemi-
cal analysis.' Provenance studies rely on the postulate that, within a given production,
ceramics share similar features that differentiate them from ceramics belonging to other
productions. Chemical and petrographic analyses of a representative sample for a produc-
tion enable us to define it analytically as a compositional group, and to separate it from
others, provided that they are not included in the same area of uncertainty. The compari-
son of the analytical features of ceramics of unknown origin with those of predefined pro-
ductions enables us to test hypotheses of attribution, and to identify origins when these
productions are localized. Localized productions stricto sensu correspond to workshops
attested archaeologically, if not by their structures (e.g. pottery kilns), at least by evidence
related to the production process, which often include reference samples of undoubted
local origin (e.g. pottery wasters). 4 Whenever such evidence is absent, field prospecting,
geological maps and reports, and textual documents concerning craftsmanship may give
indications about possible locations of the raw materials' sources. In general, provenance
studies require appropriate comparative data, usually organized in databases, in order to
test hypotheses of origin based on archaeological criteria.

IMPLEMENTATION

Contexts of Use and Related Issues

Study of a Site
The most common case is one of an archaeological site where no pottery workshops
were found, and where ceramics were initially classified according to typology and fab-
ric-' Laboratories may be requested to test this field classification by defining productions
according to analytical criteria, to determine which ceramic categories belong to the same
production, and to evaluate the choice in raw materials. Whenever appropriate compara-
tive data are available, issues concerning the local status of productions, the consumption
of imported ceramics at the site, and its location within exchange and commercial networks
can be addressed. These latter questions require reference groups stricto sensu to attribute
ceramics to their origin, and more generally comparative compositional groups to attribute
artifacts to predefined productions, and to determine whether the site is included in their
respective area of diffusion. Compatibility with a local origin or, on the other hand, imported
status might be inferred from local geological features illustrated on geological maps, espe-
cially when using petrographic analysis. However, local attribution usually requires either a
thorough field survey of the area,6 to investigate available raw materials and their specificity
(see, e.g., Gauss and Kiriatzi, zon), or evidence oflocal production, which brings us to the
next point.

Study of a Workshop
Whenever evidence of pottery production is found, the corresponding reference
group(s) may be defined, and the following issues addressed: which ceramic categories
 150 YONA WAKSMAN

and types belong to the local repertoire? to the same local production? choice of spe-
cific raw materials and reasons for this choice (technical? cultural? etc.), chronological
evolution in raw materials procurement or processing, specialization of production, and
so on. Reference groups may also enable the identification of local wares which are not
attested archaeologically (e.g. wares pre- or post-dating the available evidence of produc-
tion, see for example below, Fatimid wares in "A Case Study: The Medieval Productions of
Beirut"), provided that they correspond to similar choices in raw material procurement
and processing.
Investigations of the diffusion of pottery from a particular workshop require analysis of
sherds from consumption sites and open another area of inquiry: which part of the produc-
tion is exported? what is the area of diffusion of the workshop? is it concurrent with other
workshops manufacturing similar wares? what is its part in the market, and how does it
evolve? and so on.

Study of a Ceramic Type

Another approach in provenance studies consists in investigating a specific ceramic
type: was it manufactured in several workshops? can we distinguish the different produc-
tions? did some of the workshops dominate the market? what is their respective contribution
to the procurement of a given site? are there geographical or chronological trends? was this
type manufactured in specialized workshops, or in workshops manufacturing other types as
well? was it diffused as byproduct of another ware? and so on.
These different approaches in provenance studies are complementary but, in practice, are
rarely addressed simultaneously. Most studies correspond to, or may be broken down into,
one of these cases, which conditions the sampling strategy and the interpretation of data.

Sampling
Sampling is an important part of the process in provenance studies, and determines, to a
large extent, what may be expected from the results of analysis. The selection of samples for
analysis is closely connected to the archaeological data (context and questions, see previous
paragraph), the archaeometric data (especially availability of comparative analyses), and,
obviously, the available material.' We detail below the initial steps of sample selection lead-
ing to the analytical definition of productions; further discussion about sampling for chemi-
cal analysis is also provided.

Defining Unlocalized Production

When defining productions with unknown geographic locations, we are generally eval-
uating whether or not one or more ceramic types with similar fabric belong to a single
production. 1be samples, which may come from different sites, should be selected from
among the most common examples of the ceramic types. A frequent mistake is select-
ing atypical samples whose attribution on the basis of macroscopic criteria is difficult. In
practice, the "core" of the production has to be defined before variants and marginals can
be considered.

L
 PROVENANCE STUDIES 151

FIGURE 10.1 Local reference samples, late Byzantine workshops, Thessaloniki, Greece.
They include kiln furniture-tripod stilts, some still attached to ceramic bases (left), overfired
wasters, unfinished biscuit-fired wasters (right).

Samples should also be selected among well-documented ceramics, in terms of archaeo-

logical context, drawing, and photographs. Sherds should have enough form and decora-
tion to be representative of an identified typological category. Our ability to extrapolate the
results obtained from a batch of samples to an entire ceramic production critically depends
upon these factors.

Defining Localized Production

When analyzing ceramics from a site where evidence of pottery production is available, it is
essential to sample reference materials of undoubtedly local origin: pottery wasters rejected
at various stages of the manufacturing process, such as unfinished or overtired wares; 8 kiln
furniture made with the same material as pottery, such as saggars, tripod stilts, kiln bars
(Figure 10.1).' Evidence of production may be difficult to discern in the archaeological
record, especially in contexts that do not include structures related to pottery manufacture,
such as kilns. In these cases, it is critical to carefully check the status of potential wasters,
especially overfired sherds which may come from hearths or burned destruction layers and
not from workshops.
In order to complete the definition of a production, samples representative of the typo-
logical repertoire of finished products, whether shown by similar wasters to be local or still
152 YONA WAKSMAN
... ········-···········--················· ..

awaiting confirmation of their local status, should also be selected, using the same criteria
as in the case of non-localized production. Common assumptions may sometimes be mis-
leading, as shown by the examples of sherds found in the filling of a kiln representing a later
depositional event and not corresponding to its output; and of imported ceramics present in
workshop contexts, possibly coming from nearby warehouses. Additionally, finished prod-
ucts are not always present in workshop contexts in large quantities, requiring a second step
in tbe sampling process. Pottery from consumption sites will be sampled both to study the
diffusion of the production and to complement its definition. Consumption contexts may
significantly contribute to our knowledge of its repertoire and dating, and to the building
up of its typo-chronology (see the the section "A Case Study: The Medieval Productions of
Beirut").
In instances where several productions were manufactured in the same workshop (dif-
ferent functional categories, evolution of clay procurement or processing in time, etc.), each
production has to be defined independently..It is often necessary in these cases to supple-
ment the initial sampling in order to obtain statistically significant compositional groups for
each production. '
The number of samples required to define a production may vary according to the homo-
geneity of the raw materials, the degree of standardization of its processing, the coarseness
of the fabric, and so on. An empirical rule of thumb for chemical analysis is to take a first
sample of about zo individuals and then determine if further sampling is requested. An
iterative procedure should be carried out as much as possible: initial sampling, analyses,
examination of the results, and further sampling whenever necessary. The latter may be
needed, for instance, when too many marginals were present in the initial sampling, or in
the case of heterogeneous material or poorly standardized processing, or to strengthen less
well-defined groups in case of multiple productions. Correlation between the initial crite-
ria (typology, fabric) and members of compositional groups should guide supplementary
sampling.
1be attribution of ceramics to predefined productions is less demanding in terms of num-
ber of samples, as we are comparing them to a well-defined group to which they will add (or
not), However, we usually consider a group of sherds rather than a single example, as the lat-
ter might present chance similarities or dissimilarities.

Productions and Compositional Groups

Classifications and Attributions
Depending upon the type of analysis, the initial analytical results typically consist of tables
of quantitative data (chemical analysis) or descriptions based on mostly qualitative data
(petrographic analysis).w The next steps are generally carried out in two phases: classifica-
tion and attribution. In the case of chemical analysis, the large number of variables requests
the use of multivariate statistical tools such as cluster and discriminant analysis.
In the classification phase, samples are clustered, according to analytical criteria, into
groups considered homogeneous and distinct enough to correspond to different produc-
tions. The evaluation of the latter point is part of data interpretation, an important part
of the work of archaeological scientists, as opposed to analysts. In the classification phase
are determined: how many groups are present; what are their boundaries; should marginal
 PROVENANCE STUDIES 153

samples be considered part of a group or excluded; and, mostly, are the similarities and
differences observed significant in terms of production. This interpretation is based on
a number of factors, discussed in some detail in the section "Classifying and Defining
Productions, Using Chemical Analysis", most of which cannot be taken into account by
statistical tools.
Attribution supposes that the productions to which the samples under study potentially
belong have been defmed previously using archaeometric analysis. The attribution phase
involves comparison of analytical characteristics, between samples to be attributed and pre-
defined productions. Both cluster and discriminant analysis may be used with quantitative
data, although the latter is theoretically better suited to studies in which there is a choice
among a finite number ofhypotheses.
The combination of petrographic and chemical approaches may be useful, because these
two approaches access different types of information (e.g. Day eta!. 1999; Schneider, zooo )."
Petrographic data are more closely connected to fabrics and technological features on the
one hand and to geological features on the other than chemical data. Petrographic data may
indicate potential raw materials origin even when a priori hypotheses and reference groups
are lacking. On the other hand, mineralogical associations and petrographic features may be
too common to be indicative. Chemical analyses are usually more discriminating, and gen-
erate quantitative data which are better adapted to statistical analysis.

Classifying and Defining Productions, Using Chemical Analysis

Chemical analysis is considered here as a mean to characterize ceramic productions by
determining the bulk composition of ceramic pastes. Given that ceramic pastes are com-
posite and heterogeneous by nature (see, e.g., Montana, Chapter 7, this volume), the sample
taken from a sherd for analysis, and more precisely the volume analyzed, should be large
enough to be representative of the material. In addition, because statistical analyses are
generally used to compare the chemical data from the current investigation and previous
chemical data stored in the laboratory database, it is essential that the analytical method
used provides reproducible results. Homogenized samples (analyzed as powders, pellets, or
beads) and stable experimental conditions are critical in this respect.
A production is defined chemically by the distribution of elemental concentrations in
ceramic pastes within a batch of representative samples. The assumption that distribu-
tions are normal, or log-normal, is often implicit in multivariate statistical treatments. This
assumption is not always verified, especially for small batches of samples, or for produc-
tions corresponding to ellipsoidal rather than spherical distributions (see, e.g., "A Case
Study: The Medieval Productions of Beirut")." A distribution is often summarized by its
mean value (m) and standard deviation (o), which characterizes the dispersion of values
around m. Variable dispersions may be observed within a single production, depending
on the element, the mineralogical features of the components, the geological context from
which they derive, and so on. For example, the CaO content in calcareous pastes may vary
by more than 10% in absolute weight percent; Ti concentrations above 1% Ti0 2 in kaolinite-
rich pastes may be fairly variable too; in clayey materials related to ultrabasic contexts, con-
centrations of Cr and Ni may also vary widely from sample to sample within a range of
high to very high values. For the same element, a large dispersion may be considered "nor-
mal" in one geochemical context and "abnormal" in another, in the latter case indicative for
154 YONA WAKSMAN

instance of more than one production or of a pollution. As a result, compositional groups

may be defined at different levels of aggregation within the same hierarchical clustering
analysis.
Each chemical element, or group of related elements in Mendeleiev's periodic table,
may have a different behavior and be affected differently by a variety of factors. As far as we
know, there is no general rule for these behaviors. Instead, from raw materials to statistical
treatment of the data, there are combinations of geochemical, technological, and analytical
parameters which archaeological scientists have gradually come to recognize and integrate
in their interpretative schema. Lines of interpretation include, but are not necessarily limited
to, the following (see also Maggetti, 1982):

geological features of the initial environment, whenever the latter is known, and gener-
ally speaking, the nature of the material as a geological material, which will condition
its mineralogical and geochemical features
• technological aspects: raw material processing (tempering, refining, mixing), shaping,
decoration, firing, and so on.
alterations due to the use of the object
post-depositional alterations
analytical precision and biases related to instrumental or analytical aspects
biases introduced by statistical analysis
last but not least, archaeological data.

In our opinion, the latter should be taken into account while interpreting analytical data,
which does not mean that the archaeological scientist is influenced by possible expectations
about the results.
Although a limited number of parameters may be formalized and integrated in statistical
analysis (e.g. Beier and Mommsen, 1994), a large part is left for the archaeological scien-
tists to determine connections between the patterns observed in the data and their possible
causes. In our opinion, which follows Picon's, multivariate statistics should be considered as
a guide to interpretation, and not a substitute for it. Statistical analyses are very useful for
highlighting the structure of the data and provide convenient outputs for the graphical pre-
sentation of results, but it is always necessary to come back to the initial individual chemical
compositions of the samples for interpretation.

A CASE STUDY: THE MEDIEVAL

PRODUCTIONS OF BEIRUT

Large-scale excavations were carried out in Beirut after the civil war, prior to the reconstruc-
tion of its city center. Remains of pottery workshops from the Roman and Crusader periods
were unearthed (Fran~ois et al., 2003; Reynolds et al., 2oo8-2009), providing us with the
opportunity to analytically define the corresponding productions. Research on medieval
wares, carried out at the Laboratoire de ceramologie in Lyon, 13 are summarized below as an
illustration of different aspects of provenance studies.
 PROVENANCE STUDIES 155
-----~

Beirut red-paste wares

e wasters and kiln furniture

<> ceramics from kiln contexts

···1ffi11
Beirut buff-paste wares

FIGURE 10.2 Beirut medieval wares: main compositional groups as determined by hier-
archical clustering analysis, and corresponding wares. Local productions, identified thanks
to reference samples stricto sensu (black dots), complemented with sherds coming from
pottery workshop contexts (gray dots), correspond to different compositional groups and
sub-groups. Two very different clayey materials were used: low to moderately calcareous for
red-paste cooking and table wares (part of the classification shown at the top and bottom
left), and highly calcareous for table wares of a different technical tradition (bottom right)
(after Waksman 2011).

Definition of Reference Groups

The first step in provenance studies in workshop contexts is sample selection for the defini-
tion of local reference groups. Beirut workshop contexts provided local reference samples,
chosen among pottery wasters (biscuit-fired unfinished wares, over-fired wares) and kiln
furniture (kiln bars). Additional sampling of the medieval ceramic corpus was conducted to
include representatives of most pottery types present in large quantities in these workshop
contexts. The classification according to chemical compositions of the samples distinguished
two main groups; one containing several loosely defined subgroups (Figure 10.2). Local ref-
erence samples are spread among all the different groups and subgroups, confirming the
local status of the whole sampling considered, with some noticeable exceptions such as a
Cypriotimport found in a workshop context (not included in the classification Figure 10.2).
Two very different raw materials were used by the potters. One group is composed of low
to moderately calcareous pastes, of variable chemical compositions but sharing a number
of common features, such as low alkali and fairly high to high iron and titanium contents.
In this specific case, compositions are too variable to be well represented by a single mean
and standard deviation. The classification tends to split the samples in a large number of
156 YONA WAKStViAN

subgroups, but all these subgroups follow roughly two main geochemical behaviors, indi~
cated by inter~element correlations and associated with their calcium contents (Figure 10.3,
low CaO and mid CaO groups). Mahalanobis distances, which are able to take such correla-
tions into account, may be preferred to Euclidean distances in this case. The clayey materi-
als corresponding to Beirut red-paste group (Figure 10.2) were used to manufacture glazed
cooking wares, for the less calcareous ones, and slipped and glazed table wares presenting
with various decoration techniques (plain glazed, reserved-slip, slip-painted, and sgraffito
wares). The other main chemical group corresponds to a production of buff-paste table
wares following a completely different technical tradition, which is based on the association
of highly calcareous pastes (around 30% CaO) and alkali or lead-alkali glazes (making pos-
sible the turquoise color). This technical tradition is more specifically related to the Islamic
world.
The first part of the study enabled us to constitute reference groups, and suggests that the
choice of raw materials corresponds either to technical criteria (use of low~calcareous clays
for cooking wares and of high-calcareous clays to favor bonding of the alkali and lead-alkali
glaze) or to cultural ones (symbolic value of turquoise). It also demonstrated that the tradi-
tional typological categories (plain glazed, reserved-slip, slip-painted, and sgraffito wares),
usually considered separately in archaeological publications, are in fact part of the same pro-
duction, which represents a significant change in perspective when studying commercial
fluxes.

Diffusion of Beirut Wares and Complements of Definition

Beirut red wares were already known archaeologically, and partially defined analytically,
before the Beirut workshops were unearthed (Stern and Waksman, 2003; Waksman et al.,
zoo8). In these early studies,' 4 compositional groups corresponding to the, as yet unlocated,
productions were defined using a sample from consumption contexts, and especially from
Crusader Acre. They helped approaching the diffusion of Beirut wares, widespread in the
Eastern Mediterranean and occasional in the Western Mediterranean and the Black Sea
regions. Petrographic analysis carried out by Porat identified lower Cretaceous formations,
extending through Lebanon, Israel, and jordan, as the likely source of the clayey material
used to manufacture these productions (Waksman et al., 2oo8). The discovery of the work-
shops, and subsequent inclusion of Beirut reference samples into the compositional groups
defined by the early studies, set their exact location to Beirut (Waksman, 2002).
Consumption sites also provided valuable information about the Beirut productions: pre-
cise chronological data; variability of the typological repertoire; evidence on which types
from the production were preferentially exported; quantities of Beirut wares found in
consumption contexts, and thus the relative part that Beirut played in the sites' procure-
ment; identification of other productions associated in the same trade networks; and so on.
These "complements of definition" are, for instance, well illustrated by the contribution of
Stern's studies of the pottery of Crusader Acre to our knowledge of Beirut wares (Stern and
Waksman, 2003; Stern, 2012). Stern established their typochronology during the Crusader
period, and, through quantification of pottery finds, pointed out their massive presence in
the region. Contrary to still common prejudices, cooking wares constitute the part of Beirut
productions which experienced the largest diffusion.
 PROVENANCE STUOTES 157
·~-

14

12

10

8
£
0' low CaO
S'
~
6
4> Mid CaO

4 f1 High CaO

00 20 40 60 80 100
Si0 2 (%}

20

~ 15
a.
E
~
13
~
~
E
"
2
6
5
3
1
0
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7
Mahalanobis distance

FIGURE 10.3 Beirut medieval wares: binary plot iron-silicon (top) and histogram of
Mahalanobis distances (bottom). The low-calcareous pastes show large variations in abso-
lute concentrations values, but also strong inter-elements correlations, related to a same
geochemical behavior and interpreted as a same production (top). Fatimid cooking wares
coming from terrestrial contexts (in black) may be attributed to Beirut using discriminant
analysis, as they fit the low-calcareous Beirut reference group (in gray), whereas the attribu-
tion of sample LEV548, coming from the Sen;e Limam shipwreck and altered by sea water,
requests to come back to the initial chemical data (bottom).
 1

158 YONA WAKSMAN

Attribution to Beirut of Other Types

Pottery production also existed in Beirut at periods which lack the corresponding archae-
ological evidence, such as workshops and kilns. 1be reference groups defined for the
Crusader productions may be used to identify other local products, provided that their
manufacture involved similar raw materials and processing. For example, Beirut Fatimid
wares, which just precede the Crusader ones, can be positively identified as locally man-
ufactured in Beirut by their chemical similarity with the Crusader reference groups
(Waksman, 2011). Figure 10.3 presents the histogram of Mahalanobis distances between
a sampling of Fatimid cooking wares and the Crusader low-calcareous reference group.
Cooking wares from terrestrial excavations are well integrated in the reference group on
the histogram, unlike examples of similar typology coming from the Sen;e Limam ship-
wreck (Bass and van Dorninck, 1978), one of which (LEV548) is shown in Figure 10.3. On
closer examination, the shipwreck samples can be attributed to Beirut as well, provided
that the chemical alterations associated with marine environment are taken into account
(Pradell et al., 1996; Waksman, 2011). This is an obvious example of why coming back to the
unprocessed chemical data is criticaL
The Sen;e Limam shipwreck, well dated thanks to glass stamps and coins, is an impor-
tant chronological reference point for the Fatimid period. In the present case, it helped iden-
tify the Beirut Fatimid repertoire, including a type of sgraffito ware previously attributed to
Egypt, Palestine, or North Africa (Jenkins, 1992; Mason, 2004). The results also suggested a
Levantine origin for the main cargo of the shipwreck, consisting of glass cullets.
Laboratory investigations of Beirut medieval productions provide a concrete example of
the following aspects of ceramic provenance studies:

definition oflocal productions (in this case, multiple productions) and establishment
of chemical reference groups, based on the analysis of pottery wasters and kiln fur-
niture together with finished products. It is notable that these productions could be
defined before the discovery of the workshops, which established their location, and
that petrographic analysis indicated potential areas of origin
the diffusion study contributed to the typo-chronological definition of the productions
and provided information about trade networks and fluxes
" reference groups were also used to attribute to Beirut Fatimid wares whose local status
was not attested archaeologically

CONCLUDING REMARKS

Provenance studies of ceramics may appear a well~established res·earch area. However,

instrumental developments, in portable equipment (e.g. portable X-ray fluorescence
devices), and in large research infrastructures (synchrotron), have stimulated new field
and laboratory practices. The latter may provide some interesting results (e.g. Molera et al.,
2013), but also urge us to remember fundamental constructs, such as the complex nature of
 PROVENANCE STUDIES 159

ceramic material and the range of parameters involved in the interpretation of analytical
results, sampling procedures, and archaeological issues. Engagement with the latter is fruit-
ful in provenance studies of ceramics owing to the need to build up the corpus of geochemi-
cal and petrographic data adapted to specific archaeological questions. Furthermore, unlike
other materials, we cannot only reason in terms oflocalization of raw materials. The ubiquity
of clays, their processing by potters, and the composite nature of ceramic pastes imply that
we should rather think in terms of the final output; that is, the productions, defined by both
their archaeological and archaeometric features.
The development of provenance and technological studies of ceramics has generated large
chemical and petrographic databases in different laboratories. An important issue currently
facing the discipline concerns the status of archaeometric data and good practices for its sen-
sible use, depending on the level of archaeological information recorded in archaeometry
databases. This issue involves both the safeguarding of"historical" databases and the inter-
connection of ceramics databases containing complementary information. 15 The building
up of such networks, using IT and statistical tools of complex data modeling, sharing, and
handling,' 6 may open new perspectives in the field.

NOTES

1. An extended version may be found in Waksman (2014).

2. The term "workshop" does not suppose here a specific level of organization of the produc-
tion unit (Peacock, 1982). The concept of"production;' however, implies a certain degree
of standardization in raw material selection and processing.
3. We use here "chemical" analysis in the sense of"elemental" analysis.
4· Compositional groups including reference samples become reference groups.
s. i.e. the features of the paste as observed with the naked eye, using a hand lens, or under the
binocular microscope; see, for example, Tomber and Dore (1998).
6. In most cases clay materials are expected to come from the close surroundings of a pro-
duction site (Arnold, 1985), although some rare examples of clay transport over long dis-
tances are known (Ballet and Picon, 1987).
J. In practice, it often comes as a limitation when trying to define productions using material
from a single site.
8. Overfired wasters are more likely to be chemically altered during burial (Picon, 1987), so
that other reference samples should be preferred whenever possible.
9. Fragments of kiln walls were shown to be inadequate in the cases we examined, as differ-
ent raw materials had to be selected for them.
10. Quantitative approaches to petrographic data are seldom used (Whitbread, 1991).
n. Other analytical methods, such as heavy mineral analysis and X-ray diffraction, may be
useful as welL
12. In ann-dimension hyperspace, n being the number of elements analyzed.
13. Analysis is carried out by wavelength-dispersive X-ray fluorescence. TwentyMfour ele-
ments are determined, seventeen of which, including major and minor elements (MgO,
Al 2 0y SiO:P K2 0, CaO, Ti0 2 , MnO, Fe2 0 3 ) and trace elements having various geochemi-
cal behavior (V, Cr, Ni, Zn, Rb, Sr, Zr, Ba, Ce), are used on a routine basis in clustering and
discriminant analyses. Classifications are carried out by hierarchical clustering analysis
on standardized data, using Euclidean distances and average linkage.
160 YON A WAKSMAN

14. A first report appeared in 1999: Waksman, S. Y., Segal, !., Porat, N., Stern, E. )., and
Yellin,). (1999). ''An Analytical Study of Ceramics Found in Crusader Acre: Levantine
Productions and Imports from the Byzantine World" (Jerusalem, Geological Survey of
Israel Internal Reports GSI/8/99 ).
15. See a selection of online resources in References.
16. Ongoing doctoral research is carried out on this subject by A. bztiirk at the University
of Lyon.

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della Ceramica. Problemi di Metoda, Atti 8° Simposio Internazionale della Ceramica
(Bologna: Int. Centro Ceramico ), 3-26.
Picon, M. (1995). "Grises et grises: quelques retlexions sur les ceramiques cuites en mode
B." In: Aetas das ws fornadas de Ceramica Medieval e Pas-Medieval (Porto, Maio: Camara
Municipal de Tondela), 283-292.
Pradell, T., Vendrell-Saz, M., Krumbein, W.-E., and Picon, M. (1996). "Alterations de
ceramiques en milieu marin: les amphores de repave romaine de la Madrague de Giens
(Var):' Revue d'Archeometrie 20:47-56.
Reynolds, P., Waksman, S. Y., Lemaltre, S., Curvers, H., Roumie, M., and Nsouli, B. (2008-
2009). 'An Early Imperial Roman Pottery Production Site in Beirut (BEY 015): Chemical
Analyses and a Ceramic Typology:' Berytus 51-52:71-115.
Schneider, G. (2ooo). "Chemical and Mineralogical Studies of Late Hellenistic to Byzantine
Pottery Production in the Eastern Mediterranean:' In: RCRF Acta 36 (Abingdon), 525-536.
Shepard, A. 0. (1963). Ceramics for theArchaeologist(Washington D.C.: Carnegie Institution).
Speakman, R. j. and Glascock, M.D. (eds).Archaeometry 49(2).
Stern, E. j. (2012). 'Akko I, The 1991-1998 Excavations. The Crusader-Period Pottery. 2 vols.IAA
Reports 51 (Jerusalem: Israel Antiquities Authorities).
Stern, E. j. and Waksman, S. Y. (2003). "Pottery from Recent Excavations in Crusader Acre:
Typological and Analytical Study:' In: Actes du VIle Congres International sur Ia Ceramique
Medievale en Mediterranee (Athens: Caisse des Recettes Archeologiques), 167-18o.
Tite, M. S., Kilikoglou, V., and Vekinis, G. (2001). "Review Article: Strength, Toughness and
Thermal Shock Resistance of Ancient Ceramics, and Their Influence on Technological
Choice:' Archaeometry 43(3): 301-324.
Tomber, R. and Dore, j. (1998). The National Reference Roman Fabric Reference Collection.
A Handbook (London: Museum of London Archaeological Service).
Waksman, S. Y. (2002). "Ceramiques levantines de l'epoque des Croisades: le cas des produc-
tions apate rouge des ateliers de Beyrouth:' Revue d'Archeometrie 26: 67-77.
Waksman, S. Y. (2011). "Ceramics of the 'Sen;e Limam type' and Fatimid pottery production in
Beirut:' Levant 43(2): 201-212.
Waksman, S. Y. (2014). "Etude de provenances de ceramiques:' In: Circulation des matiriaux et
des objets dans les sociitis anciennes (Paris: Archives Contemporaines), 195-215.
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Developments in Ceramic Petrology. British Museum Occasional Papers, 81 (London: British
Museum),369-391.
 CHAPTER 11

MINERALOGICAL AND
CHEMICAL ALTERATION

GERWULF SCHNEIDER

INTRODUCTION

PoTTERY is a very stable material compared to wood, metal, and glass. In consequence,
sherds of archaeological ceramics have survived for up to 10,ooo years while buried in
the ground. This, in addition to its occurrence on nearly every archaeological site, is one
of the reasons why pottery is important as a carrier of information about ancient cultures.
Many ancient cultures are even named after their typical pottery type. On the other hand,
archaeological sherds buried in the ground are part of the surrounding soil and will behave
accordingly.
The study of ancient pottery in the archaeo~ceramologicallaboratory is aimed at recon-
structing the technology used in its manufacture and determining the date and place of its
manufacture. The interpretation of analyses is based on the assumption that the potsherds
have not been altered during deposition in the ground. That this possibility exists, however,
was already mentioned by Sayre et al. (1957) when they used neutron activation analysis
(INAA) to determine the provenance of archaeological potsherds from the Mediterranean
region. The many analyses of archaeological ceramics done thereafter using NAA, optical
emission spectrometry (OES), AAS (atomic absorption spectroscopy) and WD-XRF (wave-
length dispersive X-ray fluorescence), and later also inductively coupled plasma emission
or mass spectrometry (ICP-OES and ICP-MS), yielded a large body of evidence relating to
possible post-depositional chemical and mineralogical changes in ceramic materials. Nearly
everybody working on analysis of ancient ceramics has at least once been faced with the
problem of alteration, and there are many published papers on this issue, which has also
been discussed at various archaeometric meetings. Suggestions for further reading may be
found in the articles referred to herein.
Three approaches have been used to study the possible alteration of ceramic material during
deposition in its burial environment (Schwed! et a!., 2004). The most common approach is that
of comparative studies. Products made by a single workshop within a fixed period should have
the same composition given that material changes due to technical reasons can be excluded,
"I
i'v!INERALOGICAL AND CHEMICAL ALTERATION 163

such as, for example, changing the recipe for pottery designed to serve a special purpose. The
differing chemical composition of sherds buried in different environments can, thus, be inter-
preted in terms of chemical alteration (Freeth, 1967). A special case is presented when mate-
rial from an excavated kiln can be analyzed (Buxeda i Garrig6s et al., 2001). The advantage of
this approach is that the effects of the depositional environment on many sherds of differing
ceramic quality are considered. As another approach, profile studies can be employed in order
to avoid the assumption that the examined sherds originally had the same composition. In this
approach, different layers of a large sherd cut parallel to its surface are analyzed. Because the
surface of the sherd is most vulnerable to environmental influences, it will show a different
composition to that of the sherd's core (e.g. Picon, 1976; Thierrin-Michael, 1992, Schwedt eta!.,
2004). The third approach is the experimental simulation of burial conditions to study pos-
sible changes (e.g. Segebade and Lutz, 1976, 1980; Franldin and Vitali, 1985; Bearat eta!., 1992).
However, the interpretation of the results here is limited by the question of whether short-term
experiments on a few selected samples can really be compared with the post-depositional
alteration of sherds varying in composition and ceramic quality and buried in very different
depositional environments for thousands of years. Thus, experiments can only highlight some
possible tendencies.
It is very difficult to define general rules on how post-depositional alteration can be
recognized and how severe its effects on a ceramic object can be. This is due to the large
chemical and structural variability of ceramics and of the post-depositional environ-
ments encountered in different climates (e.g. humidity, temperature, pH, and redox
conditions). Therefore, any generalization of results is limited. The original clay compo-
sition, preparation of the body, forming, and firing have a big influence on the size and
number of dosed and open pores within the ceramic body, and thus on the accessibility
for soil solutions. Non -calcareous and calcareous ceramics behave very differently. The
application of a slip or a glaze, as well as many other factors, must also be taken into
consideration. Another aspect is the part played by the degree of vitrification of the
sherd. A lot also depends on body composition and on temperature, atmosphere, and
time of firing. Furthermore, post-depositional chemical changes are very much bound
to the corrosion of glass as discussed, for example, by Freestone (2001). Products with
the same composition and made at the same pottery workshop can differ significantly
depending on frring in their resilience to weathering, because of the varying amount of
glass in the sherds.
When comparing results from different studies, another factor which must also be con-
sidered is how the samples were taken and prepared for analysis. It is common practice
to remove a surface layer before drilling, or before powdering a fragment in a mill, for
chemical analysis. In these instances, the issue of whether the post-depositional alteration
effects on the chemical data are significant or negligible depends on the thickness of the
removed surface layer. This may explain some contradictory experiences. In our labora-
tory we clean fragments before analysis by removing all surface layers of about 1 mm or
more> if possible. Maybe therefore, among our 30,ooo or so chemical analyses of archaeo~
logical ceramics by WD-XRF only a minority are seriously affected by post-depositional
alteration effects. Non -destructive chemical analysis of the surfaces or old breaks of a
sherd using a portable energy-dispersive XRF-analyzer will, however, be far more greatly
affected by such alteration.
164 GERWUI..F SCHNEIDER
-----~~----

MINERALOGICAL ALTERATION

Rehydration and Rehydroxylation

During firing, clay loses water in several stages. Below soo'C mainly physically adsorbed
water is lost (dehydration). Between about soo'C and 90o'C the clay minerals more or less
lose their structural water (dehydroxylation) forming new badly crystallized or amorphous
phases. During burial and exposure to environmental humidity these mineral and amor-
phous phases can take up water again (Grim and Bradley, 1948). This results in an expansion
and in an increase in weight of the ceramic. Incompletely destroyed clay minerals will be
rehydrated and rehydroxylated in a humid surrounding. If the newly formed crystals are
large enough, reflexes of clay minerals appear again in X-ray diffraction diagrams and may
then be detected in pottery fired between soo'C and woo'C. The most important implica-
tion of rehydration and rehydroxylation is that the abundance of clay minerals in ceram-
ics does not exclude high firing temperatures. It must be mentioned, however, that the
basal peak of the clay mineral illite may be seen in diffractograms of pottery fired to about
woo'C. In non-calcareous high-fired illitic clays, illite thus may appear together with mull-
ite (Maggetti, 1982).
An example of rehydration in low-fired non-calcareous Neolithic sherds from Switzerland
was given by Maggetti (1982). The X-ray diffractograms frequently showed a large peak indi-
eating the presence of very fine-grained clay particles of a mixed layer type that disappeared
after re-firing above 30o'C, which was well below the original firing temperatures. The dis-
appearance, therefore, is an indication that these minerals were formed during burial.
Rehydroxylation of clay minerals caused by environmental humidity was observed long
ago (Grim and Bradley, 1948; Hill, 1953; Kingery, 1974: Hamilton and Hall, 2012). This uptake
of water is very slow. It was, therefore, proposed that determining the quantity of water
required for rehydroxylation be used as a means of dating fired ceramics (Zaun, 1982; Wilson
et al., 2009). The problem is that even sherds made from the same clay behave differently
depending on their original firing temperature and on environmental conditions. This may
be partly overcome when each sample is refired at soo'C or 6so'C (Bowen et al., 2011) to
determine its original water content, and then the experimental gain of mass in a humid
environment is detected for every individual sample (individual kinetic constant). The age of
this sample can then be determined through extrapolation. There are many assumptions: the
temperature of re-firing must be sufficient for a total dehydration and dehydroxylation with-
out decomposing eventual carbonates; eventual contributions to the loss of weight by oxida-
tion of carbon or organic contents must be excluded; the influence of the environmental
temperature and of other possibly varying burial conditions over a long time span must be
corrected. It is, therefore, still an open question as to how reliable such data are and how
much they depend on the assumptions made.

Formation of Gehlenite and Calcite

Mineralogical changes occur in calcareous pottery fired above about 8so'C. Calcium
from the decay of calcite reacts with the new phases after decomposition of the clay
F

MINERALOGICAL AND CHEMICAL ALTERATION 165

minerals to calcium silicates and calcium-aluminum silicates. In experiments, gehlenite,

diopside, wollastonite, and anorthite are then observed as new phases by X-ray diffrac-
tion. The gehlenite problem, however, was that this mineral was not found in the Roman
pottery which was supposed to have been made from the clay used in the experiments
and fired at similar temperatures. This was explained by the breakdown of gehlenite as
a metastable mineral to calcite during burial in humid climates (Maggetti, 1981). The
decomposition of gehlenite to calcite was confirmed in experiments by Heimann and
Maggetti (1981).
In thin sections of medium-fired calcareous pottery (between about 85o'C and 95o'C)
where all primary calcite is decomposed secondary calcite derived from gehlenite
appears finely distributed within the matrix (Plate 2a). It explains the presence of cal-
cite in calcareous pottery fired above 85o'C. At lower firing temperatures, between
6oo°C and 8oo°C, secondary calcite is formed by recarbonatization of calcium oxides
and hydroxides after the decomposition of primary calcite. In thin sections it can mostly
be distinguished from primary calcite which survives in very low-fired pottery (below
about 7oo'C depending on grain sizes and time). In high-fired calcareous pottery (above
c.10oo'C) in thin sections only precipitated calcite appears in open pores of a vitrified
matrix. X-ray diffraction will detect calcite in all these sherds but only primary calcite
proves a low firing temperature below 7oo'C or 750'C, depending on firing atmosphere
and time.

Formation of Zeolites
In experiments, zeolites are formed together with rehydroxylation (Hill, 1953) or with the
breakdown of gehlenite (Heimann and Maggetti, 1981). The formation of small amounts of
zeolites is common in altered sherds of high-fired calcareous pottery (e.g. Picon, 1991). This
process has also been observed in experiments (Heimann and Maggetti, 1981). Analcime
(or wairakite) derives from the decomposition of gehlenite and from the alteration of the
glassy phase. This has been shown by X-ray diffraction of samples from sites in Switzerl<md
(Maggetti, 1981), in Spain (Buxeda i Garrig6s, 1999; Schwedt et al., zoo6), and on Crete
(Buxeda i GarrigOs et al., 2001). The formation of analcime is connected with an enrichment
of sodium derived from the surrounding soil and thus changing the chemical composition
of the sherd significantly(e.g. Buxeda i Garrig6s et al., 2002).

Alteration in Seawater
Bearat et al. (1992) found some changes in experiments with low-fired pottery where
calcium was exchanged through magnesium in carbonate minerals. In lagoon-like
conditions special alteration effects may appear, such as the formation of tiny crystals
of pyrite at the expense of hematite, which was noted by Sec co et al. (2ou). The sub-
sequent crystallization of jarosite and gypsum after pyrite was interpreted in terms of
changing environmental burial conditions differing between the two sites examined in
the aforementioned paper.
166 GER\VULF SCHNEIDER

CHEMICAL ALTERATION

Some of the chemical post-depositional alterations are clearly connected to mineralogical

changes which could be detected by X-ray diffraction, but absorption as well as leaching pri-
marily concern the badly crystallized phases after the decay of the clay minerals, glass, and
other amorphous phases,

Absorption and Contamination

Quantitative chemical analysis of the body of a sherd is mainly aimed at determining its
provenance by comparison with chemical analysis of sherds of known origin. ~Therefore>
possible post-depositional alterations must be taken into account Rehydration and rehy-
droxylation only change the water content However, of the elements determined by WD-
XRF or NAA, it seems that significant absorption effects exist for a series of chemical
elements, such as Ca, Sr, P, Ba, Fe, Mn, Na (and Cs), including possible post-depositional
contamination by Cu, Zn, and Pb, Many of these effects depend on the high cation exchange
capacity of ceramics, which may be of the same order as it is in clay (Hedges and McLellan,
1976). To remove possible contamination by soluble salts, the fragments to be prepared for
analysis should be washed with distilled water in an ultrasonic device. Some of the miner-
alogical alterations change the bulk chemical composition of a sherd. This is the case, for
example, when calcite is precipitated within the sherd or if zeolites are formed in high-fired
calcareous pottery. Other post-depositional changes, such as, for example, recarbonatiza-
tion, do not change the elemental chemical composition which is used to determine the
provenance of sherds.
The post-depositional alteration effects differ for non-calcareous and calcareous pottery
and depend very much on firing temperatures. Therefore, the effects of absorption, as well
as those ofleaching, in overfired calcareous pottery may be very different from those in the
lower-fired parts of the same sherd (Picon, 1991),

Water II
Rehydration and rehydroxylation result in a gain of weight because of the absorbed water. I!
This may be easily determined as loss on ignition, for example, at 950° C. However, this is I
only a measure for the water content if there is no organic matter, no sulfur, and no carbon- i
ates in the ceramic matrix. In chemical analyses, the water content acts as a dilution agent and
can be treated as such. 1 For varying water contents, chemical data can easily be accounted for
I
by comparing analyses on a water-free (ignited) basis, as is done in many laboratories,

Calcium
I
The formation of calcium silicates and calcium-aluminum silicates, such as gehlenite,
and recarbonatization does not change the initial calcium content. An example of
homogeneously distributed secondary calcite from recarbonatization after gehlenite in
 MINERALOGICAL AND CHEMICAL ALTERATION 167

a calcareous sherd of Arretine sigillata is shown in Plate 2a. The calcite within another
calcareous sherd of Eastern sigillata A (Plate 2b) very probably also originates from
recarbonatization. During burial it was leached at the surface where environmental acid
solutions had access as for example on the upper right hand site where the protective
gloss is missing. The secondary calcite does not change the original calcium content of
the samples (if not leached). On the other hand, calcite or gypsum crystallized within
cracks and open pores of a sherd derived from precipitation by invading calcium bicar-
bonate-containing solutions will change the composition significantly. In Plate 2c of a
high-fired sherd of non -calcareous North- Mesopotamian metallic ware the precipitated
calcite appears as a fine scale in the matrix and in open pores. 'Ihe precipitation here
caused an increase to about 6 wt.% CaO in. the core of this non-calcareous sherd which
previously had less than 1 wt.% CaO detected from comparison to sherds of the same
compositional group without secondary calcite. A special case of post-depositional alter-
ations is illustrated by a sherd of Tripolitanian sigillata shown in Plate zd. Here a thin
scaly layer between body and gloss makes the sherd macroscopically appear to have a
white engobe below the red gloss. For chemical analysis this layer, however, would be
removed. All four examples of calcite are connected with medium- to high-fired sherds
(c.8oo-rooo'C). The presence of calcite in diffractograms therefore cannot be attributed
to low firing temperatures.
Gypsum in ceramics may be recognized by analyzing sulfur. In thin sections, the possible
original gypsum content of the clay can be distinguished from secondary infiltrated gypsum
by the "swallow-tailed" pores left by the original gypsum crystals. After firing, these charac-
teristic pores are filled with very fine-grained secondary gypsum. Gypsum derived from pre-
cipitation will fill cracks and open pores with irregular shapes. In studies of Mesopotamian
pottery these effects play an important role and certainly must also be taken into account in
studies of pottery from other areas with similar environments. Besides the increase of cal-
cium by infiltrated calcite or gypsum, the values of strontium and its relation to calcium may
also be changed dramatically.
Analyzing profiles of four sherds using an electron microprobe, Freestone et al. (1985)
found an enrichment of calcium in the outer layers which was not connected to precipitation
of calcite. This could be excluded because only the fine matrix was analyzed and thin sec-
tions were studied. Thus, the U -shaped profiles as found for calcium, phosphorus, and iron
are clear indications of absorption within the matrix.

Phosphorus
Another very common effect of contamination is the absorption of phosphorus. In
archaeological sherds, P,0 5 concentration is nearly always higher than in the clay from
which the sherds have been made. Phosphorus contents above about 0.5 wt.% P ,0 5 gen-
erally indicate altered sherds, even if macroscopically they look intact. The fixation of
phosphorus certainly represents the largest of the alteration effects. Phosphorus origi-
nates from the soil in which the sherds are buried. It can be particularly high in pottery in
humid climates and in acid soils containing bones and organic waste, as is the case with
many archaeological finds. In some cases, for example in weathered sherds of Roman
Terra Sigillata, phosphorus can rise up to more than 10 wt.% P ,0 5 in the bulk analysis
168 GERWULF SCHNEIDER

of the body, and it would be even higher in the surface layers normally removed before
analysis. In rare instances some of the phosphorus may also derive from former organic
contents in the vessels (Duma, 1972; Dunnell and Hunt, 1990; Bearat and Dufournier,
1994). Phosphorus from temper containing crushed bones can easily be detected in thin
sections, and it normally yields much higher contents of P,0 5 which then are correlated
to calcium contents.
As phosphorus is not determined by NAA, this effect is only observed when other
techniques, such as WD-XRF, are used for chemical analysis (Schneider, 1978;
Rottlander, 1981-1983; Lemoine and Picon, 1982; Freestone et al., 1985; Picon, 1987;
Walter and Besnus, 1989). The absorbed phosphorus is homogeneously distributed
within the sherds and is not correlated to calcium or iron. Discrete grains or crystal-
line phosphate phases are not detected. Phosphorus, thus, must be bound to amorphous
and organic phases (Collomb and Maggetti, 1996). Calcareous pottery seems to be more
involved and the alteration is certainly connected to the ceramic quality of the sherds,
particularly to their porosity and to their level of vitrification. The phosphorus absorp-
tion as a rule is connected with other chemical alterations and thus can be used as a
marker for alteration. Elevated phosphorus in most instances is correlated with higher
ignition losses (rehydroxylation), with higher barium contents, and, sometimes, with
leaching of other elements.

Example: Roman Pottery at Different Sites

Finds of Roman sigillata produced at three production centers: Arezzo, Lyon, and
La Graufesenque, found in Velsen and Nijmegen in the Netherlands, were examined
in terms of alteration. The samples represent medium- to high-fired calcareous pottery
(c. 8oo-1,ooo"C), the three production centers represent sigillata of different quality and
the different find spots represent different burial conditions. For each site the element
concentrations for each of the three centers are averaged in spite of their large variation
and are compared to the values of the respective reference groups. Arezzo is represented
by forty-seven finds in Arezzo; for Lyon and for La Graufesenque data from Schneider
(1978) have been used. In Table 11.1 the values are shown for loss on ignition (l.o.i.) and
for the chemical elements associated with alteration effects. Compared to the reference
groups the absorption of water (l.o.i.), phosphorus, strontium, and barium of the finds in
Velsen may be regarded as negligible, but in the samples found in Nijmegen the increases
are obvious. The effects are least pronounced in sigillata from La Graufesenque, known
for its high quality.
Analyses of pottery from the Roman legionary camp of Dangstetten (Schneider and r
Daszkiewicz, zoo6) offer a similar example. Nearly all samples from this site showed ele- '
vated phosphorus contents. The effects on products from Lyon and from Arezzo again dif-
fer significantly. In sherds of sigillata from Lyon the average phosphorus content was 3-9
wt.% P,0 5 (n ~ 19) and all samples had more than 1.3 wt.% P,0 5. In sherds ofsigillata from
Arezzo the average was 1.3 wt.% P,0 5 (n ~ 148). Here 121 of 148 samples (82%) had more
than 0.5 wt.% P,0 5. This may be compared to analyses of sherds of Arretine sigillata found
in Arezzo where only six of 96 samples (6%) had more than 0.5 wt.% P,0 5• The elevated
phosphorus contents noted at Dangstetten, Nijmegen, and Velsen, as well as in Arezzo,

I
h
 iYHNERALOGICAL AND CHEMICAL ALTERATION 169

Table 11.1 Chemical alteration of Roman sigillata from Arezzo, Lyon, and La
Graufesenque found at Velsen and Nijmegen in the Netherlands. The
values for absorption are as analyzed. For leaching, the analyses results
have been normalized without phosphorus to a constant sum of 100%
Production site find spot l.o.i(wt%) P20 5 (wt<l'o) Sr (ppm) Ba (ppm)
···-~---···

absorption:

Arezzo (n ~ 47) 1.38 0.28 274 459

Arezzo Velsen (n ~ 20) 1.07 0.19 282 367
Nijmegen (n ~ 20) 4.61 3.85 350 1069
Reference group 0.27 260 425
Lyon Velsen (n ~ 7) 4.21 0.48 265 458
Nijmegen (n ~ 11) 8.15 7.20 435 1406
Reference group 0.30 354 386
La Graufesenque Velsen (n ~ 19) 1.20 0.33 363 399
Nijmegen (n ~ 54) 3.55 3.32 440 729
leaching
··--··-~~ ~--·---·

Production site find spot CaO(wt%) Na 20 l;v!'io) ~;vt%) Rb (ppm)

---·~·-----·--

Arezzo (n ~ 47) 9.61 0.77 2.63 134

Arezzo Vel sen (n ~ 20) 8.75 1.00 2.82 140
Nijmegen In ~ 20) 8.35 0.82 2.69 134
Reference group 17.60 0.56 2.16 114
Lyon Velsen (n ~ 7) 6.73 0.57 2.25 124
Nijmegen (n ~ 11) 6.86 0.50 2.19 131
Reference group 10.40 0.35 3.75 173
La Graufesenque Velsen In ~ 19) 11.10 0.37 3.67 165
Nijmegen In~ 54) 10.17 0.25 3.73 171

were mostly detected in samples with increased losses on ignition indicating rehydroxyl-
ation of weathered sherds. 2

Barium and Strontium

Together with elevated phosphorus contents, barium is increased in most cases as, for exam-
ple, in Velsen and Nijmegen (Table ILl). But this is not always the case and, depending on
burial conditions, on many occasions barium is significantly raised without remarkable
changes in phosphorus content. The uptake ofbarium has been described in various papers,
the most recent by Golitko et aL (2012). Sometimes strontium shows a similar behavior to
barium, but the maximal increase is lower. The explanation of this phenomenon, that bar-
ium originates from barite veins and strontium originates from a sedimentary environment
170 GERWULF SCHNEIDER

with high strontium contents, proposed by Picon (1985, 1987, 1991), seems not to cover all
cases. The effect in calcareous pottery is generally greater than in non-calcareous pottery, but
the degree of alteration seems much more connected to the ceramic quality and to the burial
conditions.
l
Figure 11.1 gives an example that shows the correlation ofbarium with phosphorus in non-
calcareous Roman Terra Nigra (orange squares) and Germanic pottery (green triangles)
compared to the local clay (pale re circles) from which the Roman and Germanic pottery
in Ladenburg was made (Schneider, 2002). The higher-fired and finer Roman pottery from
Ladenburg shows a good correlation of barium with phosphorus. '!he lower-fired Germanic
pottery from Ladenburg has higher barium and phosphorus values. Other Roman non-
calcareous pottery produced and found at three find spots in Speyer on the other side of the
Rhine (rhombuses) shows a similar correlation but with another ratio of barium to phos-
phorus. The different ratio indicates that the post-depositional conditions were different,

2500,------------------------------------------------,

Ladenburg

ro 1soo
"'E
~

-"
E
~ DO
~ 1000 - --------~-------------------··-----------------------------------------------------------
Lb 0 ~

• t ~<> o <>o
500 --~71'%?.... ~---------------------·---------------------·----------·------·------··-
~ Speyer

0+--------r--------r-------.--------r------~
0.00 0.50 1.00 1.50 2.00 2.50

FIGURE 11.1 Correlation of barium and phosphorus in Roman and Germanic pottery
from two sites in Germany. The analyses of clay supposed to have been used for !he pottery
in Ladenburg (pale circles) mark the starting point of the original composition of Roman
Terra Nigra (squares) and Germanic pottery (triangles) in Ladenburg. In Speyer one of the
three find spots is less influenced by absorption (empty rhombuses) than the other two find
spots (pale and dark rhombuses). Note the different starting composition and correlation in
Laden burg and in Speyer.
 MINERALOGICAL AND CHEMICAL ALTERATION 171

and at one of the three find spots in Speyer (empty rhombuses) post-depositional alteration
seems less pronounced than at the two others.

Sodium
The possible formation of zeolites in high-fired calcareous pottery causes a possible gain in
sodium content. In an example of calcareous pottery from Spain this could be up to three
times the original value (Schwed! et a!., zoo6). In this study, sodimn was significantly
enriched in the surface layers of the higher-fired and analcime-containing sherds. 3 In another
example, given by Buxeda i Garrig6s eta!. (2002), the average sodium contents rose from
o.84 wt.% Na 2 0 in the unaltered group to 1.75 wt.% Na 2 0 in the analcime-containing group
of the same Mycenaean pottery. In another study by Buxeda i Garrig6s eta!. (2001), sodium
contents are also clearly correlated with the peak intensity of analcime in the altered samples.
The samples presenting the highest analcime values also show the largest leaching effects of
potassium and, to a lesser extent, of rubidium. These effects in high-fired calcareous pottery
limit the use of sodimn (potassium, rubidium) as a significant element for provenance deter-
mination, but from the author's own experiences this concerns only a very minor proportion
of archaeological pottery. In any case, the effect may be overcome when possible analcime
contents are checked by X -ray diffraction, when sodium contents of sherds of different firing
temperatures within an otherwise homogeneous group are compared, and when other indi-
cations of alteration may be observed. In overtired calcareous pottery, besides absorption of
sodium, magnesium and strontium could also be enriched (Picon, 1991).

Caesium
The absorption of caesium in low-fired (below 750'C) pottery was reported by Buxeda i
Garrigos eta!. (2001) when they studied the alteration effects of alkaline elements in vari-
ous ceramics using NAA. This is likely to be related to the absorption capacity of the illites
still present in the low-fired pottery. However, in another case, in high-fired calcareous
Mycenaean sherds, caesium showed the opposite effect. It was clearly depleted in the surface
layers (Schwed! eta!., zoo6).

Manganese and Iron

Under certain circumstances manganese and iron may infiltrate buried sherds, leading to
significantly increased concentrations of these elements. For manganese this has been
described in several studies (Freeth, 1967; Dufournier, 1979; Walter and Besnus, 1989). The
content of manganese is related to the porosity and to the loss on ignition of the sherds,
indicating the alteratiou effect (Dufournier, 1979 ). It is enriched, for example, in the surface
layers of amphorae studied by Picon (1987). In a single analysis of a sherd it cannot be deter-
mined whether high manganese contents represent the original values. Outliers in a series,
however, may be due to post-depositional alteration. In certain burial conditions, iron could
also be fixed at the surfaces and within cracks in the sherds, thus causing a significant enrich-
ment of iron in the bulk chemical analysis. Mostly this is not visible macroscopically on the
original sherds but it is observable in thin sections (e.g. Daszkiewicz and Prinke, 1999) or it
can be made obvious by re-firing to about I,l00°C, when enriched iron contents appear as
172 DERWUL:F SCHNEIDER

red zones on the break or surface of the sherd, around open pores, or in cracks, in otherwise
l I
iron-poor pale sherds. Freestone et al. (1985) showed aU-shaped profile of iron using micro-
probe analysis in a study of sherds with elevated phosphorus contents at the surfaces.

Copper, Zinc, Lead, Silver

Archaeological sherds are often buried in an environment featuring metals. In such cases
corroded bronze may cause higher trace contents of copper, zinc, and lead in the surround-
ing soil as well as in the buried sherds. Such elevated trace contents were detected in pottery
found in the mining area of Lauri on in Greece (De Paepe, 1979). As the outer layers were
clearly enriched it could only be explained by accumulation of these metals from aqueous
solutions after burial. Similar effects have been shown in the author's analysis of material
from an excavated bronze casting workshop at Olympia. Here, nearly all pottery samples,
as well as the surrounding marly clay in which the sherds were deposited, evinced elevated
trace contents of copper. Accidental burial of a sherd in the vicinity of metal artifacts may
thus also explain frequent outliers of one, two, or three of the elements copper, zinc, or lead in
a series of analyses. Such outliers are mostly connected to altered sherds recognized by their
high phosphorus content and/or high ignition losses. Arretine sigillata found in Dangstetten
may serve as an example. Within the series of 148 analyzed samples at least 23 samples had
anomalously high zinc contents. These high zinc contents were always connected to elevated
traces of copper. Mostly, but not always, these sherds had higher phosphorus contents show-
ing this element as a marker for alteration effects. Six outliers caused by lead contamination
are not correlated with zinc or phosphorus.
Adan-Bayewitz et al. (zoo6) reported an example of anomalously high traces of silver
originating from in situ contamination after deposition. After ruling out other possibilities
this seemed to be the most probable explanation of higher silver contents of sherds exca-
vated in jerusalem compared to other sites in Israel.

Special Cases ofDeposition

Sherds buried in seawater show elevated magnesium which, according to Lemoine et al.
(1981), derives from a reaction of seawater with the glassy phase. In experiments, Bearat
et al. (1992) found a signifiCant decrease in calcium and an increase in magnesium, but no
changes in sodium. The latter, however, does not seem to be excluded in other cases ofburial
influenced by seawater (e.g. elevated sodium contents at Velsen, see example in Table 11.1).
Sherds buried in ash, for example, in a kiln or hearth, present another case. Such sherds
could take up significant amounts of potassium, which is then enriched in the surface layers
(Dufournier, 1979).

Leaching
Calcium
Calcite in sherds will be more or less slowly dissolved in acid soils. This is a well-known
phenomenon and has been demonstrated in various studies of chemical alteration (e.g.
Freeth, 1967). Analyses of profiles clearly point to reduced calcium content in the outer layers
 ,I\1INERALOGICAL AND CHEMICAL ALTERATION 173

(Thierrin-Michael, 1992; Schwedt eta!., 2004; Schwedt eta!., 2006). Extreme effects are pre-
sented by examples of coarse-tempered sherds where the coarse temper of crushed calcite
was totally dissolved and could only be recognized by the large rhombohedral pores left
behind. An analogous effect can be observed in shell-tempered pottery, where in thin sec-
tions only the characteristic pores left by dissolved crushed shell can be seen.
Finely distributed calcite within the matrix derived from recarbonatization is dis-
solved starting from the surface or from cracks where acid soil solutions have easy access.
Subsequently, a variably thick layer depleted in calcite appears below the surface, as can
be seen in many thin sections of medium- to high-fired calcareous pottery. An example of
Eastern sigillata A is shown in Plate 2c. These leaching effects, of course, will change the
chemical composition.4
Leaching of calcium is connected mainly, though not exclusively, to the dissolution of car-
bonates. Therefore, firing temperatures, the amount of calcium in the glassy phase, and cal-
cite contents will have large influences. Under certain burial conditions, deposition of calcite
may predominate leaching, resulting in profiles showing enriched calcium in the outer lay-
ers (Freestone eta!., 1985).

Examples:
In cross-sections of calcareous sherds re-fired at temperatures between l,I00°C and 1,2oooc
(MGR-analysis) 5 the effect of leaching can be seen very clearly. "Ihe outer layer of a calcar-
eous sherd from Tell Arbid (Iraq) exhibits the typical red color of non-calcareous ceramic
after re-firing at 12oo°C (Figure n.2b). The effect of leaching, however, cannot be seen in the
original sherd before re-firing (Figure u.2a). Chemical analyses of the yellow and of the red
parts in this example showed 19.2 -wt.% and 7.6 wt.% CaO respectively. The routine analysis
of a larger sample, as usual after removing surface layers, revealed a calcium content of 16.2
wt.% CaO, which thus is still lower than in the yellow part. 290 ppm of strontium in the yellow
part was reduced by leaching to 208 ppm in the red part (routine analysis of the whole sherd
after removing surface layers amounted to 262 ppm). It is important to note that not only the
contents of calcium and strontium but also their ratio changed significantly. Normalization of
the analyses to the same calcium contents showed that the other elements in this example have

(c)

1 em

FIGURE 11.2 Leaching of calcium in two samples of calcareous pottery: (a) sample from
Tell Arbil (Iraq) before re-firing; (b) other fragment of the same sample after re-firing at
120o"C; (c) fragment of a sample of Roman pottery from Aguntum (Austria) after re-firing
to uoo"C showing leaching at the surfaces and at the old break (left) exposed to environ-
mental influences. Photographs with macro-lens by M. Baranowski.
-
174 GERWULF SCHNEIDER

not been affected by leaching. This example is not an isolated case and most medium- to high~
fired calcareous pottery studied in thin sections shows similar effects. Some samples where the
leaching includes an old break of the sherd prove this effect to be caused by post-depositional
alteration. It can be made visible by re-firing, as illustrated with a fragment of a Roman pottery
from Aguntum (Austria) re-fired at noooC (Figure 11.2c).
Leaching was also observed in the examples discussed with the absorption of phosphorous
(Table 11.1, lower part).

These samples represent calcareous pottery in a humid climate and acid soils. All analy-
ses were carried out after removing the outer layers of the fragments before powdering
and, therefore, show reduced alteration effects. To account for the absorbed phospho-
rus contents the analyses have been normalized to a constant sum of wo% without P 20 5•
Comparing calcium contents at Velseri and Nijmegen with the reference values shows sig-
nificant leaching of calcium at both find spots for products from Lyon and Arezzo. This,
however, cannot be verified in this instance for other elements e.g. potassium and rubid-
ium (which in other cases was found to be significant). At Velsen, elevated sodium con-
tents must be explained by the influence of seawater at this coastal site, even though the
small fragments for analysis were washed thoroughly in distilled water in an ultrasonic
device.
A special effect concerns strontium, which is enriched together with barium (Table n.r)
in the same instance when calcium is reduced or unchanged. This leads to ratios of stron-
tium to calcium depending more on post-depositional alteration effects than on different
raw materials.
Considering only ten sherds (also used in Table 11.1) with phosphorus contents between
9 and n wt.% P,0 5 shows the leaching effects more obvious and how these result in signifi-
cantly higher values of the stable elements titanium, aluminum, and iron (chromium, nickel,
zirconium). Silica seems not to belong to these stable elements and may be leached to some
degree, as already hypothesized by Rottlander (1981-3).

Alkaline Elements
The possibility of leaching of the alkaline elements in pottery during burial is well known.
For potassium, it was already reported by Picon (1976).1he leaching effect on potassium and
barium is very marked in overtired calcareous pottery (Picon, 1991). Because of the negli-
gible effect for rubidium, the important ratio of rubidium to potassium changes very much.
Experiments of leaching calcareous sigillata in neutral and acid solutions by Segebade and
Lutz (1976, 1980) showed leaching for manganese, potassium, calcium, caesium, arsenic,
rubidium, but not for sodium. Based on a large series of analyses by NAA, the leaching of
all alkaline elements was discussed in several papers, including studies of profiles (Buxeda i
Garrigos et al., 2002; Schwedt, 2004; Schwedt et al., 2004, 2006). The leaching effect depends
mainly on the glassy phase and, therefore, it is significant especially in high-fired calcare-
ous pottery. But this does not exclude the effects in low-fired and in non-calcareous pottery.
The largest effect according to these studies seems to be for caesium followed by rubidium,
potassium, and sodium. But the order of elements does not always have to be the same (e.g.
Buxeda i Garrig6s et al., 2001). It is important to note that the loss of potassium can disrupt
luminescence dating, which is based on a constant dose rate from the radioactive elements
in the sherds (Zacharias et al., 2005).
 l
!
MINERALOGICAL AND CHEMICAL ALTERATION

As a consequence it was proposed not to use, for example, sodium for provenance stud-
ies, but this cannot be confirmed from the author's experiences with some 30,ooo analyses.
Certainly potassium and rubidium belong to the most significant elements in provenance
studies.

CONCLUSION§

The major aim of most studies concerning post-depositional alteration has been to see how
far alteration effects have an influence on the interpretation of pottery analyses in terms of
provenance and technology. Most papers concern only selected aspects of absorption or
leaching. The reported experiences also depend very much on the methods used for the
analysis when tbe range of the considered chemical elements depends on the detection lim-
its of the analytical technique. So phosphorus, and in some cases also calcium, is not taken
into consideration when NAA is used. On the other hand, because of the typically low
concentrations of caesium, its varying effects cannot be detected by WD-XRF. However,
the combination ofNAA and WD-XRF covers most chemical elements in archaeological
ceramics down to Jess thanr ppm (as would also ICP-MS), and it seems that the elements
not discussed here are not affected by post-depositional alteration. The combination of
chemical analysis with thin-section studies and/or X-ray diffraction analysis (XRD) has
proven to be very helpful for the discovery and interpretation of alteration effects. Re-firing
experiments' make some absorption and leaching effects clearly visible. The physical integ-
rity of a sherd, on the other hand, must not be a criterion for negligible post-depositional
alteration.
Another factor which limits the potential to generalize the results of multiple studies is
that the effects depend on the composition and ceramic quality of the ceramic object and on
its particular depositional environment Chemical and mineralogical composition, prepara-
tion, and firing of the clay determine the open porosity and the amount of glass, resulting
in different resistance against the attack of solutions during buriaL In this respect, calcare-
ous pottery and non-calcareous pottery behave very differently. For the alteration effects,
the tendencies are similar but also sometimes contradictory. The magnitude of the effects
depends very much on the specific circumstances of each case.
Post-depositional alteration mostly concerns primarily the surface layers, being more or
Jess thick, as many studies have shown. The mineralogical composition of the surfaces, how-
ever, may also differ from the composition of the core caused by other effects, such as higher
temperature (as in the core) or efflorescence of salt during the drying phase of the ceramic
object. These effects must also be considered. In consequence, samples used for the analysis
of the mineralogical or chemical composition of a ceramic object should be taken from the
core after having at least removed the surface layers of 1 mm or more all around. Even this
will not be sufficient to eliminate all alteration effects which are observed in numerous analy-
ses of such samples. Rehydroxylation, phosphorus contents, and many other effects concern
the core of the sample as well. Here, a word should be said concerning non-destructive analy-
sis using portable energy-dispersive X-ray fluorescence (p-ED-XRF). In pottery, even the
X -ray energy of the heavy elements will yield information only about a surface layer of Jess
than approximately o.s mm. Therefore serious alteration and contamination effects must be
 176 GERWULF SCHNEIDER

taken into account fOr the interpretation of the data. This may be avoided by measuring at
l I
fresh breaks, but then the analysis is not non-destructive.
The largest and the most common of the chemical alteration effects is certainly the absorp-
tion of phosphorus. 1bis element is therefore irrelevant for determining provenances, but it
may indicate possible post-depositional alterations of other elements. Sulfur and chlorine
are mostly lost during firing and are less significant for provenances, but they could also
be indicators of secondary contamination. For the rest of the elements which can be deter-
mined with sufficient precision and accuracy, the effects are normally limited and tendencies
are known from many analyses. Chemical alteration has to be taken into account at least
for calcium, strontium, barium, and the alkaline elements, in some cases also for manga-
nese, iron, zinc, copper, and lead. Experience, however, shows that the alkali and the alkaline
earths, in spite of their unstable behavior, may well be significant in distinguishing reference
groups and are certainly among the elements which should be analyzed. In any event, the
idea that a general list could be made of diagnostic elements for determining provenance,
which would be valid for all cases, should be rejected.
Mineralogical post-depositional alteration does not generally influence provenance
determinations, but must be taken into account when original firing conditions are recon-
structed. This mainly concerns the abundance of clay minerals and calcite. Their abundance
in a sample does not exclude a high firing temperature because of the possibility of rehydrox-
ylation and recarbonatization. Calcite or clay minerals detected by X-ray diffraction (XRD)
do not provide evidence of a low firing temperature. This can only be shown by the abun-
dance of undecomposed primary calcite; for example, by thin-section studies. Last but not
least, post-depositional alteration may help us to gain information about burial conditions,
and may be a possible perspective for dating.

NOTES

1. The full analysis of pottery samples, calculated as weight per cent of oxides, amounts to
100%. The non-determined major components, such as water and phosphorus (and sul-
fur), could be regarded as dilution effects and treated mathematically by calculating a best
relative fit (Olin and Sayre, 1979; Beier and Mommsen, 1994). Full chemical data for major
elements, including phosphorus, may also be normalized for comparison to a constant
sum of 100% without loss on ignition and with or without phosphorus (and sulfur). In
both methods the measured elemental concentrations are multiplied with a calculated
constant factor for each sample.
2. 1he very variable losses on ignition at 950°C here are not connected to the age of the pot-
tery, which is more or less similar for all sherds at all three sites. Besides, the effect of the
carbonates and organic contents on losses on ignition must also be taken into account. It
would be worth taking such samples as test objects for rehydroxylation dating.
3. There is also another effect which may cause enrichment of sodium in the surface layers
and which in some cases must be taken into account. This is salt in the makeup water of
the pottery which during drying is effloresced at the surface due to capillary action. "Ibis
may cause a white surface layer to appear on high-fired calcareous pottery, which is some-
times erroneously interpreted as a white slip. This, however, is not an alteration effect from
burial.

Ii
 MINERALOGICAL AND CHEMICAL ALTERATION 177

4. Lack of calcite in the surface layer of medium¥ to high-fired pottery may not only be
due to leaching. During firing, the surfaces could have been exposed for a short time
to a higher temperature, or the surface layer could have had a higher salt content due
to efflorescence during the drying stage. Both effects will result in different condi-
tions for the formation of gehlenite in the surface layer. Thus, the amount of second-
ary calcite here could be less than that in the core. In thin sections this may present
the same picture as leaching. The effect of a higher temperature on the surface can be
observed in many thin sections of calcareous and of non-calcareous pottery and can
be proved by determining the equivalent firing temperatures of the surface and of the
core separately.
5. See Chapter 27 by M. Daszkiewicz and L. Maritan in this volume.
6. See Chapter 27 by M. Daszkiewicz and L. Maritan in this volume.

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Wilson, M.A., Carter, M. A., Hall, C., Hoff, W D., !nee, C., and Betts, I. M. (zoo9). "Dating
Fired-Clay Ceramics Using Long-Term Power Law Rehydroxylation Kinetics:' Proceedings
of the Royal Society A 465: 2407-2415.
180 GERWULF SCHNEIDER l
Zacharias, N., Buxeda i Garrig6s, j., Mommsen, H., Schwedt, A., and Kilikoglou, V. (2005). I

"Implications of Burial Alterations on Luminescence Dating of Archaeological Ceramics."

Journal ofArchaeological Science 32: 49-57.
Zaun, P. E. (1982). "Influences of Soil Stratification on Prehistoric PotterY:' Neues !ahrbuch fur
Mineralogic Monatshefte 3: 106-118.
 CHAPTER 12

FORMAL ANALYSIS
AND TYPOLOGICAL
CLASSIFICATION IN THE
STUDY OF ANCIENT POTTERY

DANIEL ALBERO SANTACREU,

MANUEL CALVO TRIAS,
AND JAIME GARciA ROSSELLO

INTRODUCTION

CLAY is a highly malleable material which has been used for millennia to create vessels as
well as an endless repertoire of artifacts. Form and decoration make up two of the most vis-
ible and accessible attributes of pottery, a fact which has probably precluded their thorough
analysis and set the basis for the typological classification of archaeological pottery as early
as the mid~nineteenth century. 1
Broadly speaking, the study of pottery form and its classification can be considered on
four analytical levels, which provide the tools needed to characterize vessels and incorpo-
rate them into multiple interpretative discourses (Figure 12.1). These levels cover from the
most peculiar aspects to general ones, from the most analytical stages of research to the most
interpretative arguments, as each of them aims at solving specific problems in the study of
pottery form using, in turn, particular concepts and methodologies. Summing up, the many
analytical levels may be organized as:

( 1) Description of pottery form.

(2) Classification and elaboration of typological proposals.
(3) Typological-interpretative tools.
(4) Interpretative perspectives of typologies.

Until the 196os, these analytical levels were in step with the development of a theoretical
basis regarding vessel description and typologies. However, since the 1970s, efforts have
been mainly concentrated on promoting the methodological development of a kind of
 '

~ jLevel 2 j jLevel 3 j I level 4 j

~
Formal ------> ------> Interpretative Interpretative Fractality/Homology
descriptions tools (Extrinsic parameters)
{e.g. form-based
analysis)

fN;~=~cti_ve I
Q"''"'""
{e.g. geometric, II Quantitative
(e.g. metrical-
Intuitive/Objective Variability
symmetry/Shape/Size
Teclmological Chrono-cultural

I topological) mathematical) Theorie:al/Practica I lsomorphism/Skeuomorphism

Approach
(multidimensional)
.......
Approach
----
Fossil Index
Paradigmatic/Taxonomic Agency Seriation
Ceramic Homology
Polythetic/Monothetic Habitus Functionalist
Hydridization Approach
Class ----
Type Symbolic Product
Variety Approach Specialization
Etc:. --------
Identity
Style
-
FIGURE 12.1 Summary of the different levels to approach pottery form and typological analyses diScussed in the text. It includes the main concepts
and tools in each level.
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 183

grouping (\Vhittaker et al., 1998; Read, 2007), frequently considering the application of such
methodology as the aim of the study (Dunnell, 1986; Read, 1989). This was the case for more
systematized form analyses (e.g. form-based analysis) and their combination with mathe-
matical and statistical protocols (e.g. discriminant analysis, principal component analysis,
cluster analysis, curve analysis; Sheppard, 1971; Whallon and Brown, 1982; Read, 1989, 2007;
Hendrix et al., 1996; Gilboa et al., 2004), which gave rise to the so-called electronic paradigm
(Adams and Adams, 1991).
Nevertheless, there has always been a minor interest in moving from the application of
the different methods used to describe and classify pottery to the interpretative meaning of
the typologies proposed (Sheppard, 1971; Read, 1989). Due to their growing marginalization,
pottery typological and form studies are currently suffering in favor of archaeometric analy-
ses, a revision and revalorization of the role played by the former is needed in order to restore
them as potentially relevant tools to approach both technology and people in past societies.
Furthermore, morphological analysis is considered to facilitate the generation of multidi-
mensional and holistic interpretations of materiality. Consequently, it is assumed that vessel
form is related to certain phenomena which are not evident in the technological studies that
focus on vessel fabrics and forming.
This chapter introduces a summarized revision of some of the theoretical-methodological
aspects key to typology so as to comprehensively understand the main interpretative propos-
als which use this research tool, evaluating their particular aims, proceedings, and concepts.
Finally, a revision of the use of pottery form analysis is proposed, as well as its incorporation
into the theoretical and interpretative framework that is provided by the social theory of
technology to elaborate explanations for the active role of vessel form and to develop typolo-
gies which include a new explanatory dimension.

FORM DESCRIPTION
AND CLASSIFICATION STRATEGIES

Most of the classification efforts in the last decades have been devoted to the definition of
strategies aimed at delving into the problems postulated by the first two analytical levels.
A comprehensive revision of such research is far from the possibilities and aims of this chap-
ter; instead, a short and general outline of the most important trends currently in use is
provided.
The first strategies for the study and description of pottery form and decoration were
characterized by their limited, systematized, highly intuitive, eclectic, and subjective nature,
supported by aesthetic assessments coming from the personal experience or perspective of
the analysts. As a result, imprecise terminology usually based on morphofunctional criteria
was used (Hendrix et al., 1996). Since the 1950s, however, these guidelines have been comple-
mented by other methodological strategies-such as the form-based analysis (e.g. Sheppard,
1971; Ericson and Stickel, 1973; Hendrix et al., 1996), which was aimed at bringing greater
objectivity to the description of pottery following a strict and systematized analysis of the
form on the basis of geometrical models. Since then, morphometric quantitative analyses
have been incorporated into morphological studies, significantly increasing the number of
184 D. A. SANTACREU, M. C. TRIAS, AND J. G. ROSSELL6

attributes recorded in a pottery piece, as well as defining its form through the use of ratios,
indexes, and mathematical models.
Regarding the second level, the focus has been centered on defining typological classifi-
cations for pottery. Classifications in archaeology usually tend to organize the record into
categories which share some internal coherence, depending on the similarities and differ-
ences present in the artifacts' attributes. On the one hand, it implies the definition of catego-
ries and, on the other, the assignation of the individual pieces to such categories (Sheppard,
1971; Rice, 1987; Read, 1989). In pragmatic terms, both descriptions and classifications of pot-
tery have to be systematic and coherent in order to promote the use of a standardized ter-
minology and a typology devoid of subjective interpretations, so as to favor understanding
amongst researchers (Whittaker et aL, 1998).
At this second level, typological classifications have originated either from proposals
based on the intuitive researchers' perceptions of the differences and similarities existing
between ceramics (e.g. Krieger, 1944; Gifford, 1960; Rouse, 1960), or alternatively, on alleg-
edly more objective methodologies which used mathematical and statistical tools for group-
ing. They are intended to inductively create replicated descriptions and classifications of
the vessels which can simultaneously compare a broader number of attributes with better
definition of both the data and the variables being analyzed. This kind of tool creates groups
with a strong internal coherence and provides a less arbitrary boundary between categories
(Whallon and Brown, 1982; Read, 2007). However, these grouping strategies are not devoid
of problems, since the analysis frequently incorporates variables or attributes of the vessels
which are not relevant for archaeological questions. Nevertheless, some authors such as
Read (1989, 2007) considered that intuitive classifications could be even more informative
and useful than some of the more objective ones.
Typological groupings may also vary depending on the way the attributes are considered:
they can either be paradigmatic (Whallon, 1972) or taxonomic (Read, 1989, 2007 ). In the for-
mer, the most frequent in multivariant statistical analyses, no hierarchy is postulated for the
variables used in the classification, so all the attributes recorded for a vessel can be treated
both simultaneously and independently. In the latter, the several attributes of a vessel are
considered to have a different validity for determining pottery types; thus they have to be
used in a sequential and hierarchical order according to many different criteria.
Furthermore, pottery classifications migbt also depend on different ontologies. In this
sense, a heated debate has been generated about the ernie or etic nature of the typologies
archaeologists create. Hence, it is possible to discriminate between theoretical (e.g. Krieger,
1944; Spaulding, 1953; Gifford, 1960; Rouse, 1960) and practical typologies (e.g. Hill and Evans,
1972; Adams, 1988; Adams and Adams, 1991; Kampe! and Sablatnig, 2007). The former can be
encompassed as ernie classifications, closely related to so-called folk classifications or ethno-
taxonomies (Kempton, 1981; Rice, 1987; Fowler, 2006), where both potters and other members
of their community (i.e. consumers and non-consumers) are assumed to base their classifica~
lions on tangible aspects related to certain physical parameters of the materials (e.g. appear-
ance, form, and size) as well as on intangible or cultural phenomena. In this context, many
scholars understand the pottery classification process as proceeding from an inductive or theo-
retical nature which allows the discovery and/or replication of the natural types present in the
artisan's mind; a classification which underlies the data recorded. In this sense, the ceramic
types defined are considered to carry an important cultural and historical meaning, and, con-
sequently, to mirror the ideas and values of the people who made and used the artifacts.
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 185

As a counterpart to ernie typologies, the classifications drawn by analysts from etic perspec-
tives, also referred to as devised classifications, have dominated research since the 196os, coincid-
ing with the boom of processualist and positivist views in the typological study of archaeological
pottery. Although these perspectives consider that the pottery found in archaeological sites was
originally related to the rationality scheme of the potters and their communities, as well as to
the functional, socioeconomic, and symbolic-ideological contexts which characterized the
life-cycle of the vessels, it must be accepted that archaeological typologies designed in the pres-
ent have little to do with folk classifications. The many complex terminological and classifica-
tory shades used by the members of a certain culture to arrange a pottery assemblage in their
minds maybe impossible to perceive or replicate by foreigners. In this sense, a number of papers
have proved (Weigand, 1969; Birmingham, 1975) that many of the classificatory elements fre-
quently used by archaeologists (e.g. base, rim, lip form) have a weak connection with those used
by ancient societies. Moreover, it should be considered that several of the elements people use to
classify their surrounding material culture are difficult to see in the archaeological record.
Practical perspectives argue that rypologies imply an interpretative process, an analyti-
cal and creative operation, that originated in the ideational and conceptual realm. Similarly
to the other attributes of pottery (e.g. fabric), they suppose an action which goes beyond
the empirical world and is deeply influenced by the theoretical approach of the researcher.
However, it triggers a certain degree of artificiality and arbitrariness in the classificatory pro-
cess as, for instance, the researcher has to decide which attributes, of the seemingly endless
possibilities, should be measured and selected for formal comparison. In short, morphomet-
ric and typological analyses of pottery are considered to be born from the rational schemes
of the scholars and to be aimed at structuring a specific ceramic universe.
This idea invited some authors (Hayden, 1984; Rice, 1987; Whittaker et al., 1998) to make
a conceptual distinction between classification and typology. The former is considered as an
empirical grouping of objects based on their differences and similarities. Typology, on the
other hand, implies a classification with a clear theoretical background as well as explicit and
well-agreed norms or proceedings to solve specific problems.
According to Rice (1987), although devised classifications and folk classifications originate
from different and often opposed concepts and objectives, both can provide feedback and
interesting incentives for pottery classification. Currently, the general option is an interme-
diate position, where typologies are accepted to be subjective but are also potentially suitable
for going beyond the mere description or organization of the record and being used in an
interpretative discourse. That is, the differences perceived at the etic level can be reflected at
the ernie level (Read, 2007).
In any case, each and every different typological proposal defines its own concepts to orga-
nize the factual universe depending on its interpretative and instrumental objectives and the
kind of record it works with. This is the case particularly for concepts such as mode (Rouse,
1960 ), type-variety (Gifford, 1960 ), and type (Dunnell, 1986), among many others. This diver-
sity is a consequence of each typological classification strategy (i.e. the attributes selected and
the grouping strategies used) being drawn, either consciously or unconsciously, for specific
research objectives which vary depending on their intention of creating descriptive, com-
parative, or analytical typologies or, rather, dealing with chronological, cultural, functional
or technological aspects by using such typology (Adams and Adams, 1991). Furthermore,
as already noted by these authors, the aim of typology determines the kind of record to be
selected (for instance, if it considers only complete pieces or also includes sherds).
186 D. A. SANTACREU, M. C. TRIAS, AND J. G. ROSSELL6

TYPOLOGICAL-INTERPRETATIVE TOOLS

The third analytical level comprises a series of interpretative tools which transcend the typo-
logical classifications and morphological analyses described above. TI1ese tools, which are
understood and used differently by each perspective, allow the researcher to go beyond the
data and build coherent discourses about past societies. A large number of interpretative
tools can be included at this level, some of which are the following:

(a) Morphotypological variability. The morphological variability of the record can be

accessed by organizing the pottery assemblage into different categories and observing
the pieces' differences and similarities in different chronological and spatial segments.
This variability is informative of the routines and the repetition of actions followed
in the production process. Thus, some of its aims are facilitating a formal compari-
son of pottery and identifying the existence of either variations or continuities in
the record (Adams and Adams, 1991). As will be explained in the section "Pottery
Typologies and Main Interpretative Proposals;' the variability present in any record
has been interpreted in a myriad ways which are also related to different analytical
scales (Ericson and Stickel, 1973; Dobres, 1999) and objectives. In most interpreta-
tions, such as culture historical and processualist typologies, macroscalar analyses
are dominant as they consider extensive regional spaces and temporal segments (e.g.
Hendrix eta!., 1996), although microscalar analyses of variability can be also applied
(Dobres, 1999).
(b) Symmetry, size, and form as evidence of the potter's expertise. The analysis of symme-
try, form, and size of the individual pieces is fundamental for pottery studies. As well
as descriptors of the vessels, the symmetry, the kind of forms modeled, or the size of
the objects have been proposed as an indication, together with a number of attributes
such as the fabric, surface treatment, or wall thickness, or the potters' level of techni-
cal skill (Sheppard, !971; Budden and Sofaer, 2009; Vidal, 2011).
(c) Translation of the form (isomorphism and skeuomorphism). 1be concept of iso-
morphism implies the repetition of a given form in several objects, thus providing
them with the same meaning. In these cases, any potential variation does not trigger
changes in the behavior or relationship between the elements constituting the object;
thus its structural relation remains constant (Samaniego, 2013). Isomorphism cases
in pottery may be numerous and varied. The most common is the preservation of the
form and the metrical proportions of the vessels when their size is modified. Another
example may be the repetition of decorative patterns on different media (Figure 12.2).
Skeuomorphism, a variant of isomorphism which has been also reinterpreted by the
different schools of thought (see Frieman, 20 I 0), refers to the translation of the form
and other perceptive aspects of the ceramic universe to other technologies and vice
versa. Well-known examples of skeuomorphism in pottery are the reproduction of
forms and decorative patterns copying basketry, carpentry, or leather-work (Manby,
1995; Hurcombe, 2008), as well as the imitation of some types of metallic contain-
ers such as occurs in Etruscan bucchero pottery. The analysis of both isomorphism
and skeuomorphism has a large interpretative potential when its identification is fol-
lowed by an evaluation of the influence of these phenomena over society. Hence, it is
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 187

FIGURE 12.2 Isomorphic relation between the decorative motifs recorded on Late Iron
Age pottery and bronze discs in Mallo rca (Spain).

important to record whether the translation of the form is restricted to certain types
or affects a wide variety of forms, which is the direction of the translation, whether
the loan is limited to two technologies or affects more spheres, whether the replicated
form shares the same contextual relationship in the many materials or is significantly
different, and so on.

POTTERY TYPOLOGIES AND MAIN

INTERPRETATIVE PROPOSALS

Both pottery typologies and interpretative tools are drawn, conceived, and used in a certain
way depending on their ultimate aims. Interpretative strategies in archaeology have played
a key role in the classificatory systems which structured and organized the real world. After
briefly describing the use of form analysis and typologies by the different interpretative posi-
tion, a projection of the future of morphotypological analyses and their inclusion in more
technological-social interpretations will be discussed.

Typologies and Chronological Frameworks

Typological seriation strategies can be considered, together with stratigraphic principles,
the first methodological tools promoting modern archaeology, because one of the first
objectives of typological seriation was to organize and chronologically place the myriad of
archaeological objects already recovered, which in the early nineteenth century were con-
sidered exclusively from a collector's and antiquarian's point of view (Trigger, 1989; Orton et
al., 1993). The first modern typological proposals are therefore found at the very beginnings
188 n. A. SANTACREU, M. C. TRIAS, AND). G. ROSSELL6

of the discipline, in the development of seriation strategies according to raw material and
stylistic criteria. Archaeological objects were not only classified and organized into types,
but were also relocated in concrete chronological and stratigraphic sequences: this was the
birth of relative chronology, the essential and only dating method available before the dis-
covery of absolute dating. Thus, the late nineteenth century produced paradigmatic exam-
ples of pottery seriation (see Chapter 37, this volume) such as Smitl1s study of terra sigillata
(1854), Pottier's Normand pottery (1867), or Plique's research (1887), as well as Petrie's work
in Lachish, Palestine (1891), and Egypt (1890), where the ceramic types were identified in the
stratigraphic sequence (Sinopoli, 1991; Orton eta!., 1993; Hendrix eta!., 1996).
Originally, the association between typology, seriation, and stratigraphy rested on consid-
ering the ceramic type as the chronological reference for a culture, based on the principles
which allowed the paleontological identification of fossils with geological strata (Adams and
Adams, 1991; Orton et a!., 1993). The definition of ceramic types from different sites pro-
vided cross-datings which were grouped into regional chronological sequences, the simi-
larities between types representing temporal proximity (Trigger, 1989). This twofold nature
of pottery typology (i.e. as stylistic-formal organization and chronological reference) was
present as one of the main analytical strategies in most archaeological discourses until well
into the twentieth century, and is still in use despite the conceptual redefinition of typology.
Currently, multiple archaeological discourses still find this relationship, based on the con-
cept of relative chronology and cross-dating, essential in many typological classifications.
1bis association is clear, for instance, in the analysis of wheel-made seriated pottery, such as
amphorae, thin-walled Roman ceramics, and Terra Sigillata.

Typologies and Cultural Frameworks

Far from denying the chronological use of typology, culture history provided it with a new
meaning. A century ago, the evident relationship between certain findings and concrete geo-
graphical areas was proposed, and the definition of cultural areas as being home to different
human groups followed (Trigger, 1989). This threefold association among recurring objects,
geographical areas, and cultural groups signaled an important qualitative and conceptual leap.
Since then, types have not only provided a concrete chronology but also a regional and cultural
perspective, and even an ethnic affiliation by studying the objects recovered (Childe, 1929).
Culture history defined a new concept of culture, which was eventually integrated into
archaeology as the archaeological culture and fossil directeur, which implied the relation-
ship among the archaeological materials found in a particular place, their chronology, and a
specific ethnic group or people (Childe, 1925, 1929; Kossina, 1926).
This new perspective promoted typology to another dimension, as it fulfilled one of the
objectives of the culture historical paradigm: the interpretation of the archaeological record
as a mirror of nameless prehistoric peoples identified by the characterization of their archae-
ological cultures rather than as developmental evidence of their culture. Furthermore, dif-
fusionism as an interpretative tool was used to explain cultural change, using materiality to
define the origin, movement, and interaction of those peoples.
In these interpretations, pottery gained protagonism owing to its identification with cul-
tures and ethnic groups. Many typological strategies used for pottery analysis had an impact
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 189

on its cultural dimension (e.g. Krieger, 1944; Gifford, 1960; Rouse, 1960). Until the 1950s pot-
tery typologies and the concept of fossil directeur were prevalent for the archaeological iden-
tification of ethnocultural groups. Such was the case of the debate on the integration of the
Prague ceramic type into Slavic ethnicity, the association of Linearbandkeramik with the first
Neolithic communities in Central Europe (Childe, 1929; Klopfleisch, in Hibben, 1958), and
the first research on the ethnic group responsible for the Bell Beaker pottery (Castillo, 1928;
Bosch Gimpera, 1940 ).
Aiming at defining chronocultural typological entities, their analysis of pottery vari-
ability was focused on macroscales covering regional territories and large time periods.
Furthermore, in order to determine the scope and distribution of cultural entities, diffusion~
ism understood isomorphic phenomena as the imitation and subsequent copy of forms or
other specific elements owing to the dominance or influence of one culture over another by
means of trading (e.g. colonial), political, military, or other relations.

Typology and Functionality

The New Archaeology, closely related to a functionalist view of society, considered pottery
a product (Sackett, 1977; Binford, 1989) or tool (Braun, 1983) whose manufacture responded
to known and preconceived needs. 'Ihus, one aspect which characterized pottery life for
them was its function regarding one or more ends (Rice, 1990 ); hence, pottery was designed
following functional criteria (Sheppard, 1971; Smith, 1985; Rice, 1987; Orton eta!., 1993). Its
function determined or restricted pottery forms, so innovative forms may have responded
to new needs, making them representative ofhuman behavior.
The definition of morphofunctional relationships demanded more systematic and
(presumed) objective criteria, such as ethnographic analogy, to address vessel function-
ality: differentiating between the description of the form and the analysis of functionality
(Birmingham, 1975; Henrickson and McDonald, 1985; Rice, 1987). This close relationship
between form and function, supplemented by absolute dating which overcame the defi-
nition of chronocultural entities as the main interest of typologies, favored the develop-
ment of new classificatory and interpretative strategies. This was the theoretical context
at the peak of functional classifications characterized by organizing materiality from the
presumed function of the artifacts, usually considering the morphological attributes
inherent to the objects (Adams and Adams, 1991). Here, pottery classifications depended
primarily on vessel form to establish functional categories. In such classifications, numer-
ous parameters of the form (e.g. mouth width) were considered broad indications of its
function, the kind of contents (i.e. liquid vs. solid), and their manipulation inside the
container (Sheppard, 1971; Henrickson and McDonald, 1985; Rice, 1987; Sinopoli, 1991).
Similarly) varieties of the form were also related to the use of certain culinary techniques
(Rice, 1987).
The link between the function and effectiveness of a form and the physical properties
of the vessels was also addressed. In this sense, some morphological elements, such as the
curved profile in a pot, were proved to maximize thermal shock resistance in cooking pot-
tery (Woods, 1986) as well as impact resistance (Schiffer and Skibo, 1987), caloric efficiency,
or thermal conductivity (Hally, 1986; Schiffer and Skibo, 1987).
190 D. A. SANTACREU, M. C. TRIAS, AND J. G. ROSSELL6

In short, this functionalist interest pretended to understand the socioeconomic view of a

society. For processualism, isomorphism did not necessarily imply the direct derivation or
influence of one style on another; it may have responded to an autochthonous adaptation to
l
a specific environment and economy (e.g. agriculture) together with the use of peculiar culi-
nary practices (Sheppard, 1971), with the subsequent functional specialization of the whole
materiality.
Similarly, processualist typologies considered a limited variability in any specific form as
the evidence for both specialization and a reduced number of potters. Actually, this school
has always been interested in defining the degree of specialization and its links with more
evolved behaviors, where potters produced better quality and technically more efficient
products. This question was addressed using form and surface analyses, considering asym-
metrical profiles the production of scarcely specialized potters regarding their mastering of
technical gestures. Vessel size was also considered indicative of experience (Longacre, 1999;
Broda et al., 2009).

Typology, Textual Metaphor, and Identity

The first post-processual paradigms stressed the active role of pottery forms and decorations
as the material medium of a communicative event which was expressed with the symbols
inherent to the objects. In this context, Hodder's seminal work (1982) shook up archaeol-
ogy in general and pottery studies in particular by highlighting the symbolic and ideologi-
cal aspects of material culture. According to his views, material culture and, consequently,
pottery features were significantly constructed and should be considered an active element
in the definition of societies. He also reinforced the idea that material culture was neither
innate nor did it passively mirror society; on the contrary, it was created by people's actions
(Hodder, 1998).
1hese ideas originated the textual metaphors held by interpretative archaeology (Hodder,
1991; Tilley, 1999). Under the influence of semiotics and hermeneutics, it understood the
analysis of material culture and its interpretation as a communicational event full of signifier
and signified elements. People acted in accordance with the social symbolic system and each
individual in turn played an active role in his/her society. Thus, pottery forms and attributes
were not just a neutral product but the embodiment of the symbolic connotations of a com-
munity in a certain place and time. Pottery, as a social product, reproduced the symbolic
system of the society it was inserted in, and the similarities and differences embodied in the
stylistic tendencies of formal analysis expressed a common rationality and emphasized the
identity of a particular style against the rest (Prieto, 1999 ).
This new association with symbolic and identitarian constituents explains the new uses
of typology. In this view, the study of pottery style made visible identities related to status,
cast, ethnicity, and genre, among others. Mahias (1993), for instance, documented the link
between technological and stylistic variations and the caste-based social structure in India.
Regarding ethnic identity, a number of papers integrated typological and technological anal-
yses of pottery (Dietler and Herbich, 1989; Gallay and Huysecom, 1991; Hardin and Mills,
2000). The work of Gosselain (2ooo) exemplified the distribution and expansion of styles
regarding local languages. Alternatively, Bowser (2000) observed that Achuar and Quechua
women in Ecuador use pottery as a descriptor of political identity.
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 191

Typology and Technology: New Perspectives

and Interpretative Possibilities of Social Dynamics
.I In the last few decades, there has been a rise in the incipient application of typological strat-

i
egies to technological analyses born from a clear integration with the social dynamics of
the groups studied. This social perspective of technology has mainly been developed from
anthropological views and focused its interest in the study of the materials and techniques
associated with pottery-making. However, in addition to these issues, typological analyses
are also a useful strategy for a social approach to technology.
This analytical strategy has gained popularity since the 1980s, with the active partici-
pation of two schools from different academic backgrounds: the anthropology of tech-
niques (e.g. Lemonnier, 1986) and the analysis of technology of the social agency theory
(e.g. Dobres, 2ooo).
The inclusion of this proposal in archaeological questions implies that the study of the
objects-that is, elements made, used, exchanged, maintained, and abandoned in a social
space, usually during daily activities-can lead to the complex social practice of the techno-
logical process and its connection with rationality schemes, social praxis, power relations,
economic bases, material reality, and so on; all of them interpreted as parts of a whole and
unable to be understood separately because they are mutually constructed.
The technological process, similarly to other social activities, would originate in the daily
and contingent praxis through habitus dynamics (Bourdieu, 1977) and agency (Barrett,
1994), in a web of relations between objects and people (Latour, 2008). It implies the incor-
poration of patterns culturally chosen through constant practice. These attitudes, elections,
and perceptions of technical alternatives, embedded in social relations and configured by
the habitus, may be perceived as natural and absolutely logical, besides any consideration of
the efficiency of techniques and materials. Even if technological practice and tradition can
be seen as predetermined and static, they imply relational and dynamic phenomena. 1bey
are an historical product which is active in the present, for technological practice is mate-
rialized in a series of learnt and interiorized dispositions which allow the reproduction of
social structures and, at the same time, explain their changes through agency. Hence, tech~
nology becomes a complex cultural phenomenon, incorporated in historically contingent
worldviews, interiorized social actions, and agency. Consequently, the study of technologi-
cal processes has to transcend the analysis of the simple physical medium as it is intimately
connected with social phenomena.
Typological strategies and their interpretative contributions can be incorporated into this
discourse as the analysis of pottery form, as far as it implies a collective technological choice
in a specific social context, makes possible the identification of the conscious and uncon~
scious schemes, and praxis of the technological process. Hence, typological strategies are
understood as a valuable tool for the interpretation of technological-social dynamics. This
implies considering pottery form and the typologies developed from it as an active element
relevant for interpretation and thus different from passive views and typological mechanicist
interpretations.
In this interpretative context, vessels' morphometry and typology, accepting pottery as a
social rather than individual formalization, could be considered a priori as indirect evidence
of certain technological praxis embodied with sociocultural connotations. However, such
192 D. A. SANTACREU, M. C. TR!AS, AND j. G. ROSSELL0

evidence does not need to be defined by the structure of the classifications devised; that is,
by the types, categories, or groups created, nor by the grouping strategies used (e.g. para-
digmatic/taxonomic, intuitive/objective). So, from this perspective, typological analyses are
mainly focused in taking advantage of the interpretative potential of third-level tools. Some
examples may clarify their current use.

(a) Analysis ofMicro scale Knowledge Transfer and Agency

This perspective considers the analysis of morphotypological variability at a microscale so
as to deepen the dynamics behind two specific questions: knowledge transfer and agency. In
clear opposition to processualist typologies, social technology considers that the variability
present in the pottery forms produced by a community depends upon people's interaction
(either conscious or unconscious) with multiple and varied elements and values typical of
their society. The presence of variability is frequently considered as evidence of a break with
traditional learning patterns and the disintegration of the potters' technological-formal
schemes (Garda Rossell6, 2010).
A second interpretative position in the analysis of variability is focused on the role played
by individuals and their agency capacity. The idea of the individual has traditionally been
uncomfortable for the main interpretative paradigms; clearly seen in the many typological
grouping strategies which tended to establish highly standardized typologies insisting on
the importance of making them consistent and homogeneous (Whittaker et al., 1998). In the
search for consistent standardizations> "anomalous" cases were considered outliers-that is,
unconnected with the norm determining the perceptive difference noted by the research-
ers-thus they were difficult to classify, understand, and explain.
Since the active role of the individuals and their agency capacity has been made clear, the
analysis of marginal forms or types validated in typological classifications has offered more
interpretative flexibility to address different kinds of phenomena while explaining the com-
plexity observed in material culture with more coherent discourses (Dobres, 1999 ).
Regarding agency, it should be remembered that vessel form, as well as other highly visual
attributes such as decorative motifs, is frequently a collectively perceived aspect. These
more visible dimensions of pottery are precisely those favored by individuals to commu-
nicate messages to the rest of the community and define their social space (Herbich, 1987:
Gosselain, 2oo8). It explains the higher degree of innovation in vessel form and decoration
than in any other dimension of pottery, such as paste preparation or modeling techniques, as
the latter are less visible to the rest of the community.
A useful strategy to study the concept of variability and its interpretative potential in
knowledge transfer dynamics, agency, and technological tradition could be their artic-
ulation in the type-variety system (Gifford, 1960). Although this system was developed
as a mere taxonomic tool, some scholars (Rice, 1987; Sinopoli, 1991; Read, 2007) suggest
its use to interpret cultural aspects and observe record variability. Ihis typological sys-
tem presents the advantage of simultaneously recording the cultural patterns shared and
accepted by the whole society which originated the traditions materialized in the recur-
ring material attributes (types), while also reflecting the variations in the artifacts as a
consequence of an individual's or small social groups' actions (varieties). In short, this
kind of conceptual tool becomes useful when materiality gains an active role in the con-
figuration of society.
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSI.FICATION 193

(b) Potter's Expertise and Social Context of Production

A second variable used by this school is the analysis offormal and perceptive aspects of pot-
tery such as symmetry, size, or form complexity as representative of the potter's profile. Far
from considering the potter in evolutionary terms such as specialization and technical com-
plexity, morphology is used to identify apprentices and consider questions such as learn-
ing, knowledge transfer, and the social interaction of pottery production. The identification
of the potter's expertise using these variables demonstrates the existence of processes made
of repeated actions which produce certain standardization and technological knowledge
transfer (Budden and Sofaer, 2009). Because pottery features, which result from the specific
way-of-doing of each person> respond to social determinants and evidence the strategies
of the technological habitus used by a potter to manufacture a product in a concrete social
situation, their analysis would evidence the potter's profile. His/her technical skill and its
embodiment in certain morphological attributes of the pottery should be considered con-
tingent. Thus, tbey can be evaluated only in the concrete contexts for pottery making. In this
view, technical skill is not studied as the mere evidence of the potter's technical knowledge
per se or the existence or a specialized production, but rather as the response to a specific
social context; and, consequently, it constitutes a key element to enlarge on the dynamics of
a society.

(c) Isomorphism and Hybridization

Social technology understands that the ultimate interpretation of isomorphism and skeuo-
morphism is determined, not by simple imitation, but by the integration of praxis into a
contextual and social framework as well as into the technological and symbolic relationship
between the different kinds of materials and objects participating in any society. Thus, their
interpretation should consider that the loan of a form does not necessarily imply a functional
or symbolic translation: it cannot be automatically inferred by the sole formal similarity of
two objects, as only contextual analyses can determine the coincidence between function
and meaning.
Postcolonial perspectives, used in the analysis of material culture (Gosden, 2004; Van
Dommelen, zoo6), understand the translation of the form derived from the contact between
different cultures as hybridization. This idea is based on the premise that intercultural con~
tacts are never neutral and that the parts involved cannot be considered passive entities, but
rather active agents. The complex phenomena of hybridization occurs where the material
outcome of cultural contact is noticeably different from the original material culture of each
culture because both groups have actively modified, reinterpreted, and hybridized practices,
objects, and dynamics, giving rise to new contexts and meanings.
In the case of the typological analysis of pottery, the translation of the form, even if it
retains some reminiscence of the original, goes hand in hand with variations and reinter-
pretations which constitute a rupture in the structural relationship between the parts which
have originally made the object. Hybridizations in pottery form are quite common in the
Western Mediterranean during the Iron Age, particularly along the French coast (Dietler,
1997) and the Balearic Islands (Albero, 2011), resulting from the intensification of contact
between indigenous and Greek or Punic communities. Although formal references can
still be identified, these new hybrid types present their own peculiarities and characteris-
tics which affect many aspects related to pottery, from the manufacture system (hand-made
194 D. A. SANTACREU, M. C. TRIAS, AND J. G. ROSSELJ.,6

FIGURE 12.3 Format translation related to hybridization phenomena between Punic

wheel-thrown vessels and hand-made indigenous pottery in the Late Iron Age in Mallorca
(Spain).

pottery continues) to structural or metric elements. The result is a hybridized and reinter~
preted form, typologically different from the original schemes of both indigenous and for-
eign communities (Figure 12.3).

(d) Homology and Fractality

Conceiving ideas and matter as a group of connected webs and nodes rather than separate
elements (Latour, 2008) leads to Lemonnier's concept of representation (1993). Hence, any
technological action is related to a series of mental operations which are often unconsciously
internalized by a habitus which has to be interpreted in the global technological scheme of
the group and facilitates technological transfers and loans among crafts sharing the same
scheme. Furthermore, the concept of representation, the mental models of the sequence and
order of the action, is not exclusively related to a concrete technological action, but incorpo-
rates coutent and information of an ideological, social, and/or symbolic kind which function
in a network of supra-technological meaning affecting the totality of the signification and
semiotic schemes and models of the community.
The idea of the transversal direction of the signification schemes and technological pro-
cesses in a community suggested by Lemonnier (1993) leads to a fractal and homological
approach to society. This approach is related to the formal view of the object analyzed from
typological strategies. In this sense, the ultimate analysis of third-level tools is understood to
be inserted in an holistic interpretative framework. Thus, the study of typological identities
and correspondences which have been analyzed from third-level variables has to follow four
analytical levels: (a) an intrinsic level, restricted to pottery form; (b) a second intrinsic level
from a multidimensional view of pottery technology; (c) an extrinsic analysis covering the
diverse technological fields; and (d) a further extrinsic analysis between technology and the
remaining social spheres considering different scales, as they represent the many manifesta-
tions of the same phenomena.
 FORMAL ANALYSIS AND TYPOLOGICAL CLASSIFICATION 195

1his integral analysis is possible thanks to two strategies: the study of homology relations
among different fields and the analysis of the presence of fractal patterns.
The concept of homology, taken from Bourdieu's perspective (1977), reveals structural
similarities between different fields beyond their own peculiarities and dynamics. Applied
to the social interpretation of technology and, specifically, to typological strategies, this con-
cept of homology would refer to the similarities in the praxis and dynamics of the diverse
technological fields of the society. As an interpretative strategy, homology aims at analyz-
ing whether the behavior of each of the third-level tools used is restricted to the typological
dimension of pottery or whether structural homologies are observed in other dimensions
of the ceramic universe regarding the rest of the steps in the chaine opiratoire, such as raw
material management, paste preparation, or forming activities. This analysis provides a mul~
tidimensional picture of pottery and identifies whether the same phenomena are material-
ized throughout the pottery-making process. Later on, based on the logics of the homology
of fields, it is possible to evaluate if the dynamics identified in the pottery are present in other
technologies (e.g. metallurgy, building, glass-making, basketry).
The documentation of the same dynamics in other stages of pottery technology, as well as
their identification in the rest of the technological manifestations, furthers the analysis of the
typological differentiation, transcending the mere formal identification level to be inserted
in the dynamics of the global technological scheme of the community. This holistic view
would provide information regarding knowledge transfer dynamics, the social structures
related to the learning process, technical skill, the social value of objects, and so on.
The second tool which the comparison and signification aspects of third-level variables
allow is the application of fractal strategies which try to record the existence of recurrent
patterns or structures at several scales. Fractal patterns facilitate comparison between
microscalar and macroscalar processes, for they are understood as manifestations of the
same dynamics (Brown et al., 2005). A fractal interpretative framework constitutes an
effective tool to integrate the typological data into another manifestation of scalar models
which are expressed in the same way at upper levels, such as the technology or the social and
ideological relations of the group analyzed. This strategy aims at confirming whether the
typological patterns of pottery variability, appearance, and perception, as well as isomor-
phism and hybridization, now integrated into the technological praxis of the group and
thus with ideological, social, or symbolic contents and information, are also present in
other dimensions of the society. Documenting the patterns detected at these different scales
helps us evaluate the significance level of the typological proposal and articulate more
complex and coherent interpretative discourses beyond the classification strategy. It thus
demands integrating the typological strategy first into technological questions and then
expanding it to upper-level social and ideological discourses.

CONCLUSIONS

This chapter has examined the wide variety of systems used by archaeology to analyze
pottery form and decoration depending on the different philosophy, methodology, and
interpretative option favored, originating quite diverse typologies which respond to simi-
larly differing objectives. Nevertheless, the several interpretative proposals should not be
196 D. A. SANTACREU, M. C. TRIAS, AND J. G. ROSSELL6

considered exclusive but rather complementary: each proposal is important in the study of
the form. For instance, without the chronological determination it would have been hard to
deal with other aspects related to the use of ancient vessels. Nevertheless, once these tem-
poral and cultural parameters have been established, it should be considered whether it is
worth devoting so much effort to the description of pottery form and typological study.
Taking this view, some scholars have stated that form analysis and typology development
has turned into a "rite of passage" archaeologists have to go through. However, the descrip·
tion of vessel form and the typological classification of pottery should not nowadays be an
end in itself in archaeological research. A thorough critical reflection is needed to evaluate
the potential role and use of these kind of analyses in the study of pottery, both in historical
and anthropological terms. This question is particularly critical in the case of prehistoric
pottery, where a lack of systematization and large formal variability within a single assem-
blage could impair the development and application of reliable typologies able to achieve
accurate seriations and chronological determinations.

NOTE

L Although typological classifications of pottery may include technical aspects (e.g. fabric
or forming technique), this chapter deals with the classical concept of typology; that is, the
analysis and classifications focused on vessel form, size, and decoration.

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 CHAPTER 13

FABRIC DESCRIPTION
OF ARCHAEOLOGICAL
CERAMICS

IAN K. WHITBREAD

INTRODUCTION

CERAMICS found in the archaeological record were produced to serve many functions rang-
ing from the transportation and storage of goods, food preparation, cooking, and consump-
tion (Orton and Hughes, 2013: 247) to supporting activities involving heat, such as hearths
and crucibles, representative art, such as figurines and sculptures, and building materials
(Mills, 2013). The diversity of these functions and the wide geographical distribution of
ceramic production are reflected in the materials of which ceramics are made-their fabrics.
Ceramic fabrics can be described in terms of their compositional and structural prop-
erties; more specifically, the arrangement, size, shape, frequency, and composition of the
material constituents of the ceramic (Whitbread, 1995: 368). The term "fabric" is also used in
reference to groups of ceramics that are characterized by having specific material properties
in common (Tomber and Dare, 1998).
Ceramic fabric descriptions aim to record, so far as possible, not only significant geologi-
cal properties of the raw materials but also the potters' technological choices and actions
(the chaine operatoire; Sillar and Tite, zooo; Whitbread, 2001), such as preparation of the
clay body, vessel construction, and firing. Ceramic fabrics are synthetic in origin (Rice, 1987:
3). Their constituents reflect the geological characteristics of the regions from which the
raw materials were obtained. However, selection and processing of these raw materials are
dictated by the agency of potters with the aim of preparing clay bodies possessing physical
properties appropriate for the production methods and intended functions of specific end
products. Preparing a clay body may have required only the simple combination of water
with a natural clay, but potters often mixed different clays and matrix materials, removed
inclusions by sieving or sedimentation, that is settling in water, or added inclusions through
the process of tempering to optimize the physicomechanical properties of the vessel.
There are many reasons why a potter might make such adjustments. Often raw materials
are unsuitable for ceramic production in their original state (Nicklin, 1979). Furthermore,
 PAflRIC DESCRIPTION OF ARCHAEOLOGICAL CERAMICS 201

particular physical properties can enhance the forming and drying process, or the func-
tional performance of the resultant ceramic. For example, thick-walled vessels dry more
quickly and evenly prior to firing if inclusions are present that "open" the clay (Gibson and
Woods, 1990: 206). Ceramics that are repeatedly heated during use, such as cooking pots,
benefit from the presence of inclusions to increase mechanical toughness and thermal shock
resistance (Tite eta!., 2001). However, clay body preparation also depends on the ways in
which potters learn to engage with their materials and, in part, may reflect personal or cul-
tural preferences (Gosselain, 2000).
Construction methods such as pinching, coiling, slab construction, hammer and anvil,
molding, and wheel throwing, used individually or in combination, may leave their imprint
in the micromorphology of ceramic fabrics (Rye, 1981; Woods, 1985; Courty and Raux, 1995;
Whitbread, 1996; Raux and Courty, 1998). The most distinctive fabric characteristics, how-
ever, are produced by firing. The temperatures, oxidizing and reducing atmospheres, and
duration of firing affect the appearance and physicomechanical characteristics of ceramic
vessels. In most archaeological examples, the matrix component was converted to terracotta
or earthenware ceramic by firing it in temperatures up to 900-1000°C using a bonfire or kiln
(Gosselain, 1992). Under these conditions the crystalline structure of clay minerals breaks
down, as a result of the loss of structural water, and is converted to ceramic by the sinter-
ing and vitrification that subsequently develops (Shepard, 1956: 19-31, 49-94; Cardew, 1969:
61-68; Rhodes, 1973' 64-71; Rye, 1981: 29-40, 96-no; Rice, 1987: 93-94; Gibson and Woods,
1990: 24-56).

DESCRIPTION OF CERAMIC fABRICS

Fabric descriptions need, so far as possible, to record the critical properties of ceramic mate-
rials that fulfil the requirements of three fundamental and related areas of archaeological
interpretation (Whitbread, 1995: 366-378): characterization, technology, and provenance
determination. Characterization is the process of defining groups or classes of similar
ceramic fabrics that, in combination with additional evidence such as shape, decoration,
function, or find context, can be used to examine patterns of ceramic production, distri-
bution, and use. Technological studies investigate potting practices specific to one or more
social groups, which may reflect sociocultural identities, boundaries, and the transmission
of technical knowledge ( Gosselain, 2000 ). Finally, composition of the raw materials can be
used to study exchange and trade networks by determining the likely geological provenance
'
of ceramics that have passed into areas of different regional geology (e.g. Fitzpatrick et a!.,
2003).
At the most basic level of description archaeological ceramics are frequently divided into
two broad types of fabric, coarse and fine. There is no universally recognized distinction
between these types. In some situations "coarse ware" may simply refer to undecorated utili-
tarian ceramics in contrast to "fine ware;' which is often decorated, used for serving and
display. From a materials perspective, however, coarse and fine fabrics are normally dis-
tinguished by whether they contain inclusions visible to the naked eye (coarse fabrics) or
not (fine fabrics). Both coarse and fine fabrics can be described in hand specimen or thin
section using polarizing microscopy. Sometimes more advanced analytical methods are

J
202 IAN K. WHiTBREAD

required to address questions of characterization, technology, and provenance, and ceramic

fabric description is used in combination with these methods (Day et al., 1999: Stoltman
and Main fort, 2ooz). Generally speaking, however, thin-section petrography is better suited
for analyzing coarse fabrics and their inclusions and bulk chemical analysis is usually more
effective for fine fabrics.
A fabric description is the analyst's record of observations. So far as possible, it needs to be
kept independent of interpretations concerning technology and provenance. This approach
allows alternative interpretations to be proposed, tested, and amended without affecting
data from the original fabric analysis. The process of interpretation draws upon evidence
from fabric descriptions and characterization, but also additional sources such as regional
geology, production methods, and geochemistry. This wider analytical process of descrip-
tion and interpretation constitutes ceramic petrology (Whitbread, 1995: 28-29). As fabric
descriptions using polarizing microscopy are usually necessary to achieve adequate resolu-
tion for such interpretations, ceramic petrology commonly refers to such studies.
The greatest challenge in describing ceramic fabrics lies in recording complex visual
and physical information in ways that are meaningful and reproducible for archaeologists
unfamiliar with the fabrics in question. A second major challenge is in defining recogniz-
able, coherent, and sustainable fabric groups across different ceramic assemblages. Such
assemblages may contain overlapping ranges of material variation and are commonly stud-
ied by pottery specialists with diverse research interests. Macro- and microphotographs are
invaluable aids to fabric description but they also illustrate the difficulties outlined above.
They are severely limited in value without appropriate interpretation. Their restricted field
of view rarely conveys the full range of fabric variation encountered within a single sample,
and one photograph cannot illustrate the variation within a group of samples. Finally, they
are no substitute for the physical and optical tests carried out in hand specimen study or
under a polarizing microscope. For this reason, comprehensive written records are essen-
tial. Training in mineralogy and petrology is also necessary to gain proficiency in polar-
izing microscopy and in determining the optical properties of minerals and rocks in thin
section (Stoltman, 1989: 147: Nesse, 1991). Descriptions based on optical examination by
hand specimen or polarizing microscopy both rely heavily on the observational skills of
the analyst. As such they incorporate significant elements of interpretation and inevitably
reflect the analyst's range of experience in studying geological materials and archaeological
ceramics.

HAND SPECIMEN STUDIES

Ceramics break with a brittle fracture to leave a fresh surface that can be readily studied in
hand specimen. This analytical method lacks the accuracy and precision oflaboratory-based
techniques, such as chemical analysis or thin-section microscopy. However, it is not con-
strained by the limitations of physical damage and costs that accompany laboratory sample
preparation. For this reason, hand specimen examination continues to be the most effective
method for characterizing fabrics across ceramic assemblages from excavations and surveys
(Moody et al., 2003; Garcia-Hera, 2000; Pentedeka et al., 2010). It is often the first step in
selecting samples for more advanced analytical methods. More importantly, where fabric
 FABRIC DESCRIPTION OF ARCHAEOLOGICAL CERAMICS 203

groups defined by thin section or chemical analysis possess characteristic features in hand
specimen then it can be used to extend laboratory characterization from a set of samples to
the ceramic assemblage as a whole (Gauss and Kiriatzi, 2011).

Surface Preparation
Occasionally sherds of broken pottery display suitable breaks, but where tbese do not occur
it is necessary to create a fresh break. The most effective tool is a pair of spring-loaded pliers
that open wide enough to accommodate the thickness of the vessel walL These can produce a
clean break with little waste and minimal damage to the sherd. Pincers are effective with very
soft fabrics, but can crush or crumble harder sherds. A small hammer and chisel is best used
for producing fresh breaks on large objects such as brick, tile, or thick-walled storage jars.
Using these methods to remove samples for thin section or chemical analysis has the advan-
tage of leaving a fresh break for hand specimen examination.

Hand Specimen Description

There are many methods of describing ceramic fabrics in hand specimen, reflecting the dif-
ferent aims and experience of pottery specialists and the materials they study. One widely
used method was proposed by Peacock (1977), based on the study of Roman ceramics at
Carthage in North Africa. It describes the key components of ceramic fabrics in hand speci-
men, but aims to be simple enough for rapid sorting oflarge ceramic assemblages (Tomber
and Dore, 1998: 5-9). The method also forms the basis of fabric descriptions proposed by the
UK Prehistoric Ceramics Research Group (2010 ).
Color is a particularly distinctive property of ceramic materials in hand specimen. lt
does not feature in the definition of fabric given above because different firing conditions
can produce a wide range of colors within and between ceramic objects composed of the
same materials (Shepard 1956: 102-107; Beck, 2006). For example, there may be a different
colored core visible in a fresh break, or the external surface of a vessel may have a different
color from its interior (Velde and Druc, 1999: 122-126). The most frequent color is normally
noted, along with the range of variation observed on several sherds. Where variation appears
to be systematic it may reflect consistencies in the firing process and be a useful guide to the
technological control maintained by potters (Frankel, 1994), but relatively minor or erratic
variations should not be over-emphasized.
The most widely used method of describing color is based on comparisons with col-
ored chips in the Munsell' Soil-Color Chart (Munsell, 2009; Shepard, 1956: 107-113; Rice,
1987: 339-343). Each coded color chip provides a common reference for other researchers
to consult and interpret in their own terms. The value of these charts lies in aiding preci-
sion (repeatability) rather than accuracy (closeness to the "true" color); however, both can be
compromised as color perception varies between people and lighting conditions (Frankel,
1980; Gerharz et al., 1988). Groups of tablets are referred to by a color name which provides
a structured reference with wider tolerance than individual chip codes. For this reason,
Munsell' color names should be used rather than substituted with seemingly more "accu-
rate" personal color descriptions.
204 lANK. WHITBREAD

The hardness of a ceramic fabric depends upon its composition and degree of vitrifica-
tion and/or firing temperature. The Peacock system provides a rapid hardness assessment
in terms of soft (scratched with a fingernail), hard (scratched with a steel knife), and very
hard (not scratched with a steel knife). These divisions are simple and quick to apply, and
can be equated to Mobs' scale of mineral hardness. This is composed of ten minerals, from
talc (1) to diamond (10), each harder than the next. Hardness points based on Mobs' min-
eral scale can also be used to test pottery, but caution is necessary when interpreting results
from any scratch tests as they may reflect bonding of the material rather than its hardness
(Shepard, 1956: 113-117; Rice, 1987: 355-356). Mobs' scale is an ordinal scale. Its numerical val-
ues should therefore be treated as labels of rank and not used in mathematical calculations
(Curewitz, 2004).
Handling ceramics is a tactile process and, while subjective assessments may not be reli-
ably reproduced, the system recognizes variation in the "feel" (harsh, rough, smooth, soapy,
or powdery) of ceramic fabrics, which can be a distinctive property when processing large
quantities of material. The surface appearance of a fresh break is described by its fracture,
ranging from conchoidal to smooth, hacldy (angular facets), or laminated; although Shepard
(1956: 137) noted that this property catches the eye but tends only to be significant across
broad categories of fine and coarse fabrics.
Peacock described the frequency of inclusions as: sparse, moderate, common, or abun-
dant. These terms are subjective in the absence of independent reference points to maintain
consistency in their application, such as the percentage boundaries outlined below for thin-
section analysis. The mode (most frequent size visible) and the maximum grain diameter are
usually adequate measures of inclusion size. Equally significant is the degree of grain-size
sorting (well or ill) and rounding/angularity as assessed using comparator charts derived
from sedimentary petrography (Boggs, 2009: figures 2.3 and 2.12).
Peacock (1977: table 3) provides an inclusion identification table. With experience it is
possible to identify some inclusions accurately in hand specimen but it is also very easy to
make mistakes. Difficulties arise from the small size of most grains and their abraded sur-
faces. Inclusion color can also be misleading. For example, both quartzite and limestone can
be white, requiring use of a steel knife (which scratches limestone but not quartz) or dilute
hydrochloric acid (which fizzes if the material is calcareous) (Moody et al., 2003) to discrim-
inate between them. If in doubt, it is more reliable to describe the appearance of inclusions
first and then suggest possible compositions. Inclusion compositions can be verified by thin-
section microscopy.

Hand Specimen Description Example

This section illustrates the hand specimen fabric description for the Early Bronze Age sherd
described in thin section below (for illustration of the sherd in hand specimen see Plate 3).

Hand specimen fabric: Red, well sorted fine sand

Number of samples: 1
Sample number: 133
Color: 2.5YR 5/8 red.
Hardness: soft.
 FABRIC DESCRIPTION OF ARCHAEOLOGICAL CERAMICS 205

Feel: rough.
Fracture: hackly
Inclusion Frequency: c.20%.
Sorting: well sorted.
Maximum size: c.l mm.
Average size: c.0.5 mm.
Rounding: Subrounded-subangular.
Inclusion composition: predominant: pale yellowish gray rock fragments, rarely with
foliation, phyllite(?); very few: white limestone (softer than steel knife blade), very
dark gray quartz/feldspar(?) (harder than steel knife blade); rare: vughs

THIN-SECTION STUDIES

Analyzing thin sections of ceramic fabrics under the polarizing microscope provides
greater resolution than hand specimen study. Microstructures and the compositions of
inclusions can, for the most part, be more accurately identified down to a grain size of 0.03
mm, which is the standard thickness of a thin section (Reedy, zoo8: 109-231; Quinn, 2013:
39-68). Thin sections are studied by observing the optical properties of minerals, rock
fragments, and fired clay with respect to the path of polarized light which is transmitted
through the sample. Two types of polarized light are employed in combination. Plane polar-
ized light (PPL) uses one polarizing filter, located below the microscope stage, and crossed
polars (XPL) is applied when a second polarizing filter is inserted into the light path, above
the sample, at 90° to the lower polarizer. In this latter case, all light from the lower polar-
izer is blocked by the upper polarizer and the image appears to be black if materials in the
light path have no crystalline structure (e.g. glass) or where minerals are optically isotro-
pic, having the same optical properties in all directions. However, most minerals are opti-
cally anisotropic, having different optical properties in different directions, and refract the
polarized light passing through them such that they display a range of interference colors
(Nesse, 1991).

Sample Preparation
Samples need to be removed as chips that are large enough to be ground to a flat surface
between 1 x 2 em and 2 x 5 em in area, depending on the dimensions of the ceramic objects
and the size of the microscope slides. A larger surface area is more representative of a fabric,
especially if it contains large or sparse inclusions, and leads to a more reliable analysis. 1hin
sections are usually prepared as vertical cross-sections through the wall of a ceramic vessel
(Whitbread, 1996). Friable fabrics need to be impregnated with epoxy resin before grinding
(Quinn, 2013: 23-33). Once mounted on microscope slides the samples are ground to a thick-
ness of 0.03 mm, at which point most rock-forming minerals are translucent. Considerable
skill is required to prepare thin sections that are evenly ground to the correct thickness.
A sample should be large enough to allow at least two thin sections to be produced in the
event that there are problems in sample preparation.
206 IAN K. WHIT BREAD

Qualitative Thin Section Description

As fired sedimentary material, ceramic fabrics have been likened to metamorphosed sedi-
mentary rocks (Peacock, 1977), but there are significant differences. Sedimentary petrogra-
phy is most effective when studying materials dominated by sand-sized (o.o6zs-z mm) and
coarser grains, whereas ceramics are mainly composed of fired day-size particles or matrix,
often comprising 70% or more of the sample. While petrographic methods inherited from
geology are essential for describing igneous, metamorphic, and sedimentary rock and min-
eral inclusions (Williams et al., 1982), additional methods are required to address features
arising from the technological processes of ceramic production. For example, micromor-
phology of the matrix material can provide important technological information on pre-
ferred orien~ations arising from vessel-forming techniques and on the degree of firing used
to produce the ceramic. Ceramic fabrics can also contain anthropogenic inclusions not nor-
mally encountered in sedimentary deposits, such as grog (grains of pottery found within the
ceramic, cf. Whitbread,1986; Cuomo DiCaprio and Vaughan, 1993), industrial waste such
as slag from metal processing (Knowles and Quinlan, 1995), and agricultural waste such as
chaff(Quinn, 2013: 161).
Quantitative methods can be used to characterize ceramic fabrics (see below), but thin-
section descriptions are usually qualitative, focusing on the observation of compositional
and structural properties with supporting measurements, such as inclusion frequencies and
grain-size ranges. Early studies often focused on inclusion compositions owing to their criti-
cal role in provenance determination and often incorporated interpretation within descrip-
tions, which meant that technological assumptions were not always tested. For example,
inclusions might be referred to as "temper" without an explicit justification for their being
intentionally added by the potter. In contrast, the presence of crushed schist temper in
Hohokam buff wares was argued to be temper by Miksa (2001) based on a range of explicit
properties comprising grain size distribution, rock homogeneity, angularity, fractured
grains, finely disseminated micas from the crushed schist, and occasional grains of volcanic
rock and quartzite from implements used to do the crushing.
Greater sensitivity to recording technological properties has been introduced by applying
a more comprehensive and systematic method of description that allows analysts to record
all features observed in a ceramic thin section. By enabling the characteristics and properties
of ceramic fabrics to be isolated and recorded, their significance, in terms of technologi-
cal and provenance determination, can be more effectively established rather than merely
assumed. To this end, elements of sedimentary petrography and soil micromorphology,
using the system proposed by Kemp (1985: 15ff.; derived from Bullock et al., 1985), are com-
bined and modified for ceramic fabrics (Whitbread, 1995: 379ff.; see also Josephs, zoos). This
approach adopts existing terminologies where appropriate but remains open to adaptation
to accommodate new developments in ceramic petrology.
It is most efficient to sort samples of ceramic fabrics into groups and/or classes with
similar properties before describing them (Quinn, 2013: 73-79), rather than combining the
descriptions of individual samples as a basis for constructing a classification. Groups may
be based on broad geological characteristics, such as major rock or mineral components,
while classes may constitute subdivisions based on secondary compositions or technological
variation, such as grain size, sorting, or frequency. The classification is tested by attempting
to reassign samples to alternative or new groups and classes based on further examination
 FABRIC DESCRIPTION OF ARCHAEOLOGICAL CERAMICS 207

of their compositional and micromorphological properties. The procedure ends when the
classification achieves its greatest stability, and reassigning samples no longer improves the
definition of groups or classes within the dataset.
Fabric descriptions therefore usually refer to collections of samples rather than individual
pieces. Various degrees of diversity are often observed between the fabric characteristics of
individual samples within a fabric class. This is an important property, expressed in terms of
the homogeneity of the class, which can arise from a number of factors. It may reflect mate-
rials variation inherent within the production of certain ceramics or possibly limitations
in the sampling program for fabric analysis. Acknowledging this variation by defining the
boundaries of class membership is an effective way to establish the properties that must be
met for attributing future samples to a group or class, rather than relying on the description
of a "typical" sample without any indication as to the range of variation that may be present
between related fabrics.
The frequencies of different components within a fabric can be estimated using point-
counting or digital image analysis (see below). More commonly, however, estimates made
using comparator charts are favored as a more rapid method of evaluating proportions based
on illustrations of different percentage areas of the field of view (Matthew et aL, 1991). These
estimates have limited accuracy and precision, with a general tendency towards the over
estimation of proportions, especially where fabric properties vary widely across the thin sec-
tion or where inclusions are poorly sorted. One way of reducing such inherent errors is to
allow a degree of tolerance by referring to frequencies in ranges. Frequency ranges derived
from soil micromorphology are: predominant (>70%), dominant (70-50%), frequent (50-
30%), common (30-15%), few (15-5%), very few (5-2%), rare (2-0.5%), and very rare ( <0.5%)
(Whitbread, 1995: table A3.1; Kemp, 1985: 17).
The shape and arrangement of voids, inclusions, concentration and depletion features,
and micromass (material less than 0.01 mm, principally the fired clay and fine silt; Kemp,
1985: 15) constitute the fabric microstructure (Whitbread, 1995: 369). Voids (or pores) in
ceramic fabrics result from working the clay body, drying, and firing (Velde and Druc, 1999:
m-115), although some are derived from burnt-out organic matter (Quinn, 2013: figure
3-27). They can also provide information about forming and shaping methods through their
preferred orientation (Reedy, zooS: 191-194). Voids commonly occur in four basic catego-
ries: long, narrow planar voids, wide channels, irregular vughs, and circular vesicles, based
on types defined in soil micromorphology (Whitbread, 1995: table A3.3).
The packing of inclusions is a distinctive micromorphological property, and one that may
have been evaluated by potters in terms of the "sandiness" of the clay body. It can be effec-
tivelyrecorded in photomicrographs, but is difficult to articulate in text-based descriptions.
The coarse/fine (elf) related distribution (Stoops and )ongerius, 1975) in soil micromor-
phology is one attempt to achieve such a description; however, only the "porphyric" -related
distribution of coarser inclusions enclosed in a groundmass of finer material is really appli-
cable to ceramic fabrics (Whitbread, 1995: 381). Related distributions have not been widely
adopted in ceramic petrography as they are very difficult to assess when fabrics contain
poorly sorted grain sizes. Examination of this important technological property needs fur-
ther development. In contrast, the ratio of coarse, fine, and void components of the fabric
(c:f:v ratio, e.g. 20:JO:IO) has been more effective. 11re boundary between coarse and fine is
normally set at the upper limit of the micro mass to give a ratio between grains, fired clay
matrix, and voids.
208 IAN K. WHITBREAD

The micromass is optically active if relic clay mineral domains show the optical properties
I I
of extinction and birefringence when the microscope stage is rotated under crossed polars.
Optically inactive micromass shows no change in optical properties under crossed polars.
This property reflects the extent of firing, estimated at less than about 700 'C in oxidizing
conditions from experimental studies (Whitbread, 1995: 391) for optically active micromass,
but is subject to firing conditions and clay compo$ition. Used with caution, it can give a gen-
eral indication of the extent to which the fabric has been fired (Whitbread, 1995: 391; Roper
et al., 2010 ). Optically active micromass can display a wide range of structures, orb-fabrics
(birefringent fabrics), distinguished in soil micromorphology as: speclded, striated, poros-
triated, granostriated, monostriated, parallel striated, cross-striated, random striated, unis-
trial, and bistrial (Kemp, 1985: 24; Whitbread, 1995: table A3.6) with increasing degrees of
preferred orientation arising from manipulation of the clay body during vessel construction
and the orientation of the thin section (Whitbread, 1996).
The composition of aplastic inclusions continues to be the most important fabric property
studied in thin section. Descriptive information for mineral and rock fragments is taken
directly from geological sources (e.g. Williams et al., 1982; Nesse, 1991). Compositions are
normally recorded in diminishing frequencies of occurrence, which draWs attention to the
most frequent inclusions at the beginning of the description. Where a fabric class contains
more than one sample then some compositions are likely to be represented by a range of
frequencies that define the boundaries of variation. Distinctive properties of each composi-
tional component are briefly noted to aid comparison with samples from other assemblages.
It can be difficult to identify accurately small, weathered, or infrequent minerals and rocks in
ceramic thin sections. In such cases, a question mark and brief explanation can be used for
identifications that are subject to future verification.
The primary advantage of adopting descriptive terminology from soil micromorphol-
ogy has been in describing fabric components other than mineral and rock fragments.
This applies in particular to concentration and depletion features (Kemp, 1985: 32, 46, 53;
Whitbread, 1995: 386-388). Textural concentration features are clay-based components
with different textural properties. In most cases these are clay pellets that are natural
inclusions within the clay raw materials, as opposed to other clay-based inclusions, such
as argillaceous rock fragments and grog (Whitbread, 1986). "Amorphous'' concentration
(depletion) features are areas with increased or decreased opacity resulting from relative
amounts of "amorphous" material, such as iron oxides, in the clay. The term "amorphous"
is used because this material may not be solid but instead disseminated within the ground-
mass at a scale too fine for the resolution of optical microscopes. Crystalline concentration
(depletion) features are similar, but refer to crystallitic material, such as finely dissemi-
nated calcite. Cau Ontiveros et al. (2002) have examined the nature of secondary calcite
in ceramic fabrics, identifying its occurrence as micritic clots, micrite and microsparite
fringes around pores, microcrystalline calcite lenses, geodetic calcite pore infillings, and
surface encrustations.
This method of describing ceramic fabrics in thin section has not been universally
adopted; however, it probably remains the most comprehensive approach to date. 1o some
degree extensive description raises diffiCulties as it is time consuming to record and occu-
pies considerable space in publications. However, in addressing a wide range of properties
it has the potential for further modification and development to suit particular research
goals. So far, most adjustments have been made to reduce some descriptive elements, such
 FAll RIC DESCRIPTION OF ARCHAEOLOGICAL CERAMICS 209

as "amorphous" and crystallitic concentration and depletion features, that brought little to
the analysis of particular ceramics. Examples can be found in Wilson et al:s (1999) study of
Early Bronze Age pottery from Knossos, Crete, Day's (2ou) analysis of Bronze Age transport
stirrup jars in the Eastern Mediterranean, and Gauss and Kiriatzi's (2011) extensive hand
specimen and microscopic examination of Bronze Age pottery from Kolonna on the island
of Aegina, Greece. Quinn (2013: So, wo) has further modified the system, suggesting a sim·
pler organization with respect to inclusions, fired clay matrix, and voids, and the addition of
a summary or comment section. All such adjustments that enhance the recording, interpre-
tation, and dissemination of fabric information are beneficial to the study of archaeological
ceramics.

Qualitative Thin Section Description Example

This section illustrates a qualitative thin section description of Early Bronze Age pottery
from Kouphovouno, Greece (Cavanagh et aL, 2007). Micrographs of the sherd in thin sec-
tion (PPL and XPL) is presented in Plate 3·

Polymictic sand (phyllite, quartzite-schist, limestone, well sorted)

Number of samples: 1
Sample number: 133

Fabric Group (Class) Summary

The sample in this group is characterized by polymictic sand, that is, sand-sized grains of
different rock types. The phyllite-quartzite-limestone class is homogeneous and character-
ized by well sorted, rounded inclusions of phyllite and polycrystalline quartz with frequent
biotite and muscovite mica and very few micritic limestone. The polycrystalline quartz with
mica is probably schist, but foliation is rarely evident in the sample. Monocrystalline quartz
and sandstone occur more rarely. The fabric micromass is optically active.

Fabric Group (Class) Interpretation

The fabric composition is indicative of a region of metamorphic rocks, or of sedimentary
rocks that incorporate metamorphic clasts. The fabric appears to have been tempered with
sand based on the well-sorted, rounded character of the inclusions and absence of fine-
grained inclusions of similar composition in the groundmass. The optically active micro-
mass indicates firing temperatures below about 700°C, subject to clay mineralogy, and the
atmosphere and duration of firing.

Microstructure
There are very few meso- to microvughs and inclusions have a single-spaced porphyric
related distribution. Preferred orientation is poorly developed except where phyllite grains
lie subparallel to the top edge of the rounded rim of the vessel and where monostriated
b-fabric is locally present.
210 IAN K. WHITBREAD

Groundmass
The fabric is homogeneous, Micromass is optically active with predominant stipple-specked
and very few monostriated b-fabrics, Color is dark yellowish brown (xp and pp, x 15),
Inclusions occur in the range 1.26-0.03 mm, mode c.o.s mm. The grain-size distribution is
unimodal and well sorted. Inclusions are predominantly well rounded to rounded with few
subangular grains, mainly mono- and polycrystalline quartz,

Inclusions
Based on comparator charts, c:f:v1011 = c.20:75:5
Proportions below are expressed as percentage estimate of inclusions.

frequent: PHYLLITE. Inclusions are 1.26-0.1 mm, mode c.o.5 mm, well sorted, well-
rounded to rounded, composed of white mica, biotite, quartz, and rarely calcite, Preferred
orientation is strongly developed, POLYCRYSTALLINE QUARTZ-SCHIST, Inclusions are
1-0.15 mm, mode c. 0.5 mm, moderately sorted and well rounded to rounded, composed of
quartz with undulose extinction, biotite and muscovite micas, rarely calcite and iron oxide,
very rarely white mica and fresh plagioclase feldspar. Preferred orientation is present in few
cases; grain boundaries are frequently crenulated or straight Sub grains are frequently equi-
granular and in few cases distinctly uneven in size. Polycrystalline quartz and schist appear
to be end-members in a range of variation with increased occurrence in micas and preferred
orientation in the latter.

few: MONOCRYSTALLINE QUARTZ. Inclusions are o.64-0.o3 mm, mode c.o.os mm,
moderately sorted, angular to subangular with undulose to slightly undulose extinction.

very few: LIMESTONE. Inclusions are L2-0.27 mm, mode c.0.5 mm, poorly sorted, pre-
dominantly rounded, and rarely angular. Grains are composed of equigranular sparite and
very few micrite.

very rare: SANDSTONE(?), The inclusion is 1.25 mm, It is well rounded and composed of
fine to very fine sand-sized, well-sorted subgrains with intergranular silica and iron oxide
cement. The grain-size distribution and discrete subgrain boundaries distinguish this grain
from other inclusions, but its membership of the poly crystalline quartz-schist cannot be
ruled out

Clay Pellets (Textural Concentration Features)

Based on comparator charts, c.7% of the field
They are predominantly dark reddish brown (xp and pp, x15), o.8-o.o3 mm, mode
c.0.15 mm, well rounded, moderate apparent sphericity, high optical density, and sharp to
clear boundaries, Predominantly optically slightly active. Constituent: c.o-3%, predomi-
nantly polycrystalline quartz, c.o.07 mm.
"Amorphous" concentration (depletion) features
Based on comparator charts, <3% of the field
 FABRIC DESCRIPTION OF ARCHAEOLOGICAL CERAMlCS 211

These are predominantly very dark reddish brown (xp and pp, x15) pure nodules. They are
well rounded to subangular and c.0.24-0.o3 mm, mode c.o.os mm.
Crystalline concentration (depletion) features: absent.

Quantitative Thin Section Description

An alternative approach to the description of ceramic fabrics in thin section is to express
their salient properties in quantitative terms. The method of modal analysis, adopted from
geology, systematically samples by grid-point, line, or area (Middleton et al., 1985; van der
Plas and Tobi, 1965) the inclusion compositions and/or grain sizes, which are used to gener-
ate frequency distributions.
Potters no doubt intentionally adjusted grain-size distributions of clay bodies when refin-
ing or mixing clays and adding temper. However, such frequency distributions have to be
interpreted with care (Darvill and Timby, 1982) as grain sizes can vary naturally depend-
ing on the circumstances of sediment deposition. Recording both inclusion compositions
and grain sizes facilitates temper identification by correlating the occurrence of particular
compositions with parts of the grain-size frequency profile; for example, in discrimination
between mudstone temper and quartz/feldspar in the coarse and fine fractions respectively
of Corinthian A' transport amphora fabrics (Whitbread, 1995: figure 5.7). Interpreting these
distributions can nevertheless be challenging as the lithologies of inclusions are often cor-
related with grain size in natural sediments.
Stoltman (1989) introduced a measure in which the relative percentage proportions
of sand, temper (if separate from sand), and matrix (clay and silt) are used to character-
ize ceramic fabrics. The procedure is aimed at quantifying the relationships between natu-
ral inclusions, those intentionally added by the potter, and the fired clay matrix. He used
this approach to show that Spring Hollow Incised ceramics are technologically distinct from
Linn ware based on samples from the Upper Mississippi Valley, USA.
Petrofacies models have also been used to describe ceramic fabrics through quantifica-
tion, primarily for the purpose of provenance determination (Miksa and Heidke, 2001).
Sand deposits in a defined region are classified into different petrofacies on the basis of com-
position and spatial occurrence. These petrofacies are considered to be potential areas of
temper procurement and their characteristic compositions can be tested against quantita-
tive analyses of ceramic fabrics. The Gazzi-Dickinson method (Dickinson, 1970; Ingersoll
et al., 1984) is used, in which all sand-sized and larger grains are counted as individual
mineral compositions regardless of whether the minerals occur in isolation or within rock
fragments. 1his approach reduces the influence of sand maturity on the results when rock
fragments have broken down to their constituent minerals. It also removes the effects of dif-
ferent grain-size frequencies on composition. One particular advantage of this system is that
the results are not converted to percentages, thereby avoiding the constant-sum problem
(Aitchison, 1986). This allows statistical analyses, such as correspondence and discriminant
analysis, to be applied to the data (Heidke and Miksa, 2000).
Digital image analysis is becoming widely used to describe ceramic fabrics, especially
with the availability of public-domain software such as Image) (Rasband). The process
requires one or more digital images of the field of view from a ceramic thin section, typi-
cally one in pp and one in xp using circular polarization (Wahlstrom, 1979: 196), or two in
2l2 IAN K. WHITRF.EAD

xp with polarizing filters set at 0° and 45° so that the resultant images can be processed to
remove the effects of optical extinction. The images need to be calibrated with respect to
pixel dimensions for the scale of magnification, processed to highlight the features of inter-
est being measured, and then converted to a binary (black-and-white) image for automated
measuring of morphological dimensions and orientations (Velde and Druc, 1999: 184-189;
Reedy, zoo6).
Image analysis is an effective technique where the principal research questions can be
addressed by studying grain-size frequency distributions. Bouchain and Velde (zom) used
the technique to identify different production technologies in Gaulo- Roman cooking pots,
storage vessels, plates, and other tablewares produced locally over a 50o-year period at
St Marcel, France. The mineralogically homogeneous fabrics contain mainly quartz, potas-
sium feldspar, white mica, and biotite inclusions. The underlying similarity in grain-size fre-
quency distributions in the thirty-two samples analyzed suggest a high degree of consistency
in the sedimentary raw materials that were selected. Nevertheless, differences in raw materi-
als processing were detected, as some samples were shown to contain erratic large grains,
interpreted as temper, whilst others were found to have sharply delimited maximum grain
sizes indicative of sieving. It was thought that differences in the grain-size frequency dis-
tributions might be related to vessel function, particularly for cooking pots, where coarser
fabrics would improve resistance to heat stresses. However, the results show that rather than
containing coarser inclusions there was a propensity for cooking-pot fabrics to have greater
quantities of inclusions.
Quantitative descriptions of ceramic fabrics are aimed primarily at characterization based
for the most part on inclusion properties. The groups so formed may be according to criteria
related to manufacturing technology, raw material properties, or provenance. These quanti-
tative analyses have the advantage of utilizing graphical and statistical evaluations which are
not available in qualitative fabric description. However, by focusing on a prescribed set of
properties, quantitative descriptions are less sensitive to clay-based and micromorphologi-
cal features of ceramic fabrics.

CONCLUSION

Fabric description of archaeological ceramics can be achieved at several levels of detail. Brief
descriptions can be adequate as an aide memoire for the analyst working on a particular set
of ceramics, or for a non-specialist who does not need to engage directly with the practical
issues of fabric analysis. However, an absence of information leaves many areas of uncer-
tainty for other researchers seeking to identify the described fabrics in their own studies or to
assign new samples to previously defined groups and classes. More comprehensive descrip-
tions go some way to addressing these problems, although they can never fully substitute for
direct observation of the material itself. Perhaps more importantly, comprehensive qualita-
tive descriptions offer the greatest potential for exploring fabric properties in terms of the
chaine opiratoire and for exploring the effects on ceramic fabrics of experimental studies,
such as firing experiments, in which the origin and development of particular fabric proper-
ties can be monitored. Quantitative approaches trade flexibility in the observation of dif-
ferent fabric properties for more reliable measurements of a prescribed set of properties,
 FABRIC DESCRIPTION Of ARCHAEOLOGICAL CERAMICS 213

whether it is modal analysis of component compositions or grain-size frequency distribu-

tions. Rather than recommending the integration of qualitative and quantitative methods,
which would add considerably to the time and effort required for fabric analysis, the most
effective way forward is to regard the range of descriptive approaches as a toolkit and utilize
the most appropriate tool for the particular research question being undertaken.

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p

CHAPTER14

ANALYTICAL DRAWING

PRABODH SHIRVALKAR

INTRODUCTION

AT any archaeological site, the ceramic assemblage is the foundation of the research project
and plays an important role in the identification of cultures, cultural complexities, trading,
subsistence and utensil function, market economies, and so forth (Shirvalkar et al., 2010 ).
In spite of its importance, ceramic analysis suffers from issues of standardization related to
ceramic nomenclature, classification systems, and formal descriptions. The subjectivity in
ceramic descriptions has created enormous confusion in archaeological literature and pre-
vented, or at least hindered, cross-site and cross-cultural comparison. As early as the 1930s,
scholars were aware of these issues, and an attempt was made by March (1934) to use uniform
nomenclature for ceramic description. Part of the confusion and discontinuity in nomen-
clature is related to the various disciplines and theoretical frameworks which have shaped
archaeological ceramic analysis over the last few centuries. These frameworks can be broadly
categorized into three phases: the art-historical, typological, and contextual phases.
During the art-historical phase-that is, in the nineteenth century-the graphic represen-
tation or illustration of pottery was artistic and non-technical. Often artists were employed
by excavators to paint representations of archaeological ceramics, but only those considered
to have artistic merit, such as the decorated, glazed, and painted wares. These types of draw-
ings put more emphasis on representation of complete vessels than fragmentary vessels. In
the Indian context such drawings were made first by Meadows Taylor, and were published in
1873 by Taylor (Figure 14.1).
During the typological phase which can be dated to the arrival of Sir john Marshall in India
in 1904 onwards, archaeologists and artists paid attention to the chronological seriations of
ceramics as a source of relative dating material. Illustrations of ceramics began to focus on
ceramic types and the evolution of various forms as well as the cross-cultural comparison
of ceramics. The third phase, the contextual phase, started in India around the 196os, focused
on ceramics as a source of cultural information or a means of addressing broader archaeologi-
cal and anthropological questions, such as trade and exchange and technological development,
and as a direct outcome of scientific development and collaborative researches, such as the use
of ethnographic analogies. During this phase, ceramic illustration began to focus more on those
aspects of ceramic vessels which were considered to have functional significance.
218 PRADODH SHIRVAtKAR

Earthen Vessels, Andola Cairns, i si?,e.

Ear1hrn Vessels, ]izearji Cairns, { size.

3!..6 .. /UI!tl{ 3:.3"1111<11 3'-9"J.II6"

1~$"/PJAI>II!.fM 2'- J • #14fl!l riA. 2~3"Pfllfii(;Ttfl?

FIGURE 14.1 Art-historical period pottery illustrations.

 ANALYTICAL DRAWING 219

This approach tried to understand the function of ceramics based on the geometrical clas-
sification of forms, and is illustrated in the works of Ansari (1961), Webster (1964), Hardy-
Smith (1974), Millet (1979), Orton (1980), Miller (1985), Dales and Kenoyer (1986), and
Sinopoli (1991). The main objective or basic importance of ceramic illustrations during this
period was to convey the details of ceramics with visual aids in a scientific manner rather
than using an artistic approach. Therefore, illustrations needed to be visually clear and pres-
ent exact information, such as an accurate scale and/or metric relationships between ele-
ments, and as much detail as possible.
One of the most important changes during the contextual period was the recognition that
pottery illustrations are not realistic or artistic representations or artworks, but are techni-
cal illustrations designed to indicate dimension, form, manufacturing technology, surface
features, and decorations. Despite these changes in perception and function of ceramic
illustrations over the years, the techniques and methods used have changed very little. In
this chapter, we propose a new methodology for recording and illustrating archaeological
ceramics which combines monochrome line and shading drawings with photography and
analytical software, and facilitates their scientific and technical study.

MONOCHROME LINE AND SHADING ILLUSTRATIONS

In pottery illustration, the most important aspects that are represented include diameter,
height, thickness, angle, and decoration (if present). The basic materials required are con-
tour gauge or pottery comb, set squares, divider, vernier caliper, scale, radius chart, eraser,
tracing paper, and a good quality clutch pencil.
1be first step of pottery drawing is to hold or place a rim sherd or base sherd at the proper
angle. This angle represents the actual curvature or orientation of the rim, which depends on
the natural resting point of the rim. On the basis of this angle, the illustrator can reconstruct
the shape and form of the vessel. Therefore, the rim is placed flush on the tracing paper, so
that no light is visible between the paper and the rim. Then, using a pencil, the exact cur-
vature line of the outer portion of the rim is traced where it is resting (Figure 14.2a). This
tracing is placed on the radius chart to measure the exact diameter of the rim. Generally, the
chart provides rim diameters estimates at 1 em intervals. While placing the rim on the chart
it is necessary that both ends of the rim as well as the middle portion meet properly within
the radius (Figure 14.2b). Once the diameter of the rim is recorded, the rim is placed on the
tracing paper in a similar way as in the first step, while recording the radius. Depending on
whether the rim inclines on the inner side or outer side, a set square (45') is attached to it
to make a perfect right angle. Using this set square the height of the sherd is calculated. At
the same time the distance between the rim resting point and the set square resting point is
calculated (Figure 14.2c). These height and width measurements are important for calculat-
ing the diagonal of the pot. The diagonal calculations are made using the Pythagorean for-
mula: a'+ b' = c', where c =the diagonal. For example, if the distance between rim resting
point and set square is 2 em and the height is 4-5 em then theformula is [2]' + [4-5!' = [24.25].
--l24.25 = 4-9 em. Thus 4-9 em is the diagonal of the pot.
After initial calculations a contour gauge or profile comb is used to get the exact shape of
the rim sherd. The comb is pressed on the rim sherd, which gives a negative impression of
220 PRABODH SHIRVALKAR

(c)

FIGURE 14.2 Steps of traditional pottery illustration (part 1).

the shape (Figure 14.2d). This negative impression is traced on the tracing paper. Then the
thickness of the sherd is measured from top to bottom using a vernier caliper or divider
(Figure 14.3a). Measurements taken at different points along the inner side of the negative
impression are plotted to accurately record the inner line of the sherd (Figure 14.3b ). Once all
points are plotted and connected, the total thickness of the sherd is revealed, and the draw-
ing is referred to as the section of the pot.
The height, width, and diagonal are plotted on the tracing paper to create a right angle.
The negative impression along with its thickness is then matched with the right angle. While
placing the impression, the resting and end point of the rim drawing should perfectly match
the diagonalline (Figure 14.3c). It is very important that the line from the diagonal to the rim
fits perfectly; if it does not it is highly lilzely that the angle between the rim and the body of
the sherd might be wrong.
Once the rim sherd is placed at a perfect angle, from the resting point of the rim a hori-
zontalline is drawn across the top of the paper. The length of this line is dependent upon the
diameter of the rim. For example, if the diameter of the rim is 10 em then the line is 10 em.
Using the left side of the pot as an example, the right side is drawn (i.e. a mirror image of the
left side of the pot is created.) The height, width, and diagonal of the right side are drawn
according to the same procedure as the left. On this right side, only the outer edge of the pot
is shown and not the thickness (Figure 14.3d). At the center exactly, 5 em in our example, a
central line is drawn vertically to divide the pot into two parts, left and right. The right part
is considered the elevation of the pot, and any decoration present on the outer surface of the
pot is drawn on this side (Figure 14-4a). 1be left side is considered the section of the pot, and
any decoration on the inner side of the pot is represented in this part (Figure 14-4b). This
section or thickness is filled with black shading or hatched decorations or sometimes left
plain. If there is decoration on the top of the rim it is shown on the top of the illustration in
 ANALYTICAL DRAWING 221

><m (d)

;, ;; 5
% g ~

om om

FIGURE 14.3 Steps of traditional pottery illustration (part z).

alignment with the diameter of the pot (Figure 14-4c). This format applies to painted decora-
tion as well as to applique (Figure 14.4d) and incised decorations (Figure 14-4e).
After the completion of the drawing it is very important to insert a scale or scale bar spe·
cific to that drawing in order to accurately represent the size of the pottery. The scale is also
extremely important when the illustration is reduced or enlarged for publication. Without
this, the actual size of the pot cannot be judged.
There are various alterations that may be made to these basic and traditional guide-
lines. For example, some illustrators indicate the width of the pot using a hatched section
rather than a black or shaded one, while others leave it blank. Some illustrators draw the
section on the right-hand side instead of the conventional left-hand side. The value of the
traditional ceramic illustration style is that it is "international": archaeologists specializ-
ing in any region or time period are able to understand and interpret ceramic illustrations
from another geographic region or period. In recent publications, the traditional norms
have been completely overlooked and illustrations have been made in different formats
(Figure 14.40. These unconventional illustrations make it difficult to understand the pot-
tery, since they fail to convey analytical information and attributes of the ceramics in a
familiar and accessible way.
"Line and shading" drawings, described above and traditionally used in ceramic illustra-
tion> are simple monochrome artworks: drawings are rendered in black, and variations are
shown using different patterns of shading to give an idea of depth, motifs, and curvatures.
These drawings basically illustrate the shape of the pot, its cross-section, and its decorative
motif(if any). The remaining attributes of the vessel, such as. the actual color of the pot and
its decorations, are usually explained in the text or presented in a separate section of colored
plates or photographs.
222 PRA RODH SHIRVALKAf<.

(c)

f' ...... /
?

(d)

ID

rr =-~)=--=-1 _. i.¥1.~40 ')\("~~

j),~ ~ \
1
644
641

FIGURE 14.4 Various aspects of pottery illustration. (a) Rao (1985), (b) Shinde and
Kar (1992), (c) Dhavalikar, et aL (1996), (d) Sankalia (1963), (e) Dbavalikar and Possehl
(1992), (f) Uesugi and Meena (2012).
 ANALYTICAL DRAWING 223

The traditional method of pottery drawing has been criticized by many scholars, includ-
ing Shepard (1985), who pointed out the limitations and drawbacks of these illustrations,
whether section profile or rim profile. The section profile is used to understand shape in
outline and the thickness of the ceramic. Thickness depends upon the manufacturing tech-
nique and may vary within the ceramic itself. The black-and-white combination is very high
contrast and is not appealing. In the case of the rim profile, accuracy has to be maintained
in the angle of the pot in order to create a perfect drawing. In most cases a horizontal top
line is shown, but that is used as a convention that does not deny the possibility that the
angle is wrong. Furthermore, the accuracy of the rim profile depends upon breakage pat-
tern, which introduces an element of randomness into the illustration (Shepard, 1985). As
far as the drawing of motifs, glazes, slips, or painted decorations is concerned, black-and-
white illustrations have inherent limitations, particularly for polychrome decorations. "It
was once customary to use various symbols, such as hachure, crosshatching, stippling, etc.
to indicate different colours" (Shepard, 1985: 258). These symbols are unable to capture sub-
tleties and the relative values of different colors. The drawings are effective in illustrating
simple monochrome pottery which has very little color variation, but in cases of multicolor
ancient pottery specimens, such as bichrome and polychrome, variations are not reflected
in the drawings. Finally, all traditional drawings appear much the same, and this can make
comparing or distinguishing shapes, styles, and colors of specimens from different sites or
regions rather tedious and monotonous.

NEW METHOD OF ILLUSTRATION

1be importance of photography in archaeology is well known, but in the case of ceramics
generally handmade drawings are still preferred to photographic documentation. According
to Orton eta!. (1993: 88) this is because "it has been found that drawings give a better repre-
sentation of shape and can show both inside and outside simultaneously, which photogra-
phy cannot do:' This philosophy is a hangover from the days when photographic skills and
equipment were not as sophisticated as they are today and the cost of printing or publishing
photographs, particularly in color, was prohibitive. However, modern photographic tech-
niques, equipment, and computer software have resolved many of these issues. Therefore,
we propose a new method of ceramic illustration which takes into consideration the benefits
of both traditional line and shading drawing and photography. This new illustration style is
basically a combination of traditional line drawing and color photography, which preserves
the technical/analytical profile of the sherds (i.e. the cross-section, the left side representing
the inner surface of the pot as well as its section, and the right side representing the outer
surface of the pot and its elevation) while at the same time providing an accurate representa-
tion of a vessel's color and texture.
The first stage of the new illustration method requires the drawing of traditional line and
shading drawings of the ceramic sherds. For the photographic documentation of the sherds,
a digital SLR camera with a so mm lens is required. This standard lens helps to curtail any
distortion in the picture> which is a common problem with images taken using a wide-angle,
telephoto, or zoom lens. Photographs should be taken using natural light, filtered with a thin
white doth. Bright sunlight might change the original color of the ceramics, and filtering in
224 PRABODH SHIRVALKAR

this way helps to capture true colors. In certain cases, white thermocol (polystyrene) sheets
can be used to reflect or bounce the light, which helps to record the original or true colors of
the pottery fragment and its motifs.
While photographing the sherd, it is crucial to keep the rim flat or on a horizontal plane,
otherwise the curvature of the rim creates problems in the next stage. At the same time,
owing to the curvature of the body, the painted motifs also gain a curvature, which needs
to be avoided in order to allow their correct orientation. Owing to the natural curvature of
the rim, it is not possible simply to overlap or "digitally paste'' the photograph within the
line drawing. To overcome this methodological problem, table photography should be used
instead of traditional dimensional photography for archaeological specimens. In table pho-
tography or flat photography, the photographs are taken from 180' or vertically, also known
as a bird's-eye view, thus eliminating other attributes of the pot such as thickness and curva-
ture (Figure 14.5a).
For decorative motifs located on the top of the rim, the photograph should have proper
dimension and perspective to record the precise curvature of the rim and motif. In this
case the curvature of the rim portion has to be maintained with its original curvature
(Figure 14.5b ). This photograph can then be matched with the boundary of the line drawing
and with the diameter of the pot just as with traditional line drawings, photographic docu-
mentation requires the use of a scale: pottery fragments must be photographed using a scale
in order to match them with the scale of the line drawing. It is also important that the two
scale bars, in the drawing and photograph, be identical in size and scale (i.e. both 2 em bars
with each o.s em demarcated).
The line drawings of the sherds, made using the traditional techniques, should then be
scanned. It is important to take care that during the scanning, the drawing sheet is flat in the
scanner bed. Generally, it is thought that the highest resolution is the better one, but in real-
ity it depends upon the quality of paper. If the paper quality is not good then in high resolu-
tion scanning the paper pixels are also visible. To avoid such problems, it is essential to use
300 dot per inch (dpi) resolution for scanning.
The digital photographs are individually opened in Adobe Photoshop software (or a simi-
lar program) to combine or merge the line drawings with the color photographs. Using the
"lasso tool;' the required sections of the photograph can be selected and unwanted parts of
the image discarded (Figure 14.5c). Both the photograph and line drawings are imported
to the same page (Figure 14.5d). The scales of both the line drawings and photographs are
matched without changing their morphological features. The transparency tool can be used
so that the scales can be matched perfectly (Figure '+se). This setting makes the line drawing
and photograph visible at the same time and helps in lining them up exactly.
After matching the scales of the line drawing and photograph, the photograph is placed
within the left or right compartment, as per the motif painted on the pottery fragment.
The photograph is slightly overimposed on the line drawing of the left or right side (Figure
1+6a), and then, using Photoshop's "lasso tool" again, the photograph is digitally "cut"
(Figure 14.6b ). This stage is essential because the sherds often have irregular or uneven sides.
By digitally "cutting" the potsherd, it is possible to obtain the exact profile of the pot and gain
a more natural or realistic view (Figure 14.6c). This digital cutting is optional, because some
researchers might prefer to show the breakage pattern of the ceramics.
Special care must be taken when dealing with decoration on the top of the rim.
Photographs of these decorations are placed on top of the line drawing, aligning them to
 ANALYTICAL DRAWING 225

(a)

(d) (e)

<m
) \I )

FIGURE 14.5 Steps of new pottery illustration (part 1).

226 PRABODH SHIRVALKAR

(a)

0 5
L:+ bN?.'±+"""'w*l
em

(b)

(c)

0
La!NA'*'"'L 77~t~x•@iii61
em

FIGURE 14.6 Steps of new pottery illustration (part 2).

 ANALYTICAL DRAWING 227

the angle of the diameter which correlates directly with both ends of the reconstructed pot
and the actual diameter of the rim portion. To accomplish this, a circle should be made in
Photoshop (Figure 14.7a) and placed on the drawing in a central location. When a particular
layer is selected in Photoshop, a small cross-like symbol illustrates where the center of that
object is located. Using this central symbol as a guide, the circle can be arranged perfectly
over the diameter of the pot. Next, the photograph of the top of the rim is placed within the
curve of the diameter circle (Figure 14.7b and 14.7c). After completion of all these stages, and
before going to the last step of color correction, it is important to set all the transparent layers
back to "normal:'
Once the line drawing of the reconstructed pot with the photograph of the pottery frag-
ment inside is completed using the software, some minor corrections are necessary in order
to rectify discrepancies such as the color of the pot and/or decoration. Even if the photo-
graphs of the pottery fragments are taken using a high-quality camera, there are always
some minor variations in the colors. Although this stage is largely subjective, it is important
to attempt to adjust the color of the digital image to match the actual Munself color of the
sherd. This is done by making print-outs of the illustrations on glossy or mat 90 GSM pho-
tographic paper. The print color quality and actual specimens need to be studied and digital
colors altered accordingly for better accuracy.
Next, the brightness and contrast of the photograph are adjusted. In some cases, painted
or three-dimensional decorations require special brightness or contrast settings, different
from those used for the rest of the body, in order to highlight features of interest. In such
cases, the "lasso tool" can be used to highlight the particular area(s) of interest (Figure 14-7d)
and adjustments of these areas may be made to balance the color or accentuate features
(Figure 14-7e).
This new technique of ceramic illustration has many advantages over traditional pottery
illustration. In the traditional pottery drawing format the visualization is the basic prob-
lem. With this new format it is possible to imagine or comparatively visualize the shape and
color of the original pot in a much more comprehensive way. The traditional pottery draw-
ing fails to render the complexity of colors used in the paintings because of the shading and
stippling method. With this new method the issues related to the presentation of different
color schemes, particularly bichrome and polychrome, can be completely eradicated, as the
photograph supplements the line drawing. This new format is a combination ofline drawing
and photograph, and the attributes of the ceramic are well documented in one representa-
tion. In their traditional format, pottery drawings are often supplemented with photographs,
but with this method there is no requirement for separate photographic plates. Instead of
using selective representation, complete assemblage can be demonstrated in order to give
an excellent overview of the entire assemblage. 1be most crucial aspect of this method is
that it minimizes the subjectivity of descriptions, particularly the descriptions of color(s),
which are mentioned in the text and can also be observed directly by the researcher. In the
traditional drawing format one has to depend heavily on the written descriptions, as they
are supplemented with limited visual aids. With this method the true colors of the motifs
are visible and can be understood properly, thereby minimizing the confusion of arbitrary
color identification or subjectivity. Using this simple technique, synonymous data relating
to painted motifs can also be produced. This can help researchers to compile a database in
which there is not always a need to see original curated pottery specimens in order to see and
228 PRABODH SHIRVALKAR

(a)

0
8
.
.
.
.

(c)

(e)

L;;t ~'

FIGURE 14.7 Steps of new pottery illustration (par(3).

tP

ANALYTICAL DRAWING 229

interpret the color of pots and their motifs. The new method provides an approach that is
analytical rather than just representative.
This method of illustration was tested on the ceramic assemblage from the Harappan civi-
lization site of Padri, located in the Bhavnagar district of Gujarat state, India. It helped in a
visual comparison of ceramics from another culture in the North Gujarat region; that is, the
Anarta culture. With these visual illustrations it has become possible to demonstrate that the
cultures shared similar ceramic assemblages (Shirvalkar, 2013). In absence of such illustra-
tions it would have been difficult for researchers to carry out visual comparative analyses.
This method has the potential of making ceramic illustrations more analytical, attractive,
and research oriented.

ACKNOWLEDGMENTS

I owe sincere thanks to Prof. Vi jay Sathe, Prof. Shanti Pappu, Ms. Esha Prasad, Mr. Devadatta
Phule, and Mr. Bharat Dighe, all from Deccan College Post-Graduate and Research Institute,
Pune, India, for comments and corrections.

REFERENCES

Ansari, Z. D. (1961). "Evolution of Pottery Forms and Fabrics in India:' Marg 14:4-17.
Dales, G. F. and Kenoyer, ). M. (1986). Excavations at Mohenjo Daro, Pakistan: The Pottery
(Philadelphia: University Museum, UniversityofPennsylvania).
Dhavalikar, M. K., Raval, M. R., and Chitalwala, Y. M. (1996). Kuntasi: A Harappan Emporium
on the West Coast (Pune: Deccan College Post-Graduate and Research Institute).
Dhavalikar, M. K. and Possehl, G. L. (1992). "The Pre-Harappan Period at Prabhas Patan and
the Pre Harappan Phase in Gujarat:' Man and Environment17(1): 71-80.
Hardy-Smith, A. (1974). "Post-Medieval Pot Shapes: A Quantitative Analysis:' Science and
Archaeology u: 4-15.
March, B. (1934). Standards ofPottery Description (Ann Arbor: University of Michigan Press).
Miller, D. (1985). Artefacts as Categories: A Study of Ceramics Variability in Central India
(Cambridge: Cambridge University Press).
Millet, M. (1979). "An Approach to the Functional Interpretation of PotterY:' In: Millet, M. (ed),
Pottery and the Archaeologist (London: University of London Institute and Archaeology),
35-48.
Orton, C. R. (1980 ). Mathematics in Archaeology (Cambridge: Cambridge University Press).
Orton, C., Tyres, P., and Vince, A. (1993). Pottery in Archaeology (Cambridge: Cambridge
University Press).
Rao, S. R. (1985). Lothal a Harappan Port Town 1955-62, vol. 2 (New Delhi: Archaeological
Survey oflndia).
Sankalia, H. D. (1963). Pre- and Proto-History ofIndia and Pakistan (Pune: Deccan College Post
Graduate and Research Institute).
Shepard, A. 0. (1985). Ceramics for the Archaeologist (Washington, D.C.: Carnegie Institute of
Washington).
230 PRABODH SH!RVALKAR

Shin de, V. S. and Kar, S. B. (1992). "Padri Ware: A New Painted Ceramic Found in the Harappan
Levels:' Man and Environment XVIl17(2): 105-110.
Shirvalkar, P. (2013). Pre-and Early Harappan Cultures of Western India (New Delhi: Agamkala
Prakashan).
Shirvalkar, P., Phule, D., Pradhan, S., Dighe, B., and )adhav, S. (2010). "Traditional Pottery
Drawing and Digital Photography: An Alternative Technique from India:' Antiquity Project
Gallery: <http:/ /www.antiquity.ac.uk/projgall/shirvalkar325/> (last accessed April25, 2016).
Sinopoli, C. (1991).Approaches to Archaeological Ceramics (New York: Plenum Press).
Taylor, M. (1873). "Description of Cairns, Cromlechs, Kistvaens, and Other Celtic, Druidical or
Scythian Monuments in the Dekhan:' Transactions of the Royal Irish Academy 24(3): 329-362.
Uesugi, A. and Meena, S. (2012). "Pottery:' In: Kharakwal, ). S., Rawat, Y. S., and T. Osada, T.
(eds), Excavations at K.anmer (Kyoto: Nakanishi Printing Co. Ltd), 219-480.
Webster, G. (1964). Romano-British Coarse Pottery: A Students Guide (London: Council for
British Archaeology).
 PART IV

EVALUATING
CERAMIC
PROVENANCE
 CHAPTER 15

PETROGRAPHY
Optical Microscopy

DENNIS BRAEKMANS AND PATRICK DEGRYSE

INTRODUCTION: A BRIEF HISTORY

OF CERAMIC PETROGRAPHY

FoR all periods since the Neolithic, ceramics are the most prevalent surviving material on
nearly any archaeological site. These discarded fragments, or potsherds, are very durable
and resistant to degradation and diagenesis in burial, unlike artifacts made of cloth, leather,
wood, or even metal. Traditional ceramic studies classify pottery by its physical attributes,
such as form, fabric, and decoration. These attributes can be so unique and identifiable that
a small fragment is often all that is needed to recognize the original complete shape of the
vessel. Pottery characteristics change over time and vary from place to place. Comparison
of sherds or vessels between sites can assist in dating archaeological strata, architectural
remains, and other artifacts discovered with the sherds. While this is not an exact science, a
trained archaeologist can deduce from potsherds the details of chronology, trade networks,
and/or the technology of the settlement from which they were recovered.
In comparison with traditional typochronological studies, the use of scientific tools has
a fairly recent application to ceramic research. The use of thin sections in archaeological
research was first explored during the mid- to late nineteenth century. The first recorded
publication using ceramic petrography appeared in 1879 in a volume by Ferdinand Fouque
on volcanic rock fragments in Theran pottery (Fouque, 1879). 1be field of ceramic petrog-
raphy was considerably advanced with the work of Anna Shephard and Wayne Felts in the
middle of the twentieth century. Felts conducted a petrographic analysis of ceramics exca-
vated at Troy in western Turkey (Felts, 1942), while Shepard (1942), and later Peacock (1969)
used the characterization of ceramic inclusions and their relationship with the regional geol~
ogy of the American southwest to study archaeologically relevant phenomena such as trade
and distribution. This early application of ceramic petrography facilitated the identification
of several production centers and reconstruction of the movement, transport, and technol~
ogy of ceramic goods.
234 DENNIS BRAEKMAN':' AND PATRICK DEGRYSE

Since the 1970s and 198os, thin-section analysis has been used more frequently, espe-
cially in combination with an array of chemical techniques. Petrographic analysis remains
to this date a major, robust, and relatively cheap classification technique of ceramics, by
both qualitative and quantitative identification of mineral inclusions and rock fragments
(Arnold, 1972; Whitbread, 1992; Goren, 1995; Mason, 2003). Thin-section petrography also
provides important information about the nature of inclusions and temper materials when
interpreting chemical data, secondary processes, and production techniques (Kilka, 1992;
Maggetti, 1994; Hein et al., 2002; DiPierro, 2003; Degryse and Braekmans, 2014). Difficulties
in the determination of raw materials provenance may increase when the geological set-
ting of a study area is complicated or when elaborate mixing of different raw materials has
occurred. More detailed forms of petrographic analysis-for example, the work carried out
by Maggetti et al. (1981) on fossil shells, Quinn (2007, 2008) on microfossils, and Whitbread
(1986) on argillaceous inclusions-stresses the important implications of ceramic petrog-
raphy for archaeological ceramic studies. Moreover, technological features or production
techniques can be successfully examined by thin-section microscopy, through the examina-
tion of the fabric structure of the sherd (i.e. orientation, texture, roundness and sphericity,
levigation, and so on) (Maggetti, 1994).
Ceramic petrography is a well-established research technique which allows the construc-
tion oflarge, relatively inexpensive reference databases. The analytical equipment needed is
a standard "polarizing light microscope;' equipped with a circular rotating stage, two polar-
izers, and a Bertrand lens or phase telescope. A computer system with a digital camera and
image software is preferred for output purposes (Figure 15.1). 'Ihe large number of petro-
graphic studies done in archaeology stresses the importance of this standard technique, and
allows researchers to derive valuable information about ancient pottery production in any
area of the world.

WHAT INFORMATION Do WE AcQUIRE

WITH THIN-SECTION PETROGRAPHY?

The Constituents of a Ceramic

Thin-section petrography is especially effective when a large amount of non-plastic inclu-
sions are present in the ceramics being studied. A small sample (-1cm 3) is required, which
needs to be representative of the entire ceramic vessel. Thin-section analysis of ceramic
materials requires a trained eye, as ceramic sections can be signif1cantly different from geo-
logical samples. However, there are fewer types of minerals commonly attested in archaeo~
logical ceramics, which makes routine analysis easier. There are four main constituents of a
ceramic thin section from which we can derive information:

(1) The non-plastic inclusions or temper: minerals and rock fragments, organics.
(2) The matrix/microstructure or paste: the original clay used for firing.
(3) Porosity: a result of the production process and raw material properties.
(4) Surface decoration or treatment such as slips, glazes and paint.
 PETROGRAPHY 235

"lbe term "inclusions" or "non~plastic" inclusions points towards the mineral and rock frag-
ments contained in the sherds, which are visible using optical microscopy. For example,
Maggetti (1974, 1994) defined the size of"inclusion" as fragments larger than O.GI5 mm, but
this value can differ. Plastic inclusions, such as clay pellets, argillaceous minerals, and mud,
are also incorporated into the fabric of the sherd. These plastic and non-plastic inclusions
occur naturally in the clay deposit or deposits used to manufacture the ceramics.
Temper, however, is defined as fragments which are deliberately added to the paste.
Strictly speaking the paste relates to the clayey matrix only. This matrix can be described as
the "cement" for the mineral inclusions and rock fragments and, in a fired ceramic, consists
mostly of (sintered to molten) clay minerals. Depending on the raw material used, a silt-
sand fraction may also be considered within the matrix.
Porosity encompasses all air-filled areas in the matrix and around minerals and rocks.
Terminology describing pores includes (micro )pores, voids, vughs, and vessicles. Pores are
generally the result of different thermal expansion rates of inclusions, removal of inclusions
from the matrix, and/or drying/firing of the clay.
Textural properties of archaeological ceramics include color, optical activity of the
groundmass, sorting of grains, roundness, and sphericity of the inclusions, and maximum
(estimated) grain size. Grain-size distribution or sorting refers to the number and variation
of the range of grain sizes in non-plastic inclusions. Well, medium, and poorly sorted distri-
butions refer to ceramics in which the inclusions are all approximately the same size; X% are

FIGURE 15.1 A standard polarizing light microscope with rotating sample stage. The cam-
era and imaging software are essential tools for data output.
236 DENNIS BRAEKMANS AND PATRICK DEGRYSE

approximately the same size with a few outliers, or the inclusions are fairly different in size.
Grain-size distribution analysis often includes a documented grain-size maximum for the
paste. Roundness of inclusions is described with terms ranging from very angular to well
rounded, and sphericity is described in ordinal classes from low to high, each representing
the degree to which the shape of the inclusion approximates a sphere. Elongated pores can
also be evaluated in this way. Each of these properties may yield valuable data on the type of
raw materials and technology used for pottery production.
Thin-section analysis can be done both qualitatively as quantitatively. A qualitative
approach allows, in most cases, discrimination of different clay sources based on the type
and abundance of different minerals and rock types included in the ceramic fabric. A quan-
titative approach, on the other hand, requires a more time-consuming and difficult analysis
involving the determination of percentage values for each of the different minerals included
in the fabric. A main concern with this approach is the representative nature of the section
for a whole vessel, and identification of the mineralogy of the temper versus clay source.
Moreover, the areas selected for counting different minerals can have a direct impact on an
interpretation of the results. 1he technique most often used in a quantitative approach is
point counting. This requires the definition of a grid across the thin section to assess which
minerals are present in each grid point.

Research Questions for Ceramic Petrography

Common research questions in thin-section petrography relate to various aspects of pottery
production and technology, and include:

(1) Is it possible to distinguish local versus imported wares at a site in a region?

(Synchronic study)
(2) Is there a chronological difference in the use of raw materials? (Diachronic study)
(3) Can traces of the manufacturing process be derived from studying structural features,
and how have these been altered by firing conditions? (How were ceramics made?)
(4) Where were the ceramics under study used for?

The first two questions are related and are of great interest for the reconstruction of trade
and exchange patterns. Based on the characteristics of the clay matrix and the type of inclu-
sions, the type of geological "origin" of the clay (and its natural additives) can be deduced.
The starting point in this type of analysis, and for the comparison of ceramic fabrics to clay
sources, is often based on ethnographic studies of potters. Several ethnographic studies have
indicated that raw materials for ceramic production tend to be gathered close to the kiln site,
mainly based on a one-day return journey (Arnold, 1985). In terms of provenance, compara-
tive analysis using misfired ceramics or kiln wasters is also highly desirable,as these are often
thrown away in situ after a failed firing process (Mommsen et al., 1988). The identification of,
often rare, imported or foreign vessels has significant implications for reconstructing cul-
tural contact, exchange networks, and trade activities.
The third question relates to the technological process of making a ceramic-a process
extensively modified throughout time and refined by many different societies. A complex
chaine operatoire (Bar-Yosef et al., 1992) of different technological methods and choices is
 PETROGRAPHY 237

reconstructed. Each of the different steps of the process, from the selection, sorting, refin-
ing, and mixing of raw materials to the methods of shaping and molding the vessel, and,
ultimately, the control of temperature and oxidation state of kilns, can have a great effect on
the final product. With this information, research is carried out into how such decisions are
shaped by the culture in which potters are operating. For example, the social and economic
organization of pottery production and the place of the potter in society can be an important
goal of such study (Rye, 1981; Orton et al., 1993; Arnold, 2008).
The fourth question concerns the last phase of the vessel's life-cycle before deposition,
the actual use or function of a vessel. Most petrographic studies concentrated on the techni~
cal characteristics of ceramics: how "fit for purpose" are they? The relationship between the
presence of certain minerals (and their number and size) and the performance characteris-
tics of the ceramic (e.g. thermal shock resistance, impact resistance, and strength) may be
directly linked with technological choices made by the potter (Tite and Kilikoglou, 2002).
Furthermore, the identification and classification of decorations of various types, and the
complexity of the production process of a ceramic help to define broad groups of storage,
cooking, serving, display, and funerary wares. Recent work has shown that the concept of
a single designed use or production of a ceramic is too simplistic (McGovern et al., 1989;
Miller, 2007; Thornton and Rehren, 2009 ). Ceramics have a complex life history or "biogra-
phy" which can involve several periods of different use and reuse for purposes unrelated to
their original function.

THE MAKING OF A THIN SECTION

Fragments of sherds, often referred to as chips, representing each of the different ware or fab-
ric groups of ceramic on a site, are glued to a microscope slide and polished down until they
are only 0.03 mm thick to create a thin section. At this thickness, most minerals in ceram~
ics are translucent and the optical properties used for identification are visible. The section
is placed on the polarizing light microscope (PLM), where it sits between two polarizers
arranged at 90° to each other. The minerals in the sample interact with light, transmitted
through the section from below, revealing its interference color and other properties charac-
teristic of the mineral involved. Prior to thin~section preparation, samples are often impreg-
nated with an ultra-low-viscosity resin, sometimes tinted, which concentrates or fills pores
within the clay body and improves the quantification and classification of porosity (Oliveira
et al., 1983).

BASIC CONCEPTS OF OPTICAL MICROSCOPY

A thin section can be studied under two different light conditions, each providing differ-
ent identification tools of visible minerals, rock fragments, or other artifacts present in a
ceramic vessel. 1hese optical conditions are named after the use of one polarizer filter (plane
polarized light, PPL) and the addition of a removable second polarizer filter, called the "ana-
lyzer" (crossed polarizers, XPL) (Plate 4a-b). Minerals are generally described in terms of
238 DENNIS BRAEKMANS AND PATRICK DEGRYSE

their occurrence, composition, relief(PPL), appearance and habit, twinning, cleavage, color
(PPL), interference colors (XPL), extinction angle, and interference figures.

Color and Pleochroism (PPL)

The color of a mineral relates to the color determined when studying the mineral in plane
polarized light (PPL). Minerals can appear colorless or in a range of colors and intensities
(i.e. from weakly to strongly colored) (Plate 4c). This color is not necessarily identical to the
color of a macroscopic crystal of the same mineral. Pleochroism is a phenomenon defined as
a change in the intensity and/or color of the mineral as the microscope stage is rotated.

Relief (PPL)
In PPL, some minerals have a high relief; these minerals are recognized by their sharp grain
boundaries, showing fractures and cleavages (Figure 15.2). This (relative) phenomenon is
based on the mineral's index of refraction. When looking at several different minerals, those

FIGURE 15.2 High relief and cleavage of a pyroxene mineral. Note the very sharp boundar-
ies and slightly elevated relation to the matrix, and diagnostic 87' and 97' cleavage planes
(after Neyt 2012).
f·

PETROGRAPHY 239

with high relief will have more pronounced boundaries as opposed to minerals with a lower
refractive index. Calcite shows a different relief upon rotating, resulting from the difference
in refractive indices depending on the vibration direction of the light passing through the
mineral. There is little difference in relief between quartz, plagioclase, and K-feldspar, for
example, because they all have about the same refractive index.

Cleavage (PPL)
Cleavage can be a very helpful diagnostic feature for the identification of minerals. It reflects
the preferred ways in which a mineral breaks, representing plane weaknesses in the crystal-
lographic structure of the mineral. A mineral can have no, one, or multiple cleavages. A sin-
gle cleavage orientation may manifest as multiple parallel cracks along a single face of the
mineral, and is only visible when the mineral is oriented so that the "cracked" face is visible
(e.g. biotite). Sometimes these planes of crystallographic weakness do not manifest in visible
cracks; for example, feldspars have two cleavage directions which are often not visible in thin
section.
When more than one cleavage orientation can be determined, the cleavage angle is
often a useful property for mineral identification. Depending on grain orientation, miner-
als may show different cleavages and angles. Looking at multiple grains and determining
the maximum cleavage angle is, therefore, often necessary. A cleavage should not be mis-
taken for fractures. Fractures have a mostly random orientation and do not form parallel
cracks. Typical cleavage angles exist for pyroxenes at ~90°i and amphiboles at ~124° and ~s6°
(Figure 15.2).

Opaque, Isotropic and Anisotropic Minerals

and Interference Colors (XPL)
Three main groups of minerals are distinguished according to their opacity, or the way in
which light is or is not transmitted through their crystal structure: opaque minerals, isotro-
pic minerals, and anisotropic minerals. Opaque minerals do not transmit light in thin sec-
tion and thus appear continuously black under both light conditions. Heavy minerals such
as magnetite or ilmenite are common examples of this group of minerals. Isotropic minerals
on the other hand do transmit light. In fact, they transmit light at the same velocity through
the mineral in every direction. Not many isotropic minerals exist, but common examples
in ceramic petrography are garnet and spinel. Conversely, depending on the mineral orien-
tation, light may travel at different velocities through anisotropic minerals, thus exhibiting
interference colors or birefringence properties. Isotropic and anisotropic grains are easily
differentiated because i~otropic minerals remain black under crossed polarizers. 1
Anisotropic minerals cause polarized light to be separated in different wave lengths, as in
a prism, owing to the difference in velocity of the light passing through the mineral in differ-
ent directions. Birefringence describes the difference in velocity of these paths. After pass-
ing through the mineral grain, these different velocities of light will combine, interfere with
each other, and produce interference colors. These colors are only observable under crossed
240 DENNIS BRAEKMANS AND PATRICK DEGRYSE

polarizers, and are classified according to hue and order (first, second, third order) (Plate
4d). The higher the order the more "pastel" or "unsaturated" these colors appear. Minerals
with low order birefringence, on the other hand, show only whitish, grayish and black inter-
ference colors.
Interference colors are an important identification tool for minerals. Depending upon
grain orientation, thickness, and variations in mineral composition, these colors can vary.
When examining a sample containing several grain fragments of the same mineral, as is
typically the case in most ceramic fabrics, the interference color may vary by grain, but it
is the maximum, that is the highest order interference color that is diagnostic. Reference
tables and the Michel- Levy interference color chart for these colors are commonly available
in optical microscopy and mineralogy guides (Dyar et al., 2012; Nesse, 2012).
Anomalous interference colors do not comply with these charts and are caused by a wide
array of possible optical processes (e.g. in strongly colored minerals, the "natural'' color of
the mineral is superimposed on or distorts the interference color; wavelength differences
in biaxial minerals; birefringence and refractive index differentiation according to wave-
length). Typical, however, is the very low birefringence of minerals causing an anomalous
interference color; such anomalous colors tend to be dark (blue, violet, green, and brown are
all possible).

Extinction Angle (XPL)

Another main property of anisotropic minerals is the extinction angle; that is, the angle
between a crystallographic direction (such as cleavage) and the extinction direction. A
mineral goes extinct (black) when one vibration direction of the mineral is parallel with the
polarizer. To assess this angle the sample is rotated. Although extinction angle is specific and
diagnostic of particular minerals, like interference color, extinction angles are dependent
upon grain orientation. "The maximum measured angle is diagnostic for mineral grains. Most
minerals in thin section have elongated forms which have an easily recognizable direction;
for example, biotite and amphibole crystals. As such, parallel (angle of zero) (e.g. biotite)
or inclined extinction (greater than zero) (e.g. clinopyroxene) can be detected. Generally,
tetragonal, hexagonal, trigonal, or orthorhombic crystal systems produce straight extinc-
tion, while triclinic minerals produce an inclined extinction. Monoclinic minerals may
show both extinction types. Symmetrical extinction occurs when a mineral grain produces
two cleavages and thus two extinction angles can be measured (e.g. amphiboles). Quartz and
olivine grains commonly go extinct every 90° of rotation, but do not have a noticeable cleav-
age, and thus no extinction angle can be measured.

Twinning (XPL)
Twinning relates to the intergrowth of two crystals within a single grain. This occurs dur-
ing the growth of a crystal or when a mineral is subjected to stress and high temperature/
pressure conditions. Twinning can be observed in thin section because of the different opti-
cal orientation of the two crystals. Plagioclase is a good example of a twinned mineral. In
XPL, plagioclase shows alternating bands of white, black, and gray colors which go extinct at
 PETROGRAPHY 241
-----

diflerent times while turning the microscope's stage. This differentiated appearance is caused
by different optical orientations, and not by different compositions.

IDENTIFICATION OF COMMON MINERALS

AND ROCKS

Many excellent textbooks exist to aid the identification of common minerals in rocks in thin
section. Most of them use examples from geological contexts (Philips, 1971; Allman and
Lawrence, 1972; Folk, 1974; Scholle, 1979; MacKenzie and Guilford, 1981; Philips and Griffen,
1981; MacKenzie et al., 1982; Carozzi, 1993; MacKenzie and Adams, 1994; Adams et al., 1997;
Scholle and Ulmer-Scholle, 2003, Dyar eta!., 2012; Nesse, 2012), but recently specific hand-
books on ceramic petrography and the interpretation of ceramic thin sections have been
published (Reedy, zoo8; Quinn, 2009; Quinn, 2013). Based on these works>.adetailed, but by
no means complete, table of identification of various minerals is provided at the end of this
chapter (Table 15.1). In general, minerals can be classified as primary (e.g. quartz), secondary
(formed after firing, during burial, e.g. precipitated calcite) and formed during firing (e.g.
diopside) (Maggetti, 1982).
Rock fragments are described according to their genesis and texture and classified accord-
ing to the three basic rock types: igneous, metamorphic, or sedimentary. A short overview of
frequently encountered rocks is provided here:

Igneous rocks: Plutonic rocks comprise all magmatic rock fragments of plutonic origin and
are typically recognized by the large grain size of the crystals or phenocrysts. If the type of
plutonic rock can be determined based on its mineralogy (i.e. basic, intermediate, acidic; gab-
bro, diorite, granite), this is included in the petrographic description. Volcanic rocks refer to
all magmatic rock fragments of volcanic origin and are characterized by a finer texture than
plutonic rocks; small crystal grain size to glassy amorphous texture. Owing to the often small
size of the grains, an accurate identification of volcanic rock type can be problematic. Often
volcanic rocks can only be broadly classified according to their general composition (i.e. basic,
intermediate, or acidic). Volcanics may recrystallize, mostly by silicification, which may result
in a less exact identification of these rock fragments (MacKenzie and Adams, 1994).
Metamorphic rocks: Metamorphic rocks are the result of, in most cases, a high tempera-
ture and high-pressure recrystallization of rocks. The original rock type can be any igneous,
sedimentary, or metamorphic rock. A polyquartz fragment, for instance, refers to all types of
quartzites of metamorphic and igneous origin composed of more than two quartz crystals.
A straight extinction of the quartz grains suggests an igneous classification, while stretched
grains and an undulatory extinction suggests a metamorphic origin (GOtze and Zimmerle,
2000). Mica schist, for example, is a metamorphic rock with more than so% of mica con-
tent (mostly muscovite); common accessory minerals in mica schists are quartz and garnet.
Phyllite is a fine-grained, foliated, low-grade metamorphic rock which is typically composed
of quartz, mica (sericite), and albite.
Sedimentary rocks: Sedimentary rocks are formed through the weathering of preexisting
rocks, as well as once living organisms. Some of these rocks have a detectable layering as a
result of the accumulation of fragments and debris on the Earth's surface. Carbonate rocks,
such as limestone or dolomite, are one of the most common groups encountered in archaeo-
logical thin sections. Limestone is composed of calcite and aragonite minerals and is easily
identified by its texture and interference colors. Chert, another common sedimentary rock
Table 15.1 Mineral identification table derived from the integrated information of various geological handbooks. They represent a concise list of
characteristics in thin section
10 Occurrence Composition Relief Appearance Twinning Cleavage Color (PP) Interference Extinction Similar Remarks
(PP) and habit Colors (XP) Angle Minerals
--····~--

Biotite igneous and Annite n/a tabs, n]a excellent, pleochroic, Interference Birds-eye n/a Often contains
metamorphic rocks; KFe 3AlSi 30 10(0Hh elongated dependent varieties of colors may or pebbly pleochroic halos
immature sedimentary - phlogopite flakes which on grain brown, yellow, range up to extinction or around small
rocks KMg 3A!Si 3 0w(OHh may be bent orientation, red or green. 2nd order red wavey included zircons.
rarely Biotite with pattern of Often alters to
hexagonal low Fe-content interference chlorite.
crystals (ph!ogopite), colors,
coloration is especially
more subtle when looking
(clear, light down on flat
browns) side of flakes.
Extinction
angle is 0 to a
few degrees
from cleavage
(a-Clinopyroxene: mafic to (Ca,Mg,Fe,Na) moderate to four or eight possible basal sections light green; 2nd order inclined Orthopyroxene, distinguishing
Augite intermediate (Mg,Fe,AI) high relief sided crystals, twinning and show cleavage varieties of yellow to pink extinction pigeonite, different pyroxenes
igneous rocks and (Si,AI)z0 6 ; augite prisms or exsolution angle near 90~, light brown or interference sodic pyroxenes, and olivine can
their metamorphic [Ca,Mg,Fe)_;;Si 206 anhedral visible; exsolved longitudinal yellow colours in XP, amphiboles, sometimes be difficult
equivalents. crystals orthopyroxene sections show up to high 2nd olivine
may form fine one cleavage order
lamellae in
clinopyroxene,
simple or
polysynthetic
twins.

·~
,
I

Calcite- Dolomite primary minerals

in a wide variety of
CaC0 3 "' calcite;
CaMg{C03h""
high relief euhedral and
hexagonal,
common, one
or two sets of
rhombohedral
cleavage
colorless or
vague pastel
extreme
birefringence,
n/a colouring
required to
variable relief in PP
while rotating
,
II
I
sedimentary and dolomite more typically parallel one of two sets
metamorphic rocks anhedral in twinning of poiysynthetic
distinguish
dolomite from
I
aggregates twins PP and calcite
XP. Chemical
staining as
differentiating
tool. Very high
interference
colors, often
appearing
nearly white
Chlorite Chlorite is variable n/a PRIMARY' n/a single pleochroic, anomalous n/a n/a often ovelooked
common as a secondary chemistry similar to colorless green gray greenish minerai
mineral, forming after muscovite to pale to interference because it is
mafic minerals, in or biotite; medium/dark colors (lower secondary and thus
rocks of many types. SECONDARY' green. Rare first order) ; not develop large
ltmayalsobea flake-like other colours anomalous bleu, crystals.
primary mineral in crystal (mostly purple, brown
low- to medium-grade anhedral),
metamorphic replacement
rocks. "patch" of
biotite along
cleavage traces
Chloritoid low- to (Fe,Mg,Mn) high relief n/a simple or single greenish and low-order n/a n/a n/a
medium- grade AI 2Si05 (0Hb parallel twins pleochroic, (yellow) or
metasedimentary color anomalous
rocks
zonation with
"appearance"
Clinopyroxene Ca-Mg clinopyroxene CaMgSi 20 6 ; (Na,Ca} High Relief short prismatic incipient 90" clear to light mid to upper large n/a n/a
endmember: is found mostly in (Mg,Fe 3 +,AI)Si2 0 6 crystal, or twinning green second order
Oiopside marbles. Fe-free. Mafic (Na-clinopyroxene) well equant
and ultramafic rocks, cross-sections
and metamorphic
equivalents. Associated
with garnet

(continued)
Table 15.1 Continued
ID Occurrence Composition Relief Appearance Twinning Cleavage Color (PP) Interference Extinction Similar Remarks
(PP) and habit Colors (XP) Angle Minerals
·-··~~-

Clinopyroxene Fe-rich CaFeSi 20 6 high relief n/a n/a n/a green; more n/a n/a n/a n/a
endmember: dark coloured
Hedenbergite) and weak
pleochroism
Clinozoisite common in igneous Ca 2Al 3Si3 high relief n/a n/a n/a colorless first order, parallell in n/a nla
rods and low- to O,(OH) anomalous elongate grains
medium-grade yellow green,
methamorphic rocks. anomalous
Alteration product in blue-green
rocks of many sorts
Cordierite metamorphic, {Mg.Feh n{a generally common, n/a clear first order grays n}a plagioclase, included minerals,
high-grade pelitic AI4Si 50l 8 blocky and polysynthetic- and whites quartz f.e. zircons, burn
metamorphic rocks anhedral, marks due to
pseudohe- radiation damage
xagonal
appearance
Epidote common in igneous Caz[AI,Fe-3+) 3Si 30 12 high relief n/a lamellar, not single cleavage yellowish upper second parallel in biotite and typical anomalous
rocks and low- to common green (weakly to third order, elongate other micas green yellow color
medium-grade pleochroic) multiple colors, grains ; green or clear; pastels
metamorphic rocks. sometimes amphibole interference within
Alteration product in in concentric individual grains
rocks of many sorts rings, sometime
anomalous
colors
Garnet wide variety of solid solution of n/a euhedral: n/a n/a generally n/a n/a spinel, inclusions of quartz
metamorphic rocks and end members: 6-8 sided, colorless, perovskite and other minerals
some igneous rocks almandine(Fe3AI:J, more common slight pinkish are common
pyrope (Mg 3AI 2), subhedral or or gra image
spessatine [Mn 3A!~, anhedral
grossular (Ca 3AI 2Si 3 0n),
andradite (Cale 2)

..J
 l
Hornblende- common mineral Actinolite: Ca 2 n{a concentric or n/a 60°-120. pleochroic, max middle n/a n/a n}a
Actinolite in igneous and (Mg.Fe) 5Sis0n; patchy zonation. in shades of second order
mi:tamorphic rocks Hornblende more Form: sub brown and but may be
variable (K,Na) 0 • 1 to anhedral green, less masked by the
(Ca, Na, Fe,Mgh but maybe common color of the
(Mg,Fe.AI)5 prismatic yellow or mineral
(Si,AI) 6022 (0Hh crystals forming redbrown;
lathes. End Actinolite
views may (green) from
show diamond- light green
shaped (Fe-poor) to
cross-sections. dark green
(Fe-rlch)
Kyanite high-pressure mica AI 2Si05 high relief n/a n/a n/a colorless, pale rarely higher 30° from orthopyroxene, n/a
schists and gneisses blue, slightly than upper first cleavage dinozoisite
pleochroic order (yellow), direction,
rarely second obHque
order red)
Microcline widespread and Anorthite: n/a Anhedral cross-hatched n/a colorless low n/a n/a in gneiss, also wavy
common in a wide CaAI 2 Si 20 8 ; twinning birefringence; pattern ; exsolved
variety of igneous and Albite: white to gray ->lamellae of
metarr:orphic rocks, NaA!Si:,08 ; a!bite(strlpes in XP)
to a lesser extent Orthoclase
in some immawre KAJSi 30s
sedimentary rocks {low
temperature). SiHdc to
intermediate plutonic
rocks (not volcanics)+
metamorphic rocks

(continued)

_j
Table15.1 Continued
ID Occurrence Composition Relief Appearance Twinning Cleavage Color (PP) Interference Extinction Similar Remarks
(PP) and habit Colors (XP) Angle Minerals
~·····--·-- --~--·-

Muscovite widespread and KAI 2AISi 301o(OHh low to tabs or long n/a excellent, colorless, less upper Otoafew n/a commonest white
common in a wide moderate, skinny flakes depending commonly second order degrees from mica, distinguishing
variety of igneous and white which maybe on grain pale green interference cleavage from other whi~e
metamorphic rocks transparent bent orientation. and slightly colours (up to micas and brit!e
(+some immature mineral Hexagonal pleochroic second order micas in thin section
sedimentary rocks) tabular crystals red), birds~ can be difficult
are rare eye or pebbly or impossible.
extinction, Therefore 'white
wavy pattern mica'. Sericite is a
of interference fine grained variety
colors of muscovite;
destroyed around
600-700"

Na- Amphibole typically found in high- Na 2tv'1g 3Al 2 n/a plates or n/a n/a pleochroic in upper first order, n/a troumaline, Kaersutite (Na,Ti-
(glaucophane) pressure metamorphic (Si 80,)[0H), long slender various shades, but modified by sodic pyroxenes rich igneous
rocks. crystals, less blue or violet the color of the amphibole); has very
common are based on minerals strong red-brown
diamond- composition pleochroism
shaped
cross-sections

Na-Ciinopyroxene; high-pressure NaAlSi206 moderate also granular, simple or n/a colourless but First or n/a n/a n/a
jadeite metamorphic rocks, to low may form lamellar may be very anomalous;
blueschists fibrous pale green or often
aggregates. yellow anomalous blue
interference
colours
 '1
I
Na*Ciinopyroxene ; high-pressure AI exceeds Fe 3+ in moderate to also granular simple or o/a nondescript low order, upper n/a n/a n/a 'i
omphacite metamorphic rocks, (Na,Ca)[Mg,Fe''.AI) low lamellar light green, first or second I
eco!ogite I
Si20G faint order maximum
pleochroism
Na-C!inopyroxene; alkalic igneous rocks NaFe3..Si 206 high relief four- or eight- simple or o/a brown, aegerine-augite n/a amphiboles, acmite and aug;te
{aegirine-augite) sided cross- lamellar yellowish slightly lower epidote, zoisite are distinguishable
sections with brown, shades 3rd order from other [calcic)
two cleavages of green. birefringence. pyroxenes by their
nearly Darkest when Color may mask deeper colour
perpendicular. Fe3+ content interference and stronger
Short prisms or is high. green colours. pleochroism, al~o
plates showing varieties are their extinctior:
one cleavage pleochroic. angle is smali
are more Colour zoning (0-20"), index of
typicaL is common refraction and
birefringence are
larger
Olivine mafic to ultramafic (Mg.FehSi0 4 ; moderate triangular, none very poor colorless or up to strong n/a n/a nla
igeneous rocks and Forsterite (forsterlte) easily alters, cleavage not very pale third order
in their metamorphic (Mg 2Si04) and to very high produces deep visible in thin yellow
equivalents Fayalite (fayalite) red or brown section, fracture
(Fe 2Si04) iddingsite, in irregular
serpentinite manner
e.a. euhedral
crystals, also
in igneous
rockssubhedral
grains,
sometime
aggregated.

(continued]
 Table 15.1 Continued

ID Occurrence Composition Relief Appearance Twinning Cleavage Color (PP) Interference Extinction Similar Remarks
(PP) and habit Colors (XP) Angle Minerals

Orthoclase variety of igneous and Anorthite:CaAI 2Si 208 ; n/a anhedral simple twins; n/a colorless, low n/a n/a exsolved ~> 1ame1lae
metamorphic rods, to Albite: Carlsbad twinst frequently birefringence; of albite(stripes
a lesser extent in some NaAISi30 8 ; or contact, both incipient white to gray inXP)
immature sedimentary Orthoclase KA!Si 30 8 show straight alteration
rocks. Often in many extinction
silicic plutonic rocks,
less commonly in
volc:anic rocks. Also in
metamorphic and some
sedimentary rocks
Orthopyroxene common in mafic (Mg,fe,Ca)[Mg,fe,AI) moderate to well developed, orthopyroxenes Near 90" pale green, first order Extinction is andalusite, pleochroic halos
(hypersthene) igneous rocks, (Si,AI}.z0 6. Natural fairly high sometimes may show fine cleavage in peochroic to white to gray, parallel to the clinopyroxene around zircon
commonly associated compositions are visible as blocky twinning or basal sections. pink low order cleavage inclusions, visible as
with plagioc:\ase and dominated by two four~ or eight- exsolution Longitudinal interference,· burn marks in PP
clinopyroxene. Also major end member sided crystals. sections show up to first order
found in high-grade components: Frequently one cleavage. yellow
metamorphic rocks enstatite: stubby prisms,
Mg 2Si 20r;and rectangular
ferrosillte fe 2Si 20 6 lathes, anhedral
crystals and
masses
Plagioclase widespread and Anorthite: low to subhedral large variety two cleavages colorless, birefrigence n/a quartz, lntergrowth of
common in a wide CaAI 2Si 20s; Albite: moderate to anhedral, possible but but often not altered is low, only K-feldspar, Na-rich feldspar
variety of igneous and NaAISip8 ; Orthoclase maybe also untwinned, well developed giving grainy white to gray Cordierite with K-feldspar
metamorphic rocks, to KAISi 308 euhedral in XP: diagnostic or grayish low order (microcline or
a lesser extent in some volcanics. polysynthetic appearance in interference orthoclase)=
immature sedimentary Plates and twins; stripes or PP" Concentric colours, perthite. Alteration
rocks lathes simple twinning compositional occasionally to a fine grained
common in zoning possible first order micaceous material,
igneous rocks. (both visible in yellow partly or entirely.
Compositional PP and/or Xp)
zoning in XP.

""
 'l

Quartz common mineral Si0 2 low relief anhedral, rarely n/a never c:!eavage, colorless f1rst order white wavy extinction Plagioclase, subgrains by low
in sedimentary, euhedral. possible to gray, rare first {undulatory) Alkali feldspar, grade
metamorphic: and fractures order yellow apatite, methamorohism.
igneous rocks cordierite, Coesite as high
beryl& pressure polyrr•orph
scapolite of quartz. Ouartz
does not alter
Rutile common accessory Ti0 2 very high possibly n/a n/a usually red, extreme n/a Hematite has n/a
mineral in intermediate associated red~brown, birefringence, a deeper red
to mafic igneous with biotite yellowish Interference color and a
rocks and in many brown. colors may not more irregular,
metamorphic rocks possibly show due to platey, habit.
pleochroic. the strong color
yellowish to of the mineral.
reddish brown When present,
they are pastels
of very high
order
Sanidine widespread and Anorthite: n/a euhedral simple twins n/a colorless, low n/a n/a exsolved ->lamellae
common in a wide CaAI 2Si 208 ; generally dear birefringence; of albite (stripes
variety of volcanic, Albite: white to gray inXP)
igneous, and NaAISi3 08 ;
metamorphic rocks, Orthoclase
to a lesser extent KAISi 30 8
in some immature
sedimentary rocks (high
temperature).

(continued)
Table 15.1 Continued

ID Occurrence Composition Relief Appearance Twinning Cleavage Color (PP) Interference Extinction Similar Remarks
(PP) and habit Colors (XP) Angle Minerals
----- ·~-··-~~~-·~"- --~

Serpentine altered ultrabasic- Mg::~Si 2 0 5 (0H)4 low to irregular occasional yes; chrysotile pleochroic; birefringence parallel! fibrous lower birefringence
rocks, especially from moderate fibrous, others colourless to low, mostly first amphiboles; than micas, chlorite
ophiolites one perfect pale green, often order whites patchy and higher Rl
oxidizes to red in and grays mixed with
pottery other minerals

Sillimanite metamorphic mineral AI 2SiO.s high relief needle-like, n/a n/a clear upper second n/a n/a n/a
found in high-grade fibrous, or order
aluminous schists and bladed habit
gneisses. Polymorph of
and-alusite and kyanite
Titanite accessory mineral CaTiSi05 very high wedge, n/a n/a nearly very high n/a n/a n/a
in igneous and relief diamond, colorless, birefringence-;
metamorphic rocks, or distorted sometimes interference·
less commonly found in hexagonal brownish or colors
sedimentary rocks shape, euhedral gray due to
crystals high refractive
index
Spinel common isotropic combination of n/a n/a n/a commonly highly variable isotropic n/a n/a n/a
minerals in aluminous endmembers: anhedral
Si-poor, metapelitic spinel (MgAI 204),
rocks hercynite (FeAI 204 );
gahnite (ZnAI 204);
galaxite (MnAI:P4)
Staurolite metamorphic mineral, Fe 2AisSi 4 023 (0H) n/a often also common twins n/a yellow, up to 1st order n/a tourmaline, n/a
common in medium- comains pleoc~roic red but often epidote
grade micaceous many quartz masked by the
schists and gneisses inclusions strong colour of
the mineral
Talc marbles or as an n/a n/a similar to white n/a single clear high n/a Difficult to nfa
alteration product of micas birifrigence, distinguish
mafic and ultra-mafic 3rd order from muscovite
rocks interference and white
micas
 l

Tourmaline granites, higher grade Na(Mg,Fe,Mn,Li,AI} moderate n/a rare very poor Fe-rlch blue n/a n/a n/a n/a
metamorphic rocks, and 3AI6!Si601s](B03) to yellow,
often as detrital grains 3(0H,F), Mg-rich
yellow-pale
yellow, Li-rich
colourless-
other
Tremo!ite marbles, talc, and Ca 2 Mg 5Si 802z[OHh; n]a bladed, n/a one cleavage dear to pale upper 1st to n/a n/a n/a
forsterite some Fe may columnar, longitudinal green, slightly 2nd lower order
substitute for Mg, needle-like and two when pleochroic interference
forming solid solutions crystals viewed in more colours
towards actinolite end section pronounced
{60"-i20") with greater
Fe content
Wollastonite high-grade marbles, CaSi03 moderate to elongate and n]a n/a colorless low, 1st order n/a Ca-Mg Silicates n/a
associated with high relief bladed yellow
diopside and garnet
252 DENNIS BRAEKMANS AND PATRICK DEGRYSE

found in archaeological ceramics, is mainly composed of fine-grained ( <5 ~lm) polycrystal-

line silica and is often idenLified as quartz. Sandstones contain mostly monocrystalline quartz
and K-fetdspar or plagioclase with grain sizes ranging between o.o6 and 2 mm. Argillaceous
rock fragments are composed of angular to sub rounded non-plastic inclusions derived from
detrital sediments composed of clay, mud, and silt, which have been litWfied (Whitbread,
1986). Micritic inclusions are microcrystalline in nature and are seen as primary non-plastic
calcite inclusions (e.g. young sediments or carbonate inclusions from the soil) in the sherds.
Secondary carbonates are also common in archaeological ceramics, often as micrite (grain size
< 4~tm). This microcrystalline carbonate has been secondarily precipitated from soil solutions
after the burial of the sherd, and filled the pores and holes in it. Remains of the original inclu-
sions or void can still be detected (Plate 4e). Secondary inclusions identified in pottery studies
provide information about burial or post-depositional conditions, but are of little value for
determining raw material provenance or ceramic manufacture technology. Clay nodules are
another common sedimentary rock inclusion, which are typically rounded to well-rounded
pellets which may conceivably have been formed within a depositional environment of the
day and are distinguishable through differences in their fabrics compared to the enclosing
matrix (Whitbread, 1986).

Another common set of features directly relating to the raw materials is the presence of iron-
rich nodules and natural aggregates in the clay itself. These fragments are often (sub )rounded
particles, reddish to brown and commonly surrounded by shrinkage boundaries. The nod-
ules or pellets, and the occurrence of carbonized vegetal remains, testify to the use of readily
available clays from soils. These types of ceramics are thus derived from poorly worked clays
with a complete absence of homogenizing or purification operations. It has been discussed
that these clays are usually derived from a shallow depth (Amadori et al., 2002).

IDENTIFICATION OF POROSITY IN THIN SECTION

Pores and voids are common in ceramic materials and can result from a variety of processes.
Pores are often described as a result of the packing of minerals or grains within the ceramic
body. Voids referto spaces in the ceramic matrix that are large enough to be detected without
magnification (Rye, 1981) and are commonly created in ceramic fabrics as a result of organic
tempers burning out during firing or shrinking of the matrix material during drying. These
terms are often used interchangeably and umystematically in literature. More commonly, all
"empty" space within the ceramic is identified as a pore.
A primary cause for porosity in ceramic fabrics is the presence of air bubbles trapped
within the clay during preparation and production of ceramic vessels. Additional pores
develop during the drying and firing processes as a result of dehydration and dehydroxyl-
ation of the clay minerals in the matrix, and organic matter may burn out, partially or com-
pletely, during firing, thereby increasing porosity. A wide array of depositional processes
can also increase or decrease porosity, for example the dissolution of calcite grains or other
soluble minerals in ground water, and/or crystallization of gypsum or various salts within
the pore space (Rye, 1976; Maggetti, 1982; Freestone and Hughes, 1989). Porosity can be clas-
sified into primary and secondary pores. Primary pores are formed during the drying pro-
cess, replacing water between clay minerals. Through kneading or other day-preparation
procedures, clay minerals may be packed more closely together, diminishing the number of
 PETROGRAPHY 253

primary pores. Secondary pores are a result of first firing through shrinkage of the clay due
to its water loss, gas release (e.g. CO, after heating of CaC0 3), and burning out of organic
matter under oxidizing firing conditions. The shrinkage of clays is also reflected by a tiny
porosity band around inclusions.
Porosity can also be understood as a performance characteristic of ceramic vessels which
is controlled artificially by the potter and related to the function of the finished vessel. For
example, decorative, high-quality drinking cups should be impermeable; therefore a glassy,
hard, non-porous high-fired matrix is preferred. On the other hand, water storage vessels
may benefit from a non-closed pore structure which allows evaporation and helps keep the
contents cool. Cooking vessels are constantly exposed to drastic changes in temperature,
which often leads to cracking as a result of the variable thermal expansion coefficients of the
mineral inclusions and matrix material. Pores within the ceramic fabric reduce the effects of
this phenomenon to a large extent.
Generally, pores are identified by their irregular shape and orientation, if any are detected.
Elongated pores can be an indicator of an overfired vessel and result from shrinkage of the
matrix material during dehydroxylation (Herz and Garrison, 1998). When very high tem-
peratures are achieved, and silica minerals start to melt and form a glassy phase (including
shrinkage), this results in very rounded pores often called bloating pores. At these tempera-
tures, an increase in pore diameter has been documented that coincides with a decrease in
microporosity owing to sintering of the clay and crystallization of new minerals (Maggetti,
1982). Rice (1987) classifies pores as: (1) closed pores, (z) channel pores (connecting pores
or surface), (3) "blind-alley" pores (extending from the surface without other connections),
(4) pocket pores (having a narrow aperture or neck), (5) loop pores (two interconnected
ones), and (6) micropores. The excess of water loss in a clay matrix may induce a parallel
alignment of pores owing to (homogeneous) shrinking of the clay. Normally, these pores
are not connected in a network, can appear wavy, and may become narrower at the ends.
A consistent orientation of porosity may also point to worked areas of a vessel or be traced
back to vessel-shaping methods (Velde and Druc, 1999). For example, long elongated pores
may indicate the joining of two separate sections of the vessel, such as where handles or bases
are attached to a preform or where coils and slabs are joined and smoothed (Gibson and
Woods, 1997).
Deliberately added pores which aid in the functionality of a vessel, such as its permea-
bility to facilitate the evaporation of water, appear mostly as a network of interconnected
pores. Since this network structure of pores transfers heat out or away from the interior of
the vessel, these pores are not desirable for a cooking pot. Isolated pores in a ceramic body
allow its expansion and contraction, as a result of thermoshock, but also act as insulators
retained within these exceedingly small air pockets (Reedy, 2008). According to Rye (1976),
the advantageous range of pore size for cooking vessels is 5 mm-1 em, ideally7-9 mm. Large
pores can also substitute for large inclusions in cooking pots because they halt cracks within
a vessel body in a similar way. Likewise, extensive porosity may be useful in low-fired cook-
ing vessels, as a replacement for common mineral tempers, in resisting thermal shock prop-
erties (Rye, 1976).
Because porosity is three-dimensional, it is important to understand how pores are ori-
ented within the ceramic body. Therefore, it is of the utmost importance to document the
orientation/direction in which the sherd was cut to produce the thin-section sample: (1) per-
pendicular to the rim, (2) parallel to rim, or (3) at an oblique angle. For example, sections
254 DENNIS BRAEKMANS AND PATRICK DEGRYSE

cut perpendicular to the rims may exhibit a concentric and swirled pattern of pores while a
section, from the same vessel, cut parallel to the rim may exhibit an elongated, parallel set of
pores.
Porosity is directly influenced by the preparation and drying of the clay, firing atmo-
sphere, firing temperature, amount of temper, initial grain-size distribution of the fabric,
clay and inclusion mineralogy, and bulk chemistry of the sherd. However, differences in
pore-size distribution may help in differentiating ceramics from different time periods, loca-
tions, or even workshop groups. Although porosity data are valuable for identification of
vessel function and/or manufacture technology, the interpretation ofhow the porosity origi-
nated remains a complex issue which cannot always be resolved using ceramic petrography.

TECHNOLOGY: POTTERY FABRICATION AND USE

The Addition of Temper

A major research question in pottery studies is the treatment of a clay raw material. To
improve workability and performance, often two (or more) clays are mixed. The clay com-
ponent of a ceramic fabric is the matrix, and is normally beyond the scope and possibilities
of microscopy owing to the size of the clay minerals. Clues about the preparation of the raw
clay materials are, however, detectable using ceramic petrography. While the clay minerals
themselves are not identifiable in thin section, it has been suggested that an orange bire-
fringence of the ceramic matrix is related to the presence of illite clays (Morter and Iceland,
1995). Mixing of calcareous and more siliceous clays is often observed as swirling of colors or
textures-for example (Maggetti, 1982)-but it is often difficult to distinguish natural impu-
rities within a single clay source from the intentional mixing of sources. There are only a few
indicators to identify mixing of clays in thin sections. The systematic occurrence of differ-
ent color streaks, and thus different optical properties, may directly relate to the presence of
multiple clay minerals. Comparing ceramic samples to clay raw materials may yield accurate
information (Stoltman, 2001) but is often complicated by the alteration of raw materials dur-
ing the ceramic manufacturing process; for example, heavily tempered or levigated fabrics,
hampering or preventing a direct comparison.
Generally speaking, it is much more difficult to determine if inclusions or organics were
removed from a raw material than added (Braekmans et al., 2011). Homogeneous textural
properties and a consistent grain size and inclusions may represent considerable effort in
raw material preparation. On the other hand, lumps of clays and uneven grain-size distribu-
tion of mineral inclusions may indicate that less effort was spent on grinding, sieving, and
mixing of clays. The presence of clay pellets in a ceramic matrix deserves great care because
local variations in moisture may form these lumps during processing, but they may also
point a natural occurrence of pellets in the raw materiaJ or indicate a mixing of raw resources
(Vincent, 1988). Clay nodules or clay pellets can also be an indicator of poor kneading of
the clay paste during processing. During this kneading process, clays are blended, homoge-
nized, and inclusions are generally more evenly distributed throughout the clay matrix. Clay
pellets are distinguished by their different color and texture compared to the ceramic matrix
material. Furthermore, the presence of these clay pellets, and argillaceous rock fragments,
 PETROGRAPHY 255

might also indicate that the raw materials or clays were not well prepared, or at least not for
a long period of time. An abundant presence of voids also indicates that little kneading was
done during preparation of the material (Rye, 1981).
It has been observed ethnographically that calcareous clays are systematically levigated,
removal of inclusions above 0.1 mm using moving or flowing water, in order to prevent large
calcite inclusions in the fabric from spalling during firing (Freestone and Hughes, 1989).
Several methods exist for the removal of natural inclusions from the clay raw material in
addition to levigation, including hand sorting, sieving (after crushing and grinding), and
water-settling or sedimentation. Communities using sieving and hand sorting often have
more rock fragments and large mineral inclusions in their ceramic fabrics because of their
hardness and resistance when crushing the raw material before sieving (Vaughan et al.,
1995). Fine-grained ceramics are often the result of a carefully processed raw material, and
result in an even distribution of fine grains with a regular texture. In some coarse wares,
lumps of these fine-grained patches may be detected, indicating the mixing oflumps of day
(VeldeandDruc, 1999).
It is often difficult to differentiate intentionally added temper from natural occurring
inclusions; however, features such as angularity and frequency may provide clues as to
whether the potter deliberately added specific materials to the paste. Intentionally added
temper materials are often characterized by a high angularity, sharing no interaction with
the surrounding clay matrix. The argument for this is the absence of abrasion of the rock
and mineral fragments which would occur in a natural transportation of the raw material.
On some occasions this reasoning is problematic, however. For instance, quartz grains can
be added to a ceramic paste, although they might have been rounded by previous depo-
sition involving wind and water actions. A solution for this issue might be a comparison
between the grains themselves and the clay matrix. A bimodal grain-size distribution sug-
gests a deliberate addition of inclusions, whether rounded or not, when size, shape, and
degree of roundness is significantly different from more variable natural inclusions in the
clay matrix. Nevertheless, in some instances it remains difficult to positively identify tern-
per materials. Crushed pottery fragments on the other hand, commonly called grog or
chamotte, and organic material, such as chaff and dung, are clear indications of tempering
since these materials do not occur naturally in ceramic raw materials (Plate 4f) (Miksa,
2001). Overall, thin sections reveal differences in ceramic fabric recipes, which includes
the amount and type of non-plastic temper added and the presence and degree of mixing
separate clays.

Formation, Shape, and Surface Treatment

'!bin-section petrography may also provide information about the formation and shaping
processes of ceramic vessels not visible by macroscopic examination (Rice, 1987). Formation
and shaping methods include pinching, press molding, slab building, coil building, and
wheel throwing (Rye, 1981; Rice, 1987, 1996; Whitbread, zom). Forming a vessel is the result
of a complex sequence of activities, occasionally combining several techniques. However,
each production technique involves the application of pressure and the deformation of the
plastic ceramic paste, which results in the characteristic parallel alignment of platy minerals,
such as micas, voids, and other elongated inclusions. This characteristic orientation is easily
2)6 DENNIS BRAEKMANS AND PATRICK DEGRYSE

visible in thin section and is usually positioned with long axes at right angles to the direction
of the force (Woods, 1982).
Shaping a vessel by coiling or slab building often results in visible joins and voids, indicat-
ing the poor bonding as clay dries. ln addition, a coiled vessel can often be identified by the
circular or whirled orientation of all particles present.
Inclusions in wheel-thrown vessels are oriented with their long axes more or less paral-
lel to the vessel rim and base. However, the faster the wheel rotates the steeper the angle
of orientation away from a true horizontal position. Additional indicators of wheel-thrown
vessels include the fineness of the matrix and limited number and size of voids, since clay
for throwing needs to be thoroughly prepared, refined, and kneaded before use. Inclusions
larger than 3 mm are problematic when using a fast-turning wheel because they can cut the
hands of the potter and/or cause tears in the vessel walls (Gibson and Woods, 1997; Woods,
1982). Generally, this preferential orientation is visible only macroscopically.
Shaping and smoothing activities can also produce a parallel alignment of inclusions
(Velde and Druc, 1999 ), sometimes masking the orientation of inclusions diagnostic of shap-
ing technique. Burnishing and polishing, for example, may be detected in thin section, when
elongate inclusions have a parallel alignment near the surface and becomes more unsys-
tematic one towards the core (Vaughan, 1995). To successfully recognize such features, thin
sections are best made according to a well-defined orientation vis-<1-vis the ceramic vessel
(Whitbread, 1989). Other surface treatments, such as scraping and smoothing, also create
a preferred orientation of elongate particles. However, these techniques often produce a
weaker orientation because, like burnishing, they are performed when the vessel is less plas-
tic or leather hard. A strong orientation of the smallest elongate particles associated with the
groundmass, orientation of some inclusions and voids, and grading oflarge to small inclu-
sions are all indications of finishing techniques (Vaughan, 1991).
Thin-section analysis of wheel-thrown and hand-built pottery indicates that wheel-
thrown vessels typically have a denser fabric, random orientation and distribution of the
coarse-grained fraction, and a slight elongation of vesicular pores parallel to the clay walls
near the rim. Throwing a vessel rapidly on the wheel also produces an irregular discon-
tinuous network of fine fissures, and a random orientation of elongate inclusions in the
body of the sherd. Beating a vessel results in an increase in density of the fine mass and
alignment of pores at the outer sides of the vessel. Coil-built ceramics have clear, structural
discontinuities visible at regular intervals, such as networks of fine fissures and elongated
pores between zones of dense packing of clay aggregates and coarse inclusions. Fabrics of
pressed and/or molded ceramics demonstrate abundant fissures and subparallel orienta-
tion of pores.
To successfully attest these features, thin sections are best prepared with a known orienta-
tion. Thin-section samples are normally cut and polished perpendicular to the rim and base.
Some specifications are only visible in horizontal or tangential section, however, especially
regarding the manufacturing method (Whitbread, 1989 ).
Surface treatments, such as slips and glazes, can be easily identified in thin section. A slip
is a surface treatment based on a suspension of clay in water which is applied to a ceramic
vessel before firing. This additional layer can be decorative as well as functional. Usually it
changes the color of a vessel but may also be used to minimize the permeability of fluids or
food into the ceramic. The application of a slip layer can occur through dipping, pouring, or
painting. In thin section a slip can be distinguished as an optically inactive, separate layer on
F

PETROGRAPHY 257

the inner or outer surface. These slips are however often very thinly applied, approximately
30 fliD, of which remains may be only seen using thin sections.
A glaze, on the other hand, is a vitreous coating, a vitrified or glasslike layer usually based
on silica. A flux is added to lower the melting point of the glass. The composition of these
fluxes is typically based on lead, sodium, and potassium. The color of a glaze is determined
by the addition of metallic oxides; for example, iron and copper (Gibson and Woods, 1997 ).
Glazes are relatively easy to identify in thin section. Because of the vitrified layer a glaze will
mostly appear translucent in PPL and black, isotropic, in XPL.

Technology and Performance

1be relationship between the presence of minerals, their amounts, sizes, and the perfor-
mance characteristics of ceramics (e.g. thermal shock resistance, impact resistance, and
strength) may directly be linked to technological choices made by the potter. Thermal shock
resistance, for instance, is a measure of the ability of the vessel to undergo rapid changes
in temperature without cracking, an application sought after when dealing especially with
cooking pots. The main cause of thermal shock is the variable expansion or contraction of
inner and outer surfaces of the ceramic. These stresses occur when one surface undergoes
rapid heating, resulting in a temperature gradient through the vessel wall. The magnitude of
these stresses is affected by the thermal conductivity of the vessel body, bulk thermal expan-
sion coefficient, thickness of the wall, and shape of the ceramic (Tile and Kilikoglou, 2002).
Temper differences can point at the presence of multiple specialized production centers
rather than different clay provenances (Stoltman, 2001). Cooking vessels (as well as jugs and
jars) tend to have coarser and more abundant temper, in order to maximize resistance to
crack propagation (Bronitsky and Hamer, 1986) (Figure 15.3). Apart from coarse and fine
sand, grog, and rock fragments, calcite and shell temper are also often recognized in ceram-
ics. This temper material has the same thermal expansion properties as clay minerals: it
fractures easily into long plates with a large surface area, resulting in a greater resistance to
crack-forming (Stoltman, 2001).
Although calcite has good thermal shock resistance and heat transmission properties
(three times higher thermal conductivity than clay), the firing temperature of the vessels
should not be higher than 6oo-7oo"C in order to avoid decomposition of these grains. Up
to 6oo"C, the bulk thermal expansion of shell- or limestone-tempered fabrics is lower than
quartz, resulting in less stress. Partial decomposition and the formation of wollastonite, as
a reaction of calcite with clays, may already be detectable when firing slightly higher (Tite
and Kilikoglou, 2002). Cooking pots are generally characterized by clays low in calcium and
the addition of high amounts of mineral temper, also in reducing the cracking from ther-
mal shock. The addition of temper to cooking vessels can be explained by the heat trans-
mission properties necessary for these ceramics. Heat transmission in clays happens more
easily along sheet structures than across them. 1herefore worked clay, and subsequent paral-
lel alignment, does not transfer heat as well as particles in random order. Inclusions in the
matrix disrupt this parallel orientation and have inherently 'different thermal conductivity
properties. Abundant temper thus facilitates a more homogeneous heat flow and increases
heat retention of the vessel, resulting in improved cooking qualities. In addition, highly
porous ceramics will decrease the thermal conductivity, so that a dense or microporous
258 DENNIS BRAEKMANS AND PATRICK DEGRYSE

FIGURE 15.3 Photomicrograph of a Late Roman, quartz-tempered cooking vessel from

Carthage (Tunisia). Left texture and porosity can be evaluated under PPL, mineral identifi-
cation (mostly quartz tempered) and optical activity of the matrix is studied under crossed
polars{XPL).

matrix is preferred (Hein et al., zooS). To conclude, in order to form a vessel well suited
to function, control of mineral inclusions must ensure that a correct thermal expansion,
strength, permeability, and surface treatment is reached, depending on the desired form and
functionality.

TECHNOLOGY: EsTIMATING FIRING CoNDITIONS

IN THIN SECTIONS

Determining firing technology based on petrography is often an ambitious undertaking.

There are two main aspects of firing technology accessible through petrography: atmo-
spheric conditions and temperature. The firing process initiates removal of volatiles (H 2 0,
organics, and carbonaceous material) and fabric color is mainly controlled by the oxidation
state offerric oxides. Oxidizing conditions include the removal of carbon (C + 0,-> COJ
and produce a reddish-orange fabric color, resulting from the oxidation of iron and iron-rich
minerals (Fe,03). Black and gray fabrics, on the other hand, often indicate a reducing atmo-
sphere (0, poor/ CO rich). A reducing atmosphere allows both the reduction of iron oxides
as well as the deposition of carbonaceous material and thus yields an intensification of dark
and black colors. In reducing conditions, FeO and Fe,0 4 are prevalent phases resulting
 PETROGRAPHY 259

from1 Fe,03 +CO 7 2FeO +CO, or 3Fe,0 3 +CO 7 2Fe,0 4 +CO. In reality most prehistoric
firings are not completely oxidized nor reduced because the atmosphere can fluctuate exten-
i sively in time and temperature.
I.
Iron compounds can only be fully oxidized after removal of carbonaceous material, in the
form of C0 2 • Therefore, the presence of organic matter in the ceramic fabric is also respon-
sible for dark coloration and zonation. Under oxidizing conditions, all or most of the organic
matter is burned out, resulting in an oxidized reddish fabric. Nevertheless, even in an oxi-
dizing environment, if firing is done quickly and vessels are not allowed a sufficient "soak
time;' a dark core may be produced by the incomplete oxidation of iron in the fabric and/
or the incomplete burning of organic material. The presence or absence of different firing
cores or layering effects is influenced by the type of firing, length of firing, type of fuel, place-
ment of vessels in the kiln, and amount of air flow (Velde and Druc, 1999). Open- or pit-fired
pottery, for example, is rarely fully oxidized as a result of direct contact with fuel (e.g. wood
and ash) and, typically, insufficient firing time for complete oxidation. Dark patches and sur-
faces are in this case no result of reduction) but rather a deposition of carbon on and directly
below the surface. Kiln firing, on the other hand, involves the separation of fuel and pottery
and typically longer (controlled) firing times and higher temperatures producing oxidized
ceramics-or fully reduced ceramics (Tite, 1995, Maritan et al., 2006).
A combination of fabric color and birefringence of the matrix can be used to provide infor-
mation about the atmosphere and extent of firing (Buxeda I Garrigos et al., 2001). Owing to
the oxidation of iron-rich phases within the matrix, a birefringent, evenly colored yellow to
red matrix indicates complete oxidation, which could result from high firing temperatures,
a gradual heating rate, prolonged firing, and/or an oxidizing atmosphere. Reducing atmo-
spheres, low temperatures, and quick firing times produce a dark optically inactive matrix in
thin section. Intermediate or imperfect conditions, such as rapid firing to high temperatures
and quick cooling, lack of uniform atmosphere, and poor air circulation, result in a partial
or incomplete oxidation and will produce both optical active (exterior) and dark non-active
(interior) features in thin section (Amadori et al., 2002).
Firing features are easily visible macroscopically, but can be described more systemati-
cally with thin sections, incorporating void texture and ground mass features as described in
the section "Identification of Porosity in Thin Section': However, the color of a ceramic vessel
is more related to mineralogical composition in combination with firing techniques than to
exact firing regimes (Martin-Socas et al., 1989).
Identifying the firing temperature in thin section is based on the relationship between
firing temperature and chemical and structural changes that occur in the mineralogy and
microstructure of the vessel. Multiple factors, in addition to temperature, influence these
transformations, including the mineral composition of the raw materials, rate of cooling, the
maximum temperature attained, soak time, total duration of firing, the grain size of the non-
plastic inclusions, CaC0 3 content in the matrix or use of calcareous clays, and firing atmo-
sphere, making it very difficult to estimate firing temperature accurately. Estimating these
maximum temperatures precisely is usually not possible because of the wide range of tern-
perature variations found within a single kiln or pit, whether open or closed. Tite (1995) pre-
fers the use of"equivalent firing temperature:' defined as the temperature at which ceramics,
allowed to soak for one hour, would exhibit the observed mineralogy or microstructure.
Changes in mineralogy, microstructure, and texture result from the combination of firing
temperature and soak time or the overall heat input during firing. The benefit of thinking
260 DENNIS BRAEKMANS AND PATRICK DEGRYSE

about tiring temperature estimates as "equivalent firing temperature" is that it accounts for
both time and temperature. Equivalent firing temperatures for open firings generally range
between 550-75o'C and 750-95o'C for kiln firings. Firing temperatures up to woo'C are
relatively easy to achieve in a kiln environment, although achieving temperature between
noo-1150'C requires signif1cantly more technological sophistication (e.g. thermal insula-
tion of the kiln and throughput of hot gasses) (Tile, 1995).
Thermal decomposition of mineral phases is highly variable and dependent upon the
chemical composition, crystal structure, and grain size of the phases involved. Most fir-
ing temperature studies are conducted using X-ray diffraction (XRD), scanning electron
microscopy (SEM), electron probe microanalysis (EPMA), or physical testing procedures,
such as experimental re-firing. However, some of these features are also identifiable in thin
sections. Mineralogically, quartz is stable until approximately 1150'C, although a modifica-
tion from alpha to beta quartz takes place at approximately 570'C. When fired for a long
enough period at high temperatures, quartz will recrystallize into the higher temperature
silica forms, such as tridymite (867'C) and cristobalite (nso'C) (Freestone and Hughes,
1989; Henderson, 2ooo). Both K-feldspars and plagioclase minerals are also stable up to li
woo-wso°C. At higher temperatures, plagioclase feldspars can experienCe separation along
cleavage planes. Orthoclase feldspar, however, is only stable at <9oo'C (Chandler, 2001).
As discussed in a previous section, calcite is commonly used as a temper in archaeological
ceramics; therefore its thermal breakdown can often be used as an indicator of estimated fir-
ing temperature. Calcite (CaC03 ) has ranges commonly attributed between approximately
6oo'C and maximum 85o'C for first decomposition, while the presence of CaO (lime)
relates to an approximate temperature range of 70o-10oo°C In a ceramic matrix, CaO may
react with illite clay minerals to form higher temperature minerals, such as plagioclase,
gehlenite, and diopside (Vaughan, 1995). An experimental study concluded that firing cal-
cite-tempered pottery in a reducing atmosphere allowed better management of the firing
process and functionality of the finished product. Temperatures as high as 8oo'C could be
achieved without triggering calcite decomposition.
Clay mineral decomposition is as varied as the minerals themselves, for example illite
decomposes at 85o'C-9oo'C, while chlorite has a decomposition range between 550-65o'C
(Rye, 1981; Maggetti, 1982, 1994). Importantly, the decomposition of clay minerals at about
10oo°C often leads to the formation ofhigh-temperature minerals and phases, such as anor-
thite, mullite, cordierite, spinel, and wollastonite. The formation of these minerals is directly
related to the nature of the clay raw material itself, the presence of minerals and phases act-
ing as fluxes, firing atmosphere, temperature, duration, and the cooling time. For example,
high-lime clays tend to form plagioclase, diopside, gehlenite, and hematite under oxidizing
conditions and diopside, plagioclase, and spinel under reducing conditions, while low-lime
clays form plagioclase, sanidine, spinel, and hematite in oxidizing environments and plagio-
clase, sanidine, and spinel in reducing environments.
The optical activity or isotropism of the groundmass is a function of the degree of vitri-
fication, and thus can act as an estimate of firing temperature and soak time. For example,
presence of fine-grained high-order phases embedded in the groundmass exhibiting aniso-
tropic optical properties indicate either the use of a calcareous clay and/or a firing tempera-
ture below the decomposition of calcite at 750-8oo'C. Isotropic optical properties in the
groundmass, on the other hand, indicate either the use of non-calcareous resources or firing
temperatures of 8o0-1050'C (Maggetti, 1994). During the decomposition of clay minerals,
 PETROGRAI)HY 261

between 8oo-850°C, glass and spinel may start to form resulting in an isotropic matrix. If
the ceramic was held at this temperature only briefly, only the surface will show this altera-
tion. Thus an optical active or anisotropic matrix mostly indicates temperatures below Ssooc
(Vaughan, 1991, 1995). At a temperature above 9oo"C the grmmdmass fuses and clay min-
erals and micas deteriorate, resulting in a vitrified (glassy) matrix. Traces of a fine-grained
green silicate (probably pyroxene or olivine) have also been attested (Kamilli and Lamberg-
Karlovsky, 1979).

CONCLUSION

Thin-section petrography fulfils an important role in the scientific analysis of ceramics. In

addition, other, mostly chemical, techniques have been successfully applied in character-
izing ancient pottery. A combination of these analytical techniques is most successful for
studying the origin and the technology of ancient ceramics, as ceramic types and research
questions can be very different for various geographic areas and periods. Although
ceramic petrography is nearing a century of use in archaeology, it continues to be a robust
and viable method to unravel compositional and technological information on ancient
craft activities.

NoTE
1. However, anisotropic minerals will appear isotropic when orientated down an optical axis.
Because of the specificity of this orientation, chances are limited that every mineral frag-
ment within a sample is identically orientated, thus greatly annulling this complication.

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 CHAPTER 16

CERAMIC
MICROPALAEONTOLOGY

IAN P. WILKINSON, PATRICK S. QUINN,

MARK WILLIAMS, JEREMY TAYLOR,
AND IAN K. WHITBREAD

INTRODUCTION

THE term "microfossil" includes a number of microscopic fossil groups. Although the non-
mineralized tissues usually disappear shortly after death, the biomineralized shells and
skeletons (composed of calcite, silica, apatite, or resistant organic compounds) may be pre-
served. Micropalaeontological groups include representatives of all kingdoms, including
bacteria, fungae, single-celled aquatic eukaryotes (foraminifera, diatoms, radiolaria, silico-
flagellates, calcareous nannofossils, dinoflagellates), the reproductive bodies and cell linings
of plants (pollen, spores, phytoliths), and animals (such as ostracods and conodonts). They
display morphological evolution over time and live in a variety of environmental conditions,
making them invaluable in biostratigraphical studies and palaeoenvironmental reconstruc-
I
i
tions (cf. Armstrong and Brasier, 2005, and references therein). I
Microfossils have a number of archaeological applications including environmental and I
habitat reconstructions (e.g. Whittaker, 1999; Boomer et al., 2007; Holmes et al., zow; Smith,
zo12), provenance of building materials (e.g. O'Rourke, 19S3; Thomsen, 19S3; Ayyad et al.,
1991; Goren and Goldberg, 1991; Maritan et al., zoo3; Wilkinson et al., zooS, 2010; Tasker IIt
i'
et al., zou, in press) and statues (Alaimo et al., 2007), provenance of artifacts (Shaw, 1995;
Brooks and Darning, 1997; Fiorentino, 1998; Vermylen and Hollister, zoo6), enhancing the
stratigraphy of excavations (Groenman-van Waateringe and Jansma, 196S), and under-
standing human behavior, cultural interactions, technology exchange, and trade routes
(Vourela 1994; Quinn and Day, 2007; Quinn, zooS; Tasker et al., in press). As a result of
processing, storage, and consumption of foodstuffs, pollen, spores, and phytoliths can also
be found attached to the surfaces of ancient ceramic containers (Bryant and Morris, 19S6;
Bayman et al., 1996; Albert and Portillo, zoos), baskets (Bohrer, 1968) and tools (Hevly, 1964;
Bohrer, 1968; Shafer and Holloway, 19S3; Bryant and Morris, 19S6; Albert and Portillo, zoos).
Microfossils are occasionally used for the analysis of art (Svabenicld, 1993, 1995; von Salis
 CERAMIC MICROPALAEONTOLOGY 267

Perch~Nielsen and Plahter, 1995) and are occasionally the subject of art; indeed the earliest
illustration of a microfossil is found painted on an 850-100o-year-old Pueblo pot made by
the Mogollon culture in the Mimbres Valley, New Mexico (Arnold, 1982). Ostracods painted
on one such pot (Figure 16.1) appear to be Chlamydotheca, a genus that lives in freshwaters
of Central America and grows up to 3 mm in length, therefore being visible to the naked eye.
The presence of microfossils in archaeological ceramics has been known for some time
(e.g. Fouque, 1879; Davis, 1951), although it is only more recently that their usefulness has
been appreciated. The occurrence and nature of microfossil assemblages is related directly to
the types of raw materials used in pottery manufacture, the environment of deposition of the
raw materials, and to the methods and technologies employed in the construction of the arti-
fact, notably firing. Although the presence of microfossils has often been recorded during the
analyses of ceramics, detailed investigations are few, partly because of a misunderstanding of
their worth, partly because specialist micropalaeontological knowledge is required to ana-
lyze them, but principally because methods required to extract microfossils from artifacts
are destructive. A decision has to be made whether it is more important to keep a potsherd
as entire as possible or surrender a part of it for analysis. Micro palaeontological investiga-
tions, when carried out at all, are generally confined to stratigraphically poorly constrained
fragments or those oflittle stylistic value. For this reason, notable investigations into ceramic
micropalaeontology are few (e.g. Alhonen and Matiskainen, 1980; Trojer et al., 1996; Quinn
et al., 1998; Quinn and Day, 2007a, 2007b ), although when carried out as part of an integrated
analysis including ceramic style, petrology, and chemistry, the microfauna! and microflo-
ral content greatly enhances archaeological investigations. Not only can the provenance of
the raw materials be established and technology elucidated, but aspects of the local environ-
ment and landscape can be postulated and microfossils may also assist in identifying the
use to which pots were put. Integrated analysis is emphasized because when considered in
isolation, microfossils can lead to false conclusions unless their limitations are understood
(Gibson, 1986; Battarbee, 1988; juggins and Cameron, 1999; Kligmann and Calderari, 2012).
The value of integrated analyses of pottery was demonstrated by Tschegg et al. (2009) for
Late Cypriot Bronze Age (1750-1050 BC) Plain White Ware ceramics centered on the ancient
city ofEnkomi, on the south-eastern coast of Cyprus. Here the integrated analytical program
included major element, trace and rare earth compositions; loss on ignition; bulk miner-
alogy and clay mineralogy; textural, including microtextural, relationships; mineral chem-
istry; and micropalaeontology. These studies provide substantial evidence to determine
affiliations, provenance, and technology, the characteristic composition of Plain White Ware
ceramics being used to trace trade routes to ancient Mediterranean markets (e.g. Knapp
and Cherry, 1994 and references therein; Maguire, 1995; Gomez et al., 2002 and references

FIGURE 16.1 The earliest known image of a microfossil, putative ostracods thought to be
of the genus Chlamydotheca on a Pueblo pot made by the Mogollon culture in the Mimbres
Valley~ New Mexico, 850-1000 years ago. (Redrawn from the photograph by Arnold, 1982.)
268 l. WILKiNSON, E S. QUINN, .M. WILLIAMS, J. TAYLOR, AND I. K. WHITBREAD

therein; Tschegg et al., 2008, 2009). Some of the pottery sherds contained numerous well-
lI
preserved calcareous microfossils of benthonic and planktonic foraminifera, holothurian
sclerites, and scaphopod dentalia. The presumed Pleistocene source material in the immedi-
ate vicinity of the Enkorni excavation was found to contain an essentially similar microfau-
na! assemblage and can be suggested to be the source of the raw materials.

MICROFOSSILS IN ARCHAEOLOGICAL CERAMICS

'There are many types of microfossils, and only those that have been recovered from ceram-
ics are mentioned here. To help the non-specialist, they are arranged by the composition of
their skeleton or shell (Figure 16.2). For a good general introduction to the major microfossil
groups see Armstrong and Brasier (2005, and references therein).

FIGURE 16.2 Examples of the main microfossil groups that may be found in ceram-
ics. For further discussion, see the text. a-c. organic-walled microfossils. (a) Eocene dino-
flagellate cyst; (b) Holocene pollen grain of pine; (c) Holocene spore of sphagnum moss);
(d-f) Siliceous microfossils; (d) Quaternary pennate diatom; (e) Eocene centric diatom;
(f) Eocene radiolarian; (g-j) Calcareous microfossils; (g) Cretaceous coccosphere compris-
ing numerous plates or coccoliths; (h) Holocene benthonic foraminifera; (i) Neogene plank-
tonic foraminiferan; (j) Kimmeridgian ostracod.
 CERAMIC MICROPALAEONTOLOGY 269

Organic Walled Microfossils

Dinoflagellates are single celled protozoans (generally 20-1so flm in size) that propel them-
selves through fresh and marine waters by means of whip-like flagellae. During their life-
cycle they go through a "resting stage;' or hypnozygote, where they produce organic-walled
dinoflagellate cysts (Figure 16.2a); it is this structure that is fossilized. They are rarely found
within ceramics as they are generally destroyed during firing; however, Hunt (1996) recorded
them in Iron Age sherds from Milton Keynes, UK.
Pollen (Figure 16.2b) is the male reproductive stage of seed plants (angiosperms and
gymnosperms), their resistant organic wall permitting preservation in the fossil record.
"Lower plants" (cryptogams), including non-vascular bryophytes (mosses, liverworts, and
hornworts) and pteridophyte vascular plants (such as horsetails and ferns), produce spores,
which are similarly fossilized (Figure 16.2c). Spores and pollen are easily transported by wind
and may be incorporated into the clay or slip of ceramics during construction. Pollen has
been described from ceramics by, for example, Magid and Krzywinsld (1988), Hunt (1996),
and Ghosh et al. (zoo6).

Siliceous Microfossils
Diatoms are small (commonly between 20-200 f!m), single celled, photosynthesizing
algae with a siliceous skeleton (frustule) (Figure 16.2d-e). Some are colonial and form long
chains that may reach lengths of up to z mm. 'They are found in almost every aquatic envi-
ronment including fresh and marine waters and wet soils. Diatoms have been described
in, and isolated from, ceramic material by Alhonen and Matiskainen (1980), Alhonen et al.
(1980), Gibson (1983), Jansma (1977. 1981,1982,1984, 1990), Matiskainen and Alhonen (1984),
Hakansson and Hulthen (1986, 1988), and Hakansson (1997).
Radiolarians (Figure 16.zf) are holoplanktonic, generally non-motile, marine protozoans
(super group Rhizaria). Those that have opaline silica skeletons (about so-zoo flm iu size) are
commonly preserved as fossils, but other forms with strontium sulfate skeletons are rarely
preserved. Radiolaria have been recorded within chert inclusions in thin sections of ceramics
by many authors, including Farnsworth (1964), Whitbread (199s), and Day eta!. (2011).
Silicoflagellates are unicellular, planktonic algae that form a siliceous skeleton (about 20-
so f!m across), composed of a network ofbars, spines, and spicules (they resemble radiolaria,
but are generally much less complex). Silicoflagellates, which are found in marine environ-
ments, are rarely recorded in ceramics, although one example was reported by Hakansson
(1997).
Phytoliths (or "plant opal") are formed by certain plants that take up soluble silica (as
monosilicic acid) from the soil and deposit it (as silicon dioxide) within intracellular and
extracellular structures. After the death of the plant, the silica is released from the decayed
plant and preserved as microscopic phytoliths of varying sizes and shapes. Phytoliths have
several archaeological uses including interpreting agricult~ral practices, food sources, and
food preparation and storage, having been found associated with garden areas, ritual offer-
ings, grinders, scrapers, and cooking and storage vessels (e.g. Pearsall and Piperno, 1990;
Jones, 1993; Tubb et al., 1993; Pearsall, zooo; Hodson, 2002; Harvey and Fuller, 2oos; Albert
and Portillo, zoos; Piperno, 2oo6; Lustek, 2006).
270 I. WILKINSON, P. S. QUINN, M. WILLIAMS, J. TAYI,OR, AND L K. WHITBREAD

Calcareous Microfossils
Calcareous nannofossils are formed by extremely small (0.25-30~m) single-celled,
marine eukaryotic haptophyte algae called coccolithophores. Their calcareous skeleton
forms a spherical body (coccosphere) composed of a number of individual disk-like
plates (coccoliths) (Figure 16.zg). On death, the coccosphere usually breaks up into its
individual coccoliths. Nannofossils have been recorded only occasionally in ceramic
samples (Troja et al., 1996; Fiorentino, 1998; Quinn et al., 1998; Quinn and Day, 2007a,
2007b). This may be related to their small size, which is below the resolution of most
petrographic microscopes, or by being detrimentally affected by the firing of ceramics
(Quinn, 1999a).
Foraminifera (Figure 16.2h-i) are single-celled rhizarians bearing a shell (or test; they
are sometimes called "armored amoeba'') usually composed of calcite or sand and silt
grains that have been cemented together by calcareous or siliceous cement. The test may
be a single chamber or a group of chambers variously coiled and usually between 250 and
1000 ~min length (although some may be as small as a few tens of microns and others reach
several centimeters in length). Each chamber is connected to the next by a series of holes
called a foramen (hence the formal name of Foraminiferida, "hole-bearers"). Foraminifera
are found in all marine environments, where they have either a planktonic or benthonic
mode oflife. This group of microfossils has been observed. on numerous occasions in pot-
sherds in thin section (e.g. Fouque, 1879; Einfalt, 1978; Williams, 1978; Riley, 1981, 1982,
1983; MacGillivrayet al., 1988; Vaughan, 1990; Day, 1995; Stilborg, 1997; Vaughan et al., 1995;
Montana et al., 2003; Ajdanlijsky et al., 2oo8), and have been isolated for detailed analysis
by Quinn (1999b).
Ostracods are arthropods belonging to class Crustacea. The animal is suspended from
and enclosed by a dorsally hinged carapace composed of two low magnesium calcite valves
(typically between 500-1000 ~min length) that are commonly found as fossils (Figure 16.2j).
They are found in all aquatic environments from the deep sea to temporary freshwater ponds
where they have a nektonic or benthonic mode oflife, and a few species live in wet soils and
damp leaflitter. In order to identify ostracods at the species level, details of their morphology
such as muscle scars (preserved on the internal surface of the carapace), lobation, ornament,
and hinge type are required. These characteristics may be seen when specimens are recov-
ered after the disaggregation of a sherd into its constituent grains (Williams et al., 2015), but
not in petrological slides where it is possible only to record their presence (Day et al., 1999a;
Whit bread, 1995; Alaimo et al., 1997; Whitelaw et al., 1997 ).

Sample Preparation
There are numerous techniques available for the preparation of samples for micropalaeon-
tological analysis of artifacts. These may require the preparation of thin sections or the dis-
aggregation of a potsherd into its component grains. The method chosen must reflect the
microfossil group being analyzed; for example, very small fossils (such as coccoliths) may
be obscured by larger grains in a petrological thin section, and a technique involving acid
will isolate certain microfossils, but damage or destroy others. Detailed preparation tech-
niques are too complex to give in detail here, but techniques can be readily found elsewhere
 CERAMIC MICROPALAEONTOLOGY 271

(e.g. Kummel and Raup, 1965; Battarbee 1986; Pearsall, zooo; Albert and Portillo, zoos;
Armstrong and Brasier, 2005; Riding et al., 2007; Quinn, 2013).

WARNING: All methods of preparation require the use of hazardous materials and equip·
ment. Preparation should only be carried out in properly equipped laboratories, in a fume
cupboard, wearing the correct safety clothing, and under the supervision of, or after training
from, qualified laboratory technicians. For UK laboratories, remember to comply with the
laboratory's risk assessments and COSSH instructions (national and local regulations will
apply to laboratories outside the UK).

MICROFOSSIL ANALYSIS

All methods of analyzing microfossils in archaeological ceramics require the destruction of

a part of the artifact and should therefore be mainly applied to sherds of lesser stylistic or
contextual importance, but where numerous sherds are present; sacrificing one may result
in a better understanding of the remainder. Microfossils are best studied with the use of a
petrological or biological microscope depending on the type of microfossil, but electron
microscopy will allow the finest details to be viewed.

Petrological Thin Sections

Analysis of petrological thin sections of ceramics is the most convenient means of detect~
ing the presence of most microfossil groups. Foraminifera and ostracods have a distinctive
appearance in thin section that makes them stand out from the inorganic mineral constitu-
ents of the paste (Quinn, 2013). However, there are limitations in this method of analysis.
Whilst microfossil identification at the generic level is usually possible for foraminifera, rec·
ognition at the species level is often impossible when it depends on morphological details
(e.g. ornamentation, aperture characteristics). In addition, because microfossil analyses are
essentially destructive, sample sizes are kept to a minimum and microfossil abundance in
each thin section rarely exceeds a few individuals oflarger microfossils, such as foraminifera.
For smaller microfossils (e.g. dinoflagellates, diatoms, and pollen), identification is hindered
when specimens are obscured by larger inclusions and details of almost transparent diatoms
are obscured by the clay matrix in ceramic thin sections (Hakansson and Hulthen, 1986;
Hakansson, 1997). Calcareous nannofossils, being extremely small in dimension (less than
10 f!m), can often be observed as complete specimens in thin sections (which are normally
about 30 f!m thick); however, as they are often obscured by other grains, it is better to prepare
smear slides (Quinn et al., 1998; Quinn and Day, 2007).
Despite the problems associated with working with petrological thin sections, this
technique provides the best way of assessing the relationship between microfossils and
the ceramic. Microfossils occur in several different contexts within a ceramic sherd: in
the raw clays used in pottery making, in particles added as a filler or temper, in slips and
paints added as decorative coatings, or via unintentionally ai'rborne contamination during
manufacture. Thin sections therefore complement analyses of disaggregated or digested
272 1. WILKINSON, P. S. QUINN, M. WILLIAMS, J. TAYLOR, AND L K. WHIT BREAD

residues and smear slides by elucidating the context, occurrence, and distribution of the
microfossils in relation to the artifact and add a further dimension to the interpretation of
ceramics. They are also a good means of assessing the microfossil content of archaeologi-
l
cal ceramics and determining whether it is worth submitting samples for further, destruc-
tive analysis.

Disaggregated Samples
Isolation of individual microfossil specimens by the disaggregation of ceramic sherds
into their individual grains by mechanical and chemical treatment is the preferred
method of analysis as it permits the three-dimensional analysis of specimens. Most fora-
minifera and ostracods need to be isolated from the surrounding clay matrix in order
to identify them to species level at low magnifications (often less than x 100 through
to about x zoo) (Davis, 1951; Quinn, 1999b; Quinn and Day, 2007). Disaggregation is
the only viable means of studying smaller microfossils such as diatoms (Gibson, 1983;
Hakansson and Hulthen, 1986; Jansma, 1990), silicoflagellates (Hakansson, 1997), and
palynomorphs (Magid and Krzywinski, 1988, Hunt, 1996; Ghosh et al., zoo6), when mag-
nifications required are high (at least x woo). Calcareous nannofossils can be studied
by taking a minute scraping from a pot in order to make a smear slide for examination
in polarizing light (Fiorentino, 1998; Quinn et al., 1998; Quinn and Day, 2007a, 2007b).
Both organic walled microfossils and siliceous microfossils have to be isolated by dissolv-
ing the sediment that surrounds them with strong chemicals such as hydrogen peroxide,
hydrochloric acid, or hydrofluoric acid (Gibson, 1983a; Hakansson and Hulthen, 1986;
Magid and Krzywinski, 1988; Jansma, 1990; Hakansson, 1997; Ghosh et al., 2006, Riding,
2007). Some can then be studied in normal transmitted light at magnifications ofx 100-
400, but others require magnification in excess of x woo and oil immersion lenses. For
magnifications in excess of x 1500, samples should be viewed in the scanning electron
microscope (SEM) (Quinn, 1999a, 1999b; Quinn, zoo8).

THE APPLICATION OF MICROFOSSILS IN THE

INTERPRETATION OF CERAMIC TECHNOLOGY

Microfossil analysis can be used to elucidate the technological processes used in the manu-
facture of archaeological ceramics, particularly in terms of methods of paste preparation and
ancient firing technology in spatial, temporal, and cultural contexts.

Materials and Manufacturing

The process of preparing clays in readiness for pot manufacturing often involves the
intentional combination of different materials, including the addition of temper or
the mixture of two or more clay sources, and where these different materials ·contain
 CERAMIC MICROPALAEONTOLOGY 273

microfossils, a record of their different origins may be preserved (Jansma, 1977, 1981,
1984; Matiskainen and Alhonen, 1984; Hunt, 1996) (Figure 16.3). A complex intermixing
of microfossils may result when clays and tempers of different geological ages and/ or of
different environments of deposition have been used, rendering interpretation of the
conflicting information a challenge. For example, calcareous marly inclusions within
the clay matrix of Middle Bronze Age pyxides from Knossos, Crete, were observed to
contain well-preserved Early Pliocene planktonic foraminifera and calcareous nan-
nofossils (Quinn and Day, 2007). Fossil assemblages were essentially similar to those
recovered from marls of the Early Pliocene Finikia Formation, although that deposit
had poor workability and was considered unsuitable for the production of ceramics
(Day, 1989). It can be concluded that the marl inclusions were added as a temper, and the
presence of the same species of microfossils in the clay matrix, is indicative of the degree
of mixing.
Great care must be paid to distinguish microfossils from temper, contamination during
the preparation of the clays for pot production, and microfossils from the clay matrix. For
example, pottery from a Neolithic site at Mahagara in North Central India contains rice
husks and phytoliths that were apparently used as temper, rather than being accidentally
added during production (Harvey and Fuller, 2005).

FIGURE 16.3 Examples of microfossils in ceramic matrices that can be applied in prov-
enance studies: (a-c) Siliceous microfossils in thin sections of Bronze Age archaeological
ceramics from Crete: (a) fragment of radiolarian skeleton within a calcareous inclusion
(width of view 50 ~m); (b) spherical radiolarians within a chert inclusion (width of view
L5 mm); (c) a pennate diatom within the calcareous slip (width of view= o.S mm); (d-h)
Calcareous microfossils in thin sections of Bronze Age archaeological ceramics from Crete;
(d) calcareous nannofossil (disco aster) in the groundmass of the ceramic and e. isolated in
a smear slide (width of view = 25 flm); (f) foraminifer (Dentalina terquemi) from a thin
section of an Iron Age shelly potsherd at Burrough Hill, Leicestershire (width 300 ~m);
(g) Ostracod in a thin section of a Garamantean potsherd from North Africa (width of
view 0.5 mm); (h) ostracod in a thin section of Bronze Age archaeological ceramics from
the Mediterranean demonstrating the preservation of an articulated hinge (width of view
0.5 mm).
274 L WILKTNSON, P. S. QUINN, M. WILLIAMS, J. TAYLOR, AND I. K. WHITBREAD

Firing Temperatures
Perhaps the most important process in the manufacture of ceramics is firing, when it is given
its stability, strength, and impermeability (Quinn, 2013). Early investigations (e.g. Davis,
1951; Linne, 1957; Brissaud and Houdayer, 1986) appeared to indicate that ceramics fired
at low temperatures contained well-preserved microfossils whereas ceramics subjected to
higher temperatures contained poorly preserved microfossil assemblages. This is an over~
simplification. Although the occurrence and preservation of microfossils in ceramics is
dependent on both firing temperature and atmosphere (Quinn, 1999a, 1999b, 2013; Quinn
and Day, 2007) (Figure 16-4), the type and composition of the microfossils must also to be
taken into account in order to interpret firing technology.
Organic walled microfossils are sensitive to the firing of ceramics. Above 400°C, in the
presence of oxygen, most organic matter, including pollen and spores are destroyed (Ghosh
et aL, 2006), but, in oxygen-poor or reducing conditions, it has been discovered that paly-
nomorphs can withstand very high temperatures (>1000°C). Hunt (1996) used the thermal
alteration index of palynomorph coloration (Staplin, 1969) to determine reduction-fired
temperatures for Iron Age ceramics from North Furzton, England, concluding that they
had been fired to a temperature of around 400°C. However, laboratory experiments into the
behavior of palynomorphs during firing (Quinn, 1999b) suggest that this may be an under-
estimation, as the thermal alteration of pollen, spores, and dinoflagellate cysts appears to
proceed at a much slower rate in reduction-firedceramics.

FIGURE 16.4 Degradation during firing. (a-d) Preservation of nannoplankton (cocco-

liths) from Gault clay briquettes fired at 6oo oc (a-c) and 8oo oc (b-d) (viewed under the
scanning electron microscope): (a-b) Watznaueria barnesae; (c-d) Zeugrhabdotus erectus
(scale bars= 1 ~m); (e) The remains of a foraminiferan recovered from an Iron Age ceramic
from Burrough Hill, Leicestershire by freeze-thaw methods (specimen height 0.55 mrn);
(f) Kinkelinella sp lacking much of the calcite carapace recovered from Iron Age potsherds
from the hill fort by freeze-thaw methods (specimen length 0.55 mm); (g-h) Organic walled
microfossils: although rarely recorded in ceramics) their potential for preservation is indi-
cated by the recovery of (g) dinoflagellate cyst of Spiniferites (width of view 0.15 mm) and (h)
angiosperm pollen (width of view o.8 mm) in reduction-fired London clay briquettes.
 CERAMIC MICROPALAEONTOLOGY 275

Calcareous microfossils are known to be detrimentally affected during the firing of

ceramics (e.g. Cau et al. eta/., 2002) by the alteration of calcite (Rice, 1987), although the tern·
perature at which calcite transforms depends on several variables, as demonstrated exper-
imentally by Quinn (1999a). The latter author fired briquettes of the Gault clay (used for
millennia for pottery and roofing tiles) at various temperatures in an oxidizing and a reduc-
ing atmosphere in order to determine changes in the calcareous nannofossil assemblage
(Figure 16-4a-d). The rich calcareous nannofossil assemblages began to change at tempera·
tures as low as 6oo°C by deterioration in preservation, a reduction in abundance, and pref-
erential taxonomic change as they were fired to increasing temperatures. Similar processes
have been observed in two archaeological potsherds from the island of Mozia, Sicily (Quinn
et al., 1998), the firing temperatures of which were calculated by X-ray diffraction (XRD)
to be c.6oo-700°C (Alaimo et al., 1997). The sample fired to c.600°C revealed an abundant,
diverse nannoplankton, whereas the higher-fired artifact contained only very rare, poorly
preserved specimens. This demonstrates that preservation of calcareous nannofossil assem-
blages is a potential proxy for ancient firing temperatures.
Siliceous microfossils may also be destroyed during the firing of archaeological ceram-
ics, although no experiments into this phenomenon have been carried out and the tem-
perature at which it occurs may vary. Jansma (1981) considered that firing at temperatures
above 8oo°C destroys diatom frustules, although Hakansson and Hulthen (1986) consid·
ered that diatoms can still be preserved at temperatures of 925°C.. based on the melting
point of amorphous silica at165o°C. However, certain substances within the clay paste may
act as fluxes, lowering the temperature at which siliceous microfossils melt (Rice, 1987).
Based on the conclusions of Davis (1951) and Linne (1957), Jansma (1990) suggested that
two technological phases of ceramic production could be demonstrated at a Neolithic site
at Schokland, The Netherlands. Jansma (1990) identified an earlier phase oflow tempera·
ture firing, characterized by ceramics containing abundant well-preserved diatoms, and a
later phase of firing at higher temperatures, resulting in diatoms being less common and
poorly preserved.

THE APPLICATION OF MICROFOSSILS

IN DETERMINING CERAMIC PROVENANCE

Clay is a high-bulk, low-value commodity and, except in exceptional instances (such as

the absence of suitable water and energy source), is unlikely to have been transported far
from its source (Vander Leeuw, 1977; Nicldin, 1979; Rice, 1987). Arnold (1980, 1985) con·
eluded that about 85% was sourced within 7 km of the point of manufacture, although this
clearly depends on the historical context, availability of transport routes, and the technol-
ogy available. There are two principal methods of determining ceramic provenance using
microfossils, a biostratigraphical and a palaeoenvironmental approach, and the combina-
tion of both approaches may result in more rigorous conclusions. Taphonomic processes
may affect both approaches and have to be taken into account during analyses, and fossil
identification is made difficult when degradation removes morphological characteristics
(Figure 16-4).
276 I. \VILKINSON, P. $. Q~JINN, M. WILLIAMS, J. TAYLOR, AND I. K. WHITBREAD

Biostratigraphical Analysis
Biostratigraphy is the method by which rock successions can be dated using their fossil con-
tent (Rawson et al., 2002; Armstrong and Brasier, 2005). It depends on the morphological
evolution of fossils and their relationship to geochronology and stratigraphy. Key index spe-
cies (which should be easily identifiable, commonly present, have a broad spatial distribu-
tion, and have a short chronological range) can be used to recognize biozones and subzones
within a rock succession that allows regional and global correlation of rocks of similar age.
Microfossils in archaeological artifacts can be correlated with known biozonal schemes and
the geology of the region in which they were found, in order to determine the geological
age of the raw material used for pottery production. This in turn can be used, in favorable
circumstances, in combination with petrographic and geochemical data to locate the actual
deposits used in the past (Quinn and Day, 2007a, 2007b).
Contamination and alteration of microfossil assemblages in archaeological ceramics can
hinder accurate biostratigraphic interpretation and thus obscure provenance. Contaminants
introduced during manufacture or usage of a ceramic artifact must be dis~inguished from
the fossil microfauna! and microfloral content of the clay and temper used in provenance
studies. During preparation, clay is kneaded, temper is mixed with it, and water is added to
achieve the necessary malleability. The material is susceptible to contaminants at every stage
from windblown pollen and spores on the surface of the wet clay to the presence of diatoms
in freshwater sources. Further contamination may be added to the surface and into cracks
after use and during burial.
In some cases the general microfossil group may be sufficient to postulate a provenance,
particularly where the source rock is not far from the archaeological excavation, but often
recognition of genera and species are required for detailed provenance studies. For example,
radiolaria in chert temper in first-millennium Greek amphorae from Corinth could be cor-
related to a nearby outcrop of radiolarite (Whitbread, 1995), indicating local manufacture.
In another instance the microfossils prove that a local provenance can be ruled out; a good
example being Bronze Age sherds excavated at Tel Haror in the Negev Desert, Israel (Day
et aL, 1999a; Quinn and Day, 2007), where microfossils in combination with compositional
and typological data prove a more distant provenance. The Tel 1-Iaror sherd is characterized
by the presence of rounded coarse grains of basic igneous rocks and ostracods, contrast-
ing with the local geology of the western Negev and the geochemical composition of other
Israeli ceramics (Oren et al., 1996), but resembles a few sites east oflerapetra on the south
coast of Crete (Whitelaw et al., 1997; Day et al., 1999b ). The sherd provides strong evidence
for maritime connections between Crete and the Levant during the second millennium
Middle Bronze Age.
There are numerous examples of calcareous, fossiliferous, shallow-marine clays, marls,
and limestones being utilized for ceramic manufacture on the southern coast of Crete, which
appears to have been a major center for ceramic manufacturing (Hein et al., 2004). The
ceramics recovered from excavations at Fournou Korifi and Pyrgos, near Myrtos, may be
taken as an illustration. The fabrics of almost half the ceramic artifacts excavated from the
final occupation level of this Early Bronze Age site are characteristic of the south coast, and
there is some suggestion that production may have been concentrated in the Myrtos area
(Quinn and Day, 2007a, 2007b). The ceramic fabric is characterized by the use of Neogene
clays and water-worn sand derived from basic igneous rocks. The presence of planktonic
--------·-··
CERAMIC MICROPALAEONTOLOGY 277

foraminifera such as Globorotalia subscitula, "dwarf" Globigerina acostaensis, and abundant

Sphaeroidinellopsis together with calcareous nannofossils indicate that south coast ceram-
ics were manufactured using Early Pliocene raw materials (Zachariasse, 1975; Spaak, 1983;
Quinn and Day, 2007a). Quinn and Day (zoo7a, zoo7b) concluded that the homogeneous
and laminated Early Pliocene marls of the Myrtos formation were combined with river or
beach sand and were probably used by the potters who formed the pottery by hand and fin-
ished it on a wheel.
Work on sites in Sicily by Troja et al. (1996), Alaimo et al. (1997), and Quinn et al. (1998)
also illustrate the usefulness in a biostratigraphical approach to provenance studies. Quinn
et al. (1998), recovered calcareous nannofossils from fifth-century sc ceramics and unused
raw materials in a Punic workshop on the island of Mozia. Individual pots and the deposit
of raw material were found to contain mixed calcareous nannofossil assemblages with spe-
cies of Cretaceous, late Palaeocene, late Eocene-early Miocene, Early Pliocene, and possibly
Pleistocene age. Ostensibly it would appear that materials had been collected from a number
of sources; however, samples of clay from a nearby stream, which was a suitable local source
of clay for the workshop, produced a comparable range of species, indicating that the clay
had a single provenance. The river had eroded sedimentary outcrops of different ages further
upstream and transported them close to the site of ceramic manufacture.
A preliminary investigation into the foraminifera in pottery sherds from the Thracian
archaeological site of Ada Tepe, near Kroumovgrad, southern Bulgaria, was carried out by
Ajdanlijsky et al. (zooS). Archaeological data places the majority of the pottery sherds to
the Late Bronze Age and Late Iron Age, but only pottery of the latter was fossiliferous. Most
microfossils occurred as indeterminate molds and fragments, but common Globobulimina
sp. and rare Globigerina eocaena were identified in the sherds. As these were also present in
late Eocene sediments of the area it was concluded that local materials were being utilized.

Palaeoenvironmental Analysis
Palaeoenvironmental analysis is used to model past changes in, for example, climate, aquatic
conditions (salinity, water depth, temperature, etc.), and vegetation coverand, in an archaeo-
logical and anthropological context, and can be used to identify human subsistence patterns,
trade, industry, agriculture, and cultural change. Reconstructing palaeoenvironmental
conditions is derived from chemical, isotopic, sedimentological, geological, and palaeon-
tological evidence. For example, microfossils of extant plants can be used to interpret past
climatic conditions as their modern requirements in terms ofhumidity/aridity, temperature,
elevation, and soil conditions are well known. Similarly extant aquatic microfossils preserve
information about water temperature, depth, and salinity, as well as changing environmental
conditions through time.
The palaeoenvironmental interpretation of microfossil assemblages occurring in ceram-
ics may also demonstrate relationships with the geology and have a potential in provenance
studies, although usually with less precision compared to the biostratigraphical analysis.
As a crude indicator, the proportion of freshwater to brackish to marine diatom species
has been used as an indicator of provenance within northwestern Europe (e.g. Foged, 1968;
Edgren, 1970; Jansma, 1977, 1981, 1984, 1990; Alhonen and Matiskainen, 1980; Alhonen
et al., 1980; Alhonen and Vakevainen, 1981; Gibson, 1983; Matiskainen and Alhonen, 1984;
278 I. WILKINSO!"', P. S. QUINN, M. WILLIAMS,/. TAYLOR, AND I. K. WHITBREAD

Stilborg, 1997). This distinction has been used to distinguish inland and coastal sources of
clays. Jansma (1984) and Stilborg (1997) attempted to differentiate local and distal prov-
enance of ceramics at coastal sites in the Netherlands and Denmark; sherds containing
marine diatoms were assumed to have been produced locally whereas those with freshwa-
ter diatom floras were thought to have been manufactured inland and transported to the
coastal site.
Phytoliths and pollen recovered from incompletely and fully fired sherds (c. 2,700 years
BP) from the Yanghai Tombs, Turpan, Xinjiang, northwest China, were used by Yao et al.
(2012) to reconstruct vegetation and climatic conditions. Bulliform phytoliths were consid-
ered to have been from Phragmites, which inhabit wetlands, and these authors went on to
suggest that highly weathered bulliform morphotypes are indicative of warm and wet condi-
tions. They also noted that a permanent change in phytolith color took place during firing,
which has potential as a thermal indicator.
Another illustration of palaeoenvironmental analysis in a provenance study is that by
Alhonen and Matiskainen (1980). Neolithic early comb ware ceramics from sites on the
Finnish archipelago of Aland were found to contain dominantly freshwater diatom species,
including Melosira arenaria and M. islandica, and were essentially similar to the assemblage
in the freshwater Ancylus Formation of the Baltic Sea. Clays of the Ancylus Formation do
not occur on the Aland Islands, but are common on the Finnish mainland. Alhonen and
Matiskainen (1980) postulated that during the Neolithic period, inhabitants of the Aland
archipelago appear to have transported comb ware ceramics from the mainland. Maritime
trade is also a possibility as the clays of the Ancylus Formation were used as a raw material
for Neolithic ceramics at other archaeological sites (Alhonen and Viikeviiinen, 1981).

THE APPLICATION OF MICROFOSSILS

IN DETERMINING CERAMIC FUNCTION

'!he function of a ceramic as suggested by its gross morphology may have been different
from its actual use in the past. The use to which a ceramic container was put, such as food
processing, storage, or consumption, can sometimes be ascertained by examining the pol-
len, spores, and phytoliths adhering to its surfaces (e.g. Bryant and Morris, 1986; Thompson,
1989, 1995; Bayman eta!., 1996; )ones, Bryant, and Weinstein, 1998).
Pollen was used to interpret the function and use of a group of sealed jars of the Proto-
Historic Period (c. AD 1500) from the Colorado Desert, USA by Bayman et al. (1996). The
contents of the sealed containers had fifty-six pollen types, some from plant species known
to have been used by native people of the area, but the dominant pollen type suggests that
the final use of the sealed jars may have been to store flowering plants such as fruits and pre-
serve them for future consumption. These data have implications with respect to the inter~
pretation of diet and agriculture (Thompson, 1989). There are, however, limitations in such
analyses because pollen may be unintentionally incorporated within ceramics during their
production in the form of "pollen rain'' (Magid and Krzywinski, 1988; Garda and Bernal,
1999; Ghosh et al., 2006), and distinguishing the contaminating pollen from that grown for
food may be difficult (Ayyad et al., 1991).
 CERAMIC MICROPALAEONTOLOGY 279

Phytoliths may be preserved, even after the decay of the original plants and after hav·
ing been heated to temperatures sufficient to cause charring. For example, scrapings from
the interior of cooking vessels from the Valdivia period at the sites of Real Alto and La
Emerenciana, Ecuador, released a number of maize phytoliths, proving its use as a food
source and providing an insight into agricultural practices (Pearsall and Piperno, 1990;
Pearsall, zooo; Piperno, 2003 and references therein).
Valdivia ceramics dating to the early occupation of Lorna Alta, Ecuador (c. 6,450 years
BP), are believed to have been used to process, cook, ferment, and serve plant foods. Zarrillo
et al. (zooS) demonstrated that charred residues adhering to the interior of cooking-pot
sherds at Lorna Alta yielded maize starch and phytoliths consistent with known maize cob
residues. Other phytoliths in the cooking-pot residues include Aracaceae (palm family) and
nodular spheres consistent with Marantaceae/Zingiberales/Bombacaceae and phytoliths of
arrowroot (Maranta spp.) seed epidermis. Maize was cultivated and consumed here at least
5,300-4,950 years BP supporting the notion that, once domesticated about 9,000 years ago,
maize spread rapidly from southwestern Mexico to northwestern South America.

CoNCLUDING REMARKS

Detailed micropalaeontological analyses of archaeological ceramics have taken place in an

ad hoc manner. This is likely to be because of a number of factors, including the destructive
preparation methods needed to study microfossil assemblages and the specialist micropal-
aeontological knowledge required to identify and interpret them. Some microfossil groups
may also have been overlooked owing to their small size and/or poor visibility in thin sec-
tion. Lastly, there remains a lack of awareness of the value of microfossils in archaeology and
the study of ancient artifacts. Microfossils clearly possess the potential to address impor-
tant issues in the analysis of archaeological artifacts including ancient ceramics, such as
their composition, processes that have affected them, their provenance, and the technology
involved in their manufacture. In integrated analyses, micropalaeontology complements
other compositional, typological, and archaeological characteristics.
Of the different groups of microfossils occurring in archaeological potsherds, calcareous
nannofossils, diatoms, and foraminifera are the most useful in provenance studies, although
for other archaeological artifacts, such as mortar, building stones, mud bricks, daub, and pit
linings, a wide range of microfossil signatures, including ostracods, foraminifera) dinoflagel-
late cysts, and pollen provide excellent markers. From the point of view of sampling rare or
archaeologically valuable artifacts, calcareous nannofossils probably remain the most useful
group as so much can be determined by scraping a minute quantity of powder from a sherd.
The provenance of ancient pottery is a subject in which micropalaeontology can be used
to supplement conventional methods of analysis, such as ceramic petrology and geochem-
istry. It requires an understanding of the nature of the artifacts and the enclosed microfossil
assemblages, and the geology and raw materials in the neighborhood of the excavation as
well as on a more regional scale. In some regions geological maps and specialist reports pro-
vide detailed geological information, whereas in other areas, primary geological investiga-
tion is required to map the distribution of suitable raw materials and fossiliferous deposits
before data can be used archaeologically.
280 I. WILKINSON, P. S. QCINN, M. WILLIAMS,). TAYLOR, AND L K. WHITBREAD

The investigation of ceramic technology can also be enhanced by micropalaeon-

tological data, although this area of research remains understudied and the nuances
remain to be understood fully. Microfossils show potential in terms of the recognition
of paste preparation methods and understanding firing technology. Firing conditions
are an important aspect of ceramic technology, and experimentation into the pres-
ervation of calcareous nannofossils (Quinn, 1999a) and palynomorphs (Ghosh et al.,
zoo6) during firing suggests that their degradation takes place in a predictable man-
ner and is related to temperature/oxygen levels. Although further experimental work
is required, it seems possible that these microfossils have the potential to provide an
archaeothermometric index by which temperature and oxygen levels during firing can
be estimated.
There is real potential in microfossil data for the investigation of archaeological ceramics,
and although there are strengths and weaknesses in the approach, more detailed studies will
prove micropalaeontology to be an important tool in the analysis of archaeological artifacts
and human development.

ACKNOWLEDGMENTS

IPW publishes with permission of the Director of the British Geological Survey (N.E.R. C.).
We are grateful to the Natural Environment Research Council (Grant NE/)o125So/l) for sup-
porting this research.

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 CHAPTER 17

ELECTRON MICROPROBE
ANALYSIS (EMPA)

CORINA IONESCU AND VOLKER HOECK

INTRODUCTION

ARCHAEOCERAMICS, such as pots, jars, cups, plates, aJilphorae, statuettes, and so on, are
generally made of a clay -based body with or without tempering material, fired at rela-
tively high temperatures (>6oo-650 °C). Therefore, the ceramic body can be regarded as
an artificial rock (Maggetti, 1986) formed through anthropogenic pyrometamorphism
(Grapes, zon). As with natural rocks, its composition can be studied by polarized light
optical microscopy (OM) and X-ray diffraction (XRD) but, for detailed information, meth-
ods such as electron microprobe analysis (EMPA), scanning electron microscopy (SEM)
(Freestone and Hunt, Chapter 31 this volume), Fourier transform infrared spectroscopy
(FT-IR) (Shoval, Chapter 28 this volume), cathodoluminiscence (CL), or Miissbauer spec-
troscopy are required.
Optical microscopy (Braekmans and Degryse, Chapter 15 this volume) is the basic method
to study ceramics in thin sections; that is, their composition, the relationship between min-
erals, the distribution and grain size of inclusions, and the texture and degree of vitrification.
However, the optical properties are often insufficient for a clear mineralogical determina-
tion, in particular when the minerals are very fine grained. Sometimes optical determination
of minerals is problematic because many of the minerals present are covered or penetrated
by iron oxide during firing, masking important optical features. Currently available chemi-
cal, structural and XRD databases are insufficient for identifying compounds and phases
newly formed during firing, which have no natural equivalents, and/or minerals thermally
modified beyond their usual composition. XRD complements OM by utilizing crystal struc-
ture (Heimann, Chapter 19 this volume). However, it does not allow the study of mutual
relationships between minerals.
Most of these issues can be successfully addressed by EMPA, an essential analytical
method in all branches of geosciences. Since the advent of commercially available elec-
tron microprobes more than fifty years ago (Long, 1995), they have become a routine tool
for detailed compositional characterization of materials. 1bis is particularly important in
 ELECTRON MICROPROBE ANALYSIS (EMPA) 289

the case of minerals forming solid solutions (e.g. feldspar) and for minerals with manifold
substitutions (e.g. pyroxene and amphibole). Maggetti (1979, 1982) has emphasized the
importance of mineralogical information in answering both provenance and technological
questions for archaeometric studies.
Electron microprobe is efficient in analyzing the matrix, the clasts, and the firing
phases in archaeoceramics. In the following, we will review the physical principles of
the electron microprobe and will present basic information about the equipment, sam-
ples, and analytical conditions. The potential outcomes of electron microprobe analyses
for the study of archaeoceramics will also be addressed. For more details, the reader is
referred to relevant literature; for example, Freestone (I982), jansen and Slaughter (1982),
Loretto (1984), Long (1995), Reed (1995, 2005), Lifshin and Gauvin (2001), and Goldstein
eta!. (2003).

THE PHYSICAL PRINCIPLE§ OF ELECTRON

MICROPROBE ANALYSIS

Electron microprobe provides insight on the composition of mineral phases using a narrow
electron beam to stimulate the emission ofX-rays. Accelerated electrons hitting a solid target
interact with the material in several ways and produce various signals (Figure 17.1a), among
which the most important are the backscattered electrons (BSE), the secondary electrons
(SE), and the X-rays (Reed, 2005). The latter include the characteristic X-rays and a continu-
ous X-ray spectrum. The scattering of the beam electrons inside the sample causes deflec-
tions and reflections in all directions. In the case of multiple deflections at a small angle or in
the case of high-angle reflections, a fraction of the incident electrons exit the sample, giving
rise to the backscattered electrons. The backscattered electrons come from a small volume,
i.e. -50-100 rm 3, inside the sample. '!heir energy distribution depends on the atomic num-
ber Z of the stimulated atom (Reed, 2005). The secondary electrons are ejected upon the
reaction of beam electrons with atoms near the surface of the sample or emerge from the BSE
when they leave the surface. TheSE have a lower energy than the BSE and provide data about
the surface. However, as they are partly produced by BSE, theSE also convey some informa-
tion about the chemistry.
The continuous X-ray spectrum is generated when an incident electron interacts with an
atomic nucleus in the sample. It may mask the characteristic lines of elements present in low
amounts.
The nucleus of an atom is surrounded by electrons in several levels (called shells), labeled
with increasing distance from the nucleus asK, L, M, N, 0, P and Q. An electron of a com-
pound within the sample hit by an electron from the incoming beam is expelled and leaves a
vacancy. Then, an electron from an outer shell fills in this vacancy and emits a characteristic
X-ray radiation. If, for example, an electron fills in a vacancy left on K-shell, the according
radiation is called K radiation. The energy and the wavelength of the X-ray radiation vary
with the atomic number Z (Reed, 1995). The characteristic X-rays enable quantitative deter-
mination of the chemical composition of a small volume of the sample, whereas the BSE and
SE are used for imaging (Figure J7.Ib-c).
290 COR INA IONESCU AND VOLKER HOECK

(a) focused incident

electron beam

secondary

electron interaction
volume within the
sample

FIGURE 17.1 (a) Origin of BSE, SE, and characteristic X-rays emitted by the interaction
between the focused electron beam and sample. The electron interaction volume within the
sample and the thickness of the electron beam are not at scale. Simplified drawing, based
on a chart from <http://www.jeol.com/>; (b) BSE image of a ceramic sample from Ibida
(Roman-Byzantine period) containing quartz (Qz), muscovite (Ms) and (chloritized) bio-
tite (Bt) embedded in a predominantly illitic (Ilt) matrix with some pores (Po). In the center
there is a siliceous test (Si), with a Ca-rich siliceous core (Si-Ca); (c) SE image of the same
area as in (b), showing the high topography of the clasts and the test, and the lower topog-
raphy of the illitic parts of the matrix. Most of the small black parts from (b) are proved
here to be areas with very low topography and not pores. Mineral abbreviations according to
Whitney and Evans (2010) are used throughout this chapter.

INSTRUMENTATION

1be electrons are generated by heating a filament commonly made from La-, Ce-hexaborate,
or tungsten. The filament acts as a cathode held at a negative voltage (15-30 kV) towards
the anode. The electrons accelerate through an aperture in the anode and form the electron
beam. This is focused by two or three electromagnetic lenses to a diameter of a few microme-
ters. The electron beam is visible when it hits luminescent material, such as scheelite or peri-
clase. For monitoring the beam current, microprobes have a swing-in Faraday cage made of
a conducting material. From the signals emerging from the electron beam-specimen inter-
action, the BSE and the SE are collected by special detectors. 1be electron microprobe is
commonly equipped with four or five wavelength dispersive (WD) spectrometer, used for
 ELECTRON MICROPROBE ANALYSIS (EMPA) 291

the quantitative analysis, and one energy-dispersive (ED) X-ray spectrometer, involved in
the qualitative analysis.
Each WD spectrometer contains a crystal of known lattice spacing d. Since one crystal
with a certain d value can detect only a limited range of characteristic wavelengths, several
crystals with different d values are necessary for analyzing the whole spectrum. The most
used crystals are: TAP (thallium acid phthalate), PET (pentaerythritol), LIP (lithium fluo-
ride), ADP (ammonium dihydrogen phosphate), muscovite, quartz, and KAP (potassium
acid phthalate).
All X-ray radiations are focused by the spectrometers and subsequently collected by gas-
filled counters. Ionization of the gas by interacting with the incoming X-ray radiations gen-
erates electric pulses, which are counted in order to measure the X-ray intensity.
The ED spectrometer has a completely different design than the WD spectrometer. It
is built up by a solid-state detector, a pulse height analyzer, and a multiple channel ana-
lyzer. The detector is made of a semiconductor crystal, mainly Si(Li) or high purity Ge.
The detectors are equipped either with a thin polymer-based or Be window. '!he first can
also detect elements below the atomic number of Na (n). The ED spectrometer shows all
characteristic X-rays simultaneously for the whole range of energies of interest. The X-rays
striking the detector generate an electric charge which is amplified by a transistor. The time
during which the system needs to process the pulses and during which no other pulses are
recorded is called "dead time:' Dead time increases with increasing input count rates. The
multichannel analyzer displays the data as counts versus energy diagram (insert in Figure
1pa).
Apart from the high overall count rate, the advantage of ED spectrometry compared with
WD spectrometry is the display of the whole range of energies produced by all elements
occurring at the measured sample point. On the other hand, WD spectrometers have better
resolution and a higher peak/background ratio. The WD spectrometers are also more pre-
cise and capable of detecting lower concentrations than the ED spectrometer.
Commonly, the beam has 10-40 nA current and a diameter of ,;5 ~m. The accelerating
voltage may vary from 1 to 30 kV, A lower beam current is necessary for obtaining high-
resolution imaging, whereas a higher beam current is used for detecting elements in low
concentrations. The detection limits of the instrument depend upon equipment perfor~
mance and specimen matrix, but are typically <o.1 mass% (Table 17.1). '!he counting time is
generally ws for the peak and 5S for the background. U1e precision is typically better than
o.os% at high concentrations, and better than o.o2% at low concentrations.

SAMPLE PREPARATION

"!he ceramic sherds must be cleaned with distilled water, in an ultrasonic cleaner. Low cohe-
sive and friable samples should be impregnated with low-viscosity epoxy resin. After the
sherd is left to dry, thin slices are cut across the thickness of the ceramic wall. These slices are
glued with epoxy resin to a glass lamella of appropriate size and then mechanically thinned
and polished with diamond paste, down to a 20-30 ~m thickness. Finally, the thin sections
are covered with carbon under vacuum and then mounted on the microprobe stage using
a sample holder. Carbon-coated, polished thin sections can also be used for polarized light
optical microscopy of mineral phases.
292 CORIN:\ IONF.SCU AND YOLK£R HOECK

Table 17.1 Mean atomic number for common minerals in ceramics. Data
from Reed (2005), except for minerals marked by*, which were
calculated by authors. The minerals are displayed in order of
increasing brightness
Mineral Zm Mineral Zm
--·-----~

Clinochlore 10.2 Clinopyroxene£ 13.0

Kaolinite 10.4 Gehlenite* 13.1
Albite 10.7 Wollastonite 13.6
Quartz 10.8 Apatite 14.1
Illite' 10.9 Hercynite 15.3
Mullite 11 '1 Epidote* 15.4
Muscovite 11.1 Rutile 16.4
Amphibole'' 11.7 Ilmenite 19.0
Anorthite 11.9 Hematite 20.6
K-feldspar 11.9 Magnetite 21.0
Calcite 12.4 Zircon 24.8

1
Magnesiohornblende
2 Augite

IMAGING

The combination of quantitative analyses with BSE images (Figure 17-2a-f) is one of the
strengths of the electron microprobe. BSE images, where the minerals can be identified by
the mean atomic number Zm (Table 17.1) reflected by brightness, carry not only qualitative
information in terms of chemical composition and element distribution but also show the
distribution and size relationship among the compounds. The size and shape of the voids are
pictured by BSE images as well. To receive an image, the beam has to scan the surface of the
sample in a rectangular manner. This is achieved by double-deflecting scanning coils (cita-
tion). The spatial resolution of the image is influenced mainly by the beam diameter, but also
by the energy of the incident electrons.
The mean atomic number of a mineral is calculated from the mass fraction of each partici~
paling element (Sanchez et al., 2012). For example, albite (Na-end member of plagioclase feld-
spars) has Zm = 10.7 and anorthite (Ca-end member) has Zm = 11.9. Plagioclases within this
compositional range can have Zm from 10.7 to 11.9 and consequently display a range of gray
levels. Micas, amphiboles, pyroxenes, and other minerals can also have a variable brightness
in BSE images, according to the possible element substitutions within the crystal lattice. The
brightness resolution (AZm) among distinguishable BSE images of minerals depends also on
Zm. At low Zm ( <20) the resolution is around 0.1-0.2; at higher Zm (>2o), the resolution is ~o-4-
_p.

ELECTRON MICROPROBE ANALYSIS (EMPA) 293

A BSE image (Figure 17.1b) and an SE image from the same area (Figure 17.1c) display strik·
ing differences. Compositionally, the analyzed sherd consists of quartz, K-feldspar, (chlori·
tized) biotite, muscovite, and illitic matrix. The large oval figure in the center of the image is
most likely the siliceous test of a microorganism containing a Ca-rich silica compound ( ~10
mass% CaO) in the core.
The BSE image (Figure 17.1b) shows a wide variety of gray levels, typical for the minerals
from which the sherd is composed; that is, dark gray for quartz, gray for muscovite, medium
gray forK -feldspar, and light gray for biotite. The core of the test is significantly brighter than
the rim, owing to the Ca.
On the other hand, the SE image (Figure 17-1c) shows the topographic variability of
the surface. The hard minerals such as quartz and feldspars are well polished and have a
higher topography than the softer minerals such as micas and clay minerals, with a lower
topography. In the SE image the brightness is more homogeneous and the Ca-bearing
core of the test is hardly discernible. Comparison of these two images shows that the
most of the small black parts in the BSE image are in fact areas of very low topography
and not pores (SE image). The real pores and voids are restricted to the areas where the
resin is exposed as dark porous material in the SE image. Therefore, the volume of pores
using BSE images can be overestimated. Textural features, such as the orientation of min-
eral compounds and voids inside the ceramic body, however, are better identified in the
BSE images (Figure 17.2 c, e, f).

COMPOSITIONAL MAPPING

An advantage of the electron microprobe is the possibility of compositional mapping of

samples. This is done mainly by ED but rarely by WD spectrometry (Jansen and Slaughter,
1982; Reed, 2005). The X-ray intensities are recorded from a rectangular area (Figure 17-3a)
and each X- ray radiation, characteristic of a certain element, is displayed as a tiny dot in the
image. Figure 17.3b-f shows the X-ray (ED) mapping of Si, AI, Fe, Ca, and Kin a ceramic
sherd. The density of dots reflects the element concentration in mineral phases. The most
obvious outcome in terms of ceramics regards the distribution of certain elements, such as
Ca and Fe. The X-ray mapping shows that these elements are finely dispersed within the
mass of clay minerals (Figure 17.3d, e). The bright spots in Figure 17.3d are tiny grains of Fe
oxides. In modern electron micro probes, the basis for mapping is the same but the "dot map·
ping" is replaced by digital mapping, converting the intensity of the X-rays into 256levels of
gray.

QUANTITATIVE MEASUREMENT

Imaging is very important as it gives a quick overview of the surface of the sample (SE
images) or a distribution of the mean atomic number over a certain area (BSE images), and
294 CORINA 10NESCU AND VOLKER HOECK
l
(b)

FIGURE 17.2 BSE images of various compounds of a ceramic body: (a) quartz and inhomo-
geneous feldspar (Fsp) crystalloclasts; feldspar shows Na-rich (dark gray) and K-rich (light
gray) parts. The white linear traverse displays the analyzed micropoints; the insert shows
the WD spectrum collected at the point indicated by the arrow; (b) profile displaying the
distribution of Na,O, K,O and CaO content obtained for the linear traverse shown in (a);
(c) muscovite, quartz, plagioclase (Pl) and K-feldspar (Kfs) in a clayey matrix with paral-
lel-oriented texture; (d) carbonate bioclast (Be); (e) ceramoclast (Cc), quartzite lithoclast
(Lc), quartz and K-feldspar; (f) pedogenic concretion (Pc); the bright parts are Fe-, Mn-, and
P-rich. Black parts are voids and most likely areas with low topography. Other abbreviations,
as in Figure q.1. Sources of the sherds: (a-b) Cucuteni (Copper Age); (c) Sarmizegetusa
Regia (Dacian period); (d) Jbida (Roman-Byzantine period); and (e-f) Ili~ua (Late Bronze
Age) in Romania.
 ELECTRON MICROPROBE ANALYSIS (EMPA) 295

FIGURE 17.3 X-ray maps of Cucuteni ceramics (Copper Age): (a) ESE image showing
K-feldspar and quartz embedded in reticulated matrix; black parts are voids and most likely
areas with low topography; (b) distribution ofSi in quartz and aluminosilicates; (c) distribu-
tion of AI in aluminosilicates; (d) homogeneous distribution of Fe, associated mostly with
clayey matrix; (e) inhomogeneous distribution of Cain the clayey matrix; (f) distribution
of K, marking K-feldspars and illitic matrix. Same scale for all images. Abbreviations as in
Figure 17.1 and 17.2.

helps to identify minerals and compounds as well as some textural features. But none of
these types of images gives the quantitative information which is essential for studies such
as provenance, firing transformations, or even a simple mineral identification and petro~
graphic description.
The quantitative analysis requires a well-defined point or area on the sample. Additionally,
a standard for each element of interest must be analyzed using the same conditions as
the sample. The elemental concentration is calculated by comparing the intensity of the
characteristic X-rays collected from the sample with those collected from the standard.
296 CORINA IONESCU AND VOLKER HOECK

Furthermore, it is important to correct for the background, which is mainly created by the
continuous X-ray spectrum (Reed, 1995). The first approximation of the "uncorrected" con-
centration of an element A in the sample (CA,) is calculated (Reed, 1995):

where !A, and IM are the intensity of characteristic X-ray for the element A in the sample and
standard respectively, and CA;t is the concentration of the element A in the standard.
According to Long (1995), the corrections to be applied to CAs depend on: (1) the primary
energy of the beam; (2) the loss of energy of the beam due to scattering in the sample; (3) the
efficiency of X- ray production; (4) the effect of the sample material on the X- ray; and (5) the
angle at which the X-ray radiations are collected by the spectrometer. The atomic number
correction (Z) accounts for points 2 and 3, the absorption correction (A) for points 4 and 5,
and the fluorescence correction (F) for point 4· Together, they establish the total correction
factor referred to as "ZAF correction." ZAF correction is routinely included in microprobe
software and is applied to both sample and standards. More details and other correction pro-
cedures are described elsewhere; for example, by Reed (1995).
The results of electron microprobe analysis appear as element concentrations and, except
for materials made of metals, metalloids, sulfides, tellurides, arsenides, antimonides, and
sulfosalts, are commonly recalculated as mass% oxides. The display of the results as oxides
is preferred for minerals, rocks, and, consequently, for ceramics. The concentrations below
detection limits are not reported (Table 17.2). Measurements should contain a maximum
of two decimals, and tables presenting the results need to include the total elemental con-
centration for each analysis. A total sum close to wo mass% for water-free and C0 2 -free
compounds is a first measure of the quality of the analysis (Reed, 2005). Lower sums can
be due to several issues related to the sample: (a) high porosity; (b) poorly polished surface;
(c) presence of H,O, OR owing to incomplete dehydration or dehydroxylation during the
firing or rehydration or rehydroxylation dnring burial; and (d) the presence of CO, (from
carbonates). Examples of EMPA data for minerals commonly found in archaeoceramics are
presented in Table 17.2.

ADVANTAGES AND LIMITATIONS

OF ELECTRON MICROPROBE

The most important outcome ofEMPA in the case of archaeoceramics is the precise char-
acterization of the chemical and mineralogical composition, as well as the microfabric
i.e. microtexture and microstructure (Ionescu et al., 2011). Many minerals vary in size
and composition, creating difficulties in their determination using other methods; for
example, OM, XRD, and SEM. In this respect, the interpretation of the BSE images is sup-
ported by the quantitative point analyses using electron microprobe. Even more, it can
analyze very small grains, down to 3-5 ~m. Another advantage of electron microprobe
lies in the high number of elements which can be determined, ranging from boron (Z = 5)
to uranium (Z = 92).
Table 17.2 Continued
Analyzed Detection !li~ua l!i~ua Sarmizegetusa Cucuteni lbida Cucuteni Sarmizegetusa Sarmizegetusa Sarmizegetusa llijua llijua
sample limit Regia Regia Regia Regia

Mn om 0.01 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.01 0.01
Mg 0.57 0.63 0.00 0.00 0.00 0.01 0.00 0.00 0.00 0.19 0.15
Ba 0.00 0.00 0.00 0.00 0.00 0.00 om
Ca 0.07 0.28 om 0.08 0.47 0.03 0.00 0.00 0.00 0.01 0.03
Na 0.05 0.26 1.81 1.28 1.68 0.42 0.36 0.08 0.11 0.12 0.13
K 0.81 0.69 0.03 0.09 0.01 1.30 1.62 1.65 1.58 1.50 1.30
Total 13.41 13.57 9.89 9.63 10.13 9.82 9.98 9.78 9.79 13.76 13.68
cations
Ab 97.9 88.2 77.6 24.3 18.3 4.7 6.6
An 0.7 5.7 21.9 1.4 0.1 0.0 0
Or 1.4 6.1 0.5 74.3 81.6 95.3 93.4
Fe/FeMg 0.55 0.66 0.45 0.66
Mg/FeMg 0.45 0.34 0.55 0.34
 ELECTRON MICROPROBE ANALYSIS (EMPA) 299

Among the limitations of electron microprobe (see Ionescu et al., 2011), the most obvious
is the lack of any structural information; in other words, whether a substance is crystalline,
amorphous, or vitreous. The polymorphs-for example, andalusite versus kyanite, or ortho-
clase versus sanidine-cannot be determined. In such cases, OM and XRD investigations are
necessary. Other problems encountered during EMPA regard the identification of compo-
nents smaller than the focused beam diameter and the occasional low totals of the quantita-
tive analyses ( see section Quantitative Measurement).

APPLICATIONS OF ELECTRON MICROPROBE

ANALYSIS TO ANCIENT CERAMICS

Ceramic body consists of various amounts of matrix (groundmass), clasts, firing phases,
and voids.

Matrix
Resolving the mineral nature of the ceramic matrix is a difficult task because it is an inho-
mogeneous very fine-grained mixture (<IS ~m or <20 ~m, according to Maggetti, 1979,
and lonescu and Ghergari, 2007, respectively) of thermally transformed clay minerals, Fe
compounds, and aplastic components. In particular, quantitative analyses accompanied by
BSE images and X-ray maps permit integrated interpretation of composition and thermal
changes (see Cultrone et al., 2001; Maritan and Mazzoli, 2004; Tschegg et al., 2009; lonescu
etal., 2011).

Clasts and Voids

Clasts may come from various environments and are generally regarded as aplastic com-
pounds. They include crystalloclasts-that is, fragments of individual crystals (Figure 17.2a,
c)-bioclasts-that is, fragments of organic origin (Figure 1pd)-lithoclasts-that is, frag-
ments of rocks (Figure 17-2e)-grog or ceramoclasts-that is, fragments of older ceramics
(Figure 17.2e)-and pedogenic concretions (Figure 17.2f). The BSE and SE images provide
valuable data about the size and spatial distribution of pores and voids, thus complementing
physical methods, such as mercury intrusion porosirnetry.

Firing Phases
Another important advantage of electron microprobe is the possibility to analyze the fir-
ing phases, often restricted to thin reaction films betvveen the grains or to isolated areas.
Basically, two important processes modify the mineralogy of a ceramic paste during firing:
(a) partial melting of aplastic inclusions and the matrix, and (b) various solid-state processes

_3{::__
300 CORINA lONESCU AND VOLKER HOECK

in the presence of a fluid phase (Ionescu and Hoeck, 2011). Firing phases include not only
compounds completely formed by the reaction of existing phases, but also minerals modi-
fied by firing and compounds formed by the breakdown of the crystalline structure and the
onset of melting.
For example, partial melting of quartz begins at the rims of the clasts. Apart from the opti-
cal isotropy, an investigation with electron microprobe shows that the glassy rims around
solid quartz relics are significantly enriched in AF+, K+, Na+, CaH, Mg2+, and FeTOT· This
indicates that the melting also involves parts of the surrounding matrix. In a similar way,
at the onset of melting the larger clastic micas still maintain their original composition.
However, as melting progresses, their chemistry is more and more influenced by the com-
position of the matrix. To accomplish this, ions from the matrix must be transported over
distances from micrometers to millimeters, requiring a fluid phase (Duminuco et al., 1998;
Ionescu and Hoeck, 2011) which comes, most likely, from the dehydroxylation of the illitic
groundmass (OH·) and/or from decarbonatization (CO,).
The firing phases may have complex and nonstoichiometric compositions (e.g. Brearley
and Rubie, 1990; Duminuco et al., 1998; Riccardi et al., 1999; Cultrone et al., 2001; Ionescu
and Hoeck, 2011). Depending on firing temperature, in CaO-rich ceramics, besides glass,
newly formed minerals such as gehlenite, akermanite, anorthite, wollastonite, diopside,
augite, larnite, and hatrurite may be present (see, e.g., Duminuco et al., 1998; Maritan et al.,
2006 and references therein). In theCa-poor ceramics, firing minerals may include spinel,
K-feldspar, mullite, cordierite, and corundum (see, e.g., Maggetti, 1995; Murad and Wagner,
1996; Khalfaoui and Hajjaji, 2009 and references therein). Fe oxihydroxides transform upon
firing into hematite, maghemite, and magnetite. Some of these newly formed mineraL1 are
rare in nature and are not likely to have existed in the ceramic raw material, either in the clay
or temper.
The matrix of many ceramics consists mostly of illitic clay, sometimes with kaolinite, and
more rarely, smectite. Table 17.2 shows examples of the microchemistry of fired illitic clays.
Despite the wide chemical variability of natural illite, the fired specimens often show a sig-
nificant depletion in K and enrichment inCa (Ionescu et al., 2011).
The onset of melting in a fired ceramic paste is very difficult to detect. Apart from meth-
ods such as electron backscattered diffraction (Stojakovic, 2012) or Raman spectroscopy
(Colomban et al., 2004) only optical microscopy is able to make the distinction between
crystalline and amorphous phases. Vitrification manifests as isotropic areas, which com-
monly have a lower refractive index than the crystalline phases nearby and show no inter-
nal structural features such as cleavage, zoning, or twinning. With electron microprobe, it
is sometimes possible to get information about melting from BSE images (Devineacr et al.,
2007; Ionescu and Hoeck, 2011), showing> for example, partial disappearance of cleavage,
and developing ofbubbles. In some cases the crystal shape becomes irregular, the rims of the
grains connect by saw-tooth patterned bridges with the neighboring phases, and the matrix
gets a reticulated appearance (Fig. rna). The glassy parts can be analyzed by electron micro-
probe (Hoeck et al., 2012). The melt in the immediate surroundings of the relic minerals
strongly resembles their chemical composition. Over larger distances, it becomes more and
more mixed with other melt patches and changes in character to an average composition.
Whether a mineral or compound has been formed during firing is often difficult to prove.
For example, feldspars and clinopyroxenes may form during firing or can be preserved as
clasts from the prefired raw materials. Some feldspars are metasomatically modified upon
 ELECTRON MICROPROBE ANALYSIS (EMPA) 301

firing. They incorporate Kc ions into their lattice, forming K- feldspar rims and patches on
plagioclase grains (Figure 17.2a-b ).
The thermal behavior of the ceramic compounds, such as decomposition, reaction, or for-
mation of new phases and melting, is indicative of the range of temperatures achieved. The
minerals, and in particular the plastic ones, suffer a series of changes, culminating with melt-
ing and eventual transformation into glass or new minerals upon rapid cooling. Even though
these thermal processes are not fully understood, they may serve as thermometers. Their
calibration requires detailed analytical work with electron microprobe and experimental
sequences, such as heating under well-defined conditions. In view of these unresolved prob-
lems, electron microprobe investigations will become more important with time, for the bet-
ter understanding of ancient ceramics.

Burial
The same considerations and limitations as above apply to the identification of changes
affecting a ceramic sherd upon burial, including deposition of foreign minerals. Such sec-
ondary phases are usually present in small amounts and are difficult to discern visually.
Furthermore, they can have the same chemistry as phases belonging to the sherd; for exam-
ple, CaC03 and SiO,. In this respect the combination ofEMPA with BSE images assists in the
separation of primary minerals from secondary phases. One important issue is the presence
ofP as a specific raw material (Ionescu et al., zon) or burial alteration (Maritan and Mazzoli,
2004).

Sourcing Raw Materials

Minerals and rocks in the ceramics have an important bearing on the area of origin, thus
acting as a key for provenance. Depending upon their geological origin, feldspars, pyrox-
enes, amphiboles, clay minerals, and micas may incorporate a wide range of elements into
their structure. A detailed interpretation of the mineralogical results combined with the
local and regional geology in the surroundings of the archaeological site often allows a
determination to be made regarding whether the mineralogy of the matrix and clasts is
compatible with the local geology or whether the ceramics are likely to have been imported
from elsewhere.
Feldspars are very common as clasts. Their overall composition and type of zoning are
excellent indicators of the geological background from which they originated. Feldspars
with high Ca content point to gabbros or diorites, whereas feldspars with low Ca are linked
to granites or granodiorites as parental rocks. Normally zoned plagioclase, with a Ca-rich
core and aNa-rich rim, as well as a complex oscillatory zoning (with albite-rich zones alter-
natingwith anorthite-rich zones), indicate a magmatic origin. Contrarily, an inverse zoning,
with aNa-rich core and a more Ca-rich rim, is characteristic. for metamorphic rocks.
Most micas and garnets are also indicators of metamorphic conditions during the for-
mation of their host rocks. A mineral assemblage of epidote and amphibole (actinolite to
magnesiohornblende) points to a metamorphic origin. Clinopyroxene with complex zoning
associated with amphiboles suggest basaltic to andesitic volcanic rocks in the source area.
302 CORINA IONESCU AND VOLKER HOECK

Chromite, clinopyroxene, orthopyroxene, and olivine remnants combined with serpentine

minerals reflect an ophiolitic background.

CONCLUSIONS

'!he electron microprobe is an appropriate tool to decipher the mineralogy and petrography
of ancient ceramics. Electron microprobe data combined with backscattered electron and
secondary electron images, WD and ED spectrometry data, and elemental mapping may
confirm or exclude certain rocks as sources of ceramic raw materials. Knowing the precise
composition of a mineral component of a sherd can support not only its formal classification
into provenance or compositional groups but also imply technological choices such as firing
temperature involved in the ceramic artifact production.

ACKNOWLEDGMENTS

Revisions and comments by Dr. Alice Hunt (University of Georgia), Dr. Miodrag PaviceviC
(Salzburg University and University of Belgrade), and De Dan Topa (Natural History
Museum Vienna) helped to improve the manuscript. Dr. Alice Hunt and Dr. Otis Crandell
are thanked for checking our use of English. Mrs. Monica Mereu (Babe1- Bolyai University
Cluj-Napoca) made the computer-assisted drawings. This study was financed by the
Romanian Ministry of Education and Research, through the PN-II-ID-PCE-2o11-3-o881
(CNCS/UEFISCDI) project. C.!. acknowledges subsidy from the Russian Government to
support the "Program of competitive growth of Kazan Federal University among world class
academic centers and universities:'

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 CHAPTER 18

ISOTOPE ANALYSIS

BETTINA A. WIEGAND

INTRODUCTION

PREVIOUS research into prehistoric ceramic provenance has focused on mineralogical, pet-
rological, and geochemical techniques, and a large number of studies are available on meth-
ods and applications from different archaeological sites (e.g. Kennett et al., 2002; Li et al.,
zoos; Cochrane and Neff, 2006; Fitzpatrick et al., zoo6; Beck and Neff, 2007; Sharratt et al.,
2009; Szilagyi et al., z012; Tiequan et al., 2012). More recently, lithogenic isotopes of the ele-
ments strontium (Sr), neodymium (Nd), and lead (Pb) are being explored for their potential
usefulness in ceramic provenance studies, for (a) the characterization of ceramic composi-
tion and identification of potential raw materials and their sources, and (b) elucidation of
organization of ancient trade and distribution of pottery wares among different cultures.
Sr and Nd isotope ratios have been used to deduce sources and characterize the composi-
tion of raw materials used in the production of pottery (e.g. Knacke- Loy, 1994; Pinter, 2005;
Li et al., 2006; Carteret al., 2011; Alex et al., 201z) and glasses (e.g. Freestone et al., 2003;
Degryse and Schneider, zooS; Huisman et al., zoo9; Degryse et al., 2010; Brems et al., 2013).
Furthermore, Sr isotopes have been used in human migration studies to investigate interac-
tion, movement, and trade of prehistoric people by comparative analysis of 87Sr/ 86 Sr in teeth
and bone tissues (e.g. Schweissing and Grupe, zoo3; Knudson et al., zoo4; Price et al., 2006;
Slovak et al., 2009; Herner et al., 2013).
Pb isotope ratios have typically been used as an indicator of the source of lead in pre-
historic metal objects and artifacts (e.g. Stos-Gale, 1992; Stos-Gale et al., 1997; Niederschlag
et al., 2003; Kuleff et aL, 2006; Weeks et al., 2009). In ceramic provenance research, Pb iso-
topes have been applied in a few studies to trace the origin of raw materials (e.g. Knacke-Loy,
1994; Renson et al., 2011, 2013) and to identify the sources ofPb in lead-based glazes applied
to ceramic products for decoration (e.g. Habicht-Mauche et al., 2ooo; Huntley et al., 2007;
Cui et al., 2010; Wolf et al., 2013). In addition, Pb isotopes are used to trace the origin of Pb
in ancient lead glasses (e.g. Henderson et al., 2005; Mecking, 2013). Provenance research by
Pb isotope ratios ofbulk ceramic sherds is based on the natural occurrence of small amounts
ofPb entrapped in minerals of the raw material, while Pb ores such as galena are usually the
source for Pb in lead-based glazes, metal artifacts, and in lead glasses.
306 BET'I'INA A. WIEGAND

Provenance analysis of archaeological materials requires knowledge of the isotopic com-

position of the source material. For example, a large collection of data on Pb isotopes cover-
ing Pb ore deposits of archaeological sites across Europe and the Near East is available from
the Oxford Archaeological Lead Isotope Database (OXALID) (Stos-Gale and Gale, 2009),
providing an indispensable reference for the study oflead-containing materials and metallic
artifacts by Pb isotopes. Concerning Sr isotopes, geographic distribution maps have been
published for a number of geographic areas. These studies are based on the analysis of stream
sediment and rock samples (e.g. Asahara et al., 2oo6) and/or include data for water, bedrock,
soils, and plants (e.g. Hodel! et al., 2004; Frei and Frei, 2013; Maurer et al., 2013; Hartman and
Richards, 2014). In general, the requirements for isotope distribution maps vary according
to the archaeological application and material type. In the case of human migration studies,
sources of biologically available Sr present in food and drinking water are of significance
(e.g. Price et at, 2002), while for ceramic provenance studies isotopic data from provinces
of raw materials (sedimentary deposits) are required. Raw materials for pottery production
are generally assumed to be derived from sources located in close proximity to the place of
ceramic manufacture. Therefore, investigations of raw material sources are mainly focused
on the vicinity of archaeological sites (e.g. Knacke-Loy, 1994; Carteret al., 2011; Renson
et al., 2013).
Previous investigations by Sr, Nd, and Pb isotope ratios confirm the great potential of
this method for a large spectrum of archaeological research questions. Nevertheless, for
provenance studies of prehistoric ceramic materials only a combination of archaeological,
mineralogical, petrological, geochemical, and isotopic techniques can provide the unique
fingerprint necessary to detect the origin of pottery wares and sources of raw materials with
high accuracy.

CERAMICS AND RAW MATERIALS

Composition of Raw Materials

Raw materials for pottery production are usually derived from fine-grained alluvial sedi-
ments and natural clay deposits, which have formed by weathering of igneous or sedimen-
tary rocks. Weathering processes result in the transformation of primary minerals such as
feldspars, amphiboles, and pyroxenes to various clay minerals (e.g. Wilson, 2004; Proust
et al., 2006; Hazen et al., 2013). Sr, Nd, and Pb are common trace constituents in both pri-
mary silicate minerals in rocks and their weathering products, and therefore isotopic ratios
of those elements in sedimentary deposits reflect the eroded bedrock in the provenance
area (e.g. Linn and DePaolo, 1993). Generally, mantle-derived basaltic and andesitic volca-
nic rocks are isotopically distinctive from crustal granitic rocks and their respective weath-
ering products. For example, basaltic rocks show 8'Sr/ 86 Sr ratios between 0.703 and 0.704
and positive eNd values, whereas rocks in old continental areas have generally high 87 Sr/
86 Sr ratios> 0.720 and negative eNd values, and·andesitic rocks in active tectonic settings

usually show intermediate Sr and Nd isotope compositions (e.g. Faure, 1986 and references
therein). Different grain-size fractions of detrital sediments derived from those rocks usu-
ally do not show significant variation in their Nd isotope composition, suggesting that
 ISOTOPE ANALYSIS 307

fractionation of Nd isotopes in coarse and fine fractions of sedimentary material from the
same rock formation is negligible. In contrast, variability ofRb/Sr ratios in different miner-
als and, consequently, differences in radiogenic 87Sr production, result in significant varia-
tion of Sr isotopes in coarse and fine fractions of sedimentary deposits (e.g. Nelson and
DePaolo, 1988).
Raw materials used in ceramic production can be derived from a single natural sedi~
ment source or artificially mixed components from several sources. In the case of a single
source and if the source is sufficiently homogeneous, raw materials will possess a distinct
mineralogical and geochemical composition that can be characterized by common petro-
graphic, mineralogical, and geochemical analytical methods, Isotope methods can pro-
vide important evidence in support of the traditional techniques for identification of the
material source. Generally, alluvial deposits are more prone to mineralogical heterogene-
ities that may be reflected in a higher variability of the isotopic composition of the mate-
riaL Heterogeneities in alluvial deposits are the result of changes in eroded bedrock in the
provenance area over geological timescales. In contrast, in volcaniclastic deposits a more
homogeneous isotopic composition can be expected. Based on the source characterization
by different geochemical and isotopic methods, distinctive clusters of the data may facilitate
finding the most likely provenance with high precision even if small heterogeneities exist in
the raw material source.

Composition of Ceramics
Sherds of pottery are usually the most abundant artifacts at archaeological excavation sites
and therefore are important evidence for cultural, social, and economic changes in ancient
societies. Understanding details about the provenance and manufacturing processes of
ceramic products provides insight into everyday life, mobility, trade, and interaction of
ancient cultures.
Ceramics are made of natural materials such as clays and fine-grained sediments, and for
this reason ceramics are analogous to sedimentary materials with respect to their miner-
alogical and geochemical composition. Bulk isotopic analysis of ceramic sherds results in
an average Sr, Nd, or Pb composition of the sample specimen that is equal to the bulk iso-
topic composition of the raw material, provided that the raw material source is sufficiently
homogeneous. Another principal requirement for the direct comparability of Sr, Nd, and
Pb isotopes in ceramic wares and their raw materials is that there is no or negligible isoto-
pic fractionation during tempering processes, which is generally assumed, but has not yet
been studied systematically, except for Pb isotopes in a metallurgic experiment (Cui and
Wu,zon),
Mineralogical heterogeneities in ceramic materials may be reflected in variable isoto-
pic compositions of the different components. For example, the Sr isotope composition of
the fine fraction (clay) may differ from the coarse fraction (small rock fragments or min-
eral inclusions such as quartz, feldspar, mica), while secondary mineral deposits (especially
calcium carbonate) resulting from the use of the vessel or later alteration processes may
additionally introduce strontium, which could alter the isotope composition of the origi-
nal material (Carteret aL, 2011). For the production of ceramics, alluvial deposits were usu-
ally used for coarse ware, while pyroclastic deposits were used for fine ware (e.g. in the Inca
308 BETTINA A. WIEGAND

empire: Szilagyi et aL, 2012). Therefore, the mineralogical heterogeneities in coarse wares
and especially the coarse mineral fraction may need special attention with respect to posH
sible variation in isotopic composition.

Composition of Glazes
Glazes are coatings of vitreous materials on ceramic objects that consist of a mixture of
silica (e.g. quartz sand), alumina (e.g. clays), and in the case of alkaline glazes also consider-
able amounts ofNa,O and K,O. Lead was added to the glaze mixture as a pigment but more
importantly to reduce the temperature during vitrification (e.g. Shepard, 1942; Tile et al.,
1998). Glazes were either applied as overall surface coating or as glaze paints for decorations
(e.g. Habicht-Mauche et al., 2000, 2002; Duwe and Neff, 2007; Crider, 2013). Lead-glazed
ceramics were commonly used in Late Hellenistic and Early Roman Asia Minor in the first
century sc but did not come into use in Europe before the medieval period (Greene, 2007).
Investigations of Pb isotopes on lead-based glazes can trace the source of Pb ores used in
the production of glazes similar to Pb isotope investigations of lead glasses (e.g. Mecking,
2013).

METHOD§

In this section the basic methodological concepts ofisotope analysis for ceramic provenance
studies are described, including a brief outline of the relevant isotope systems and technical
aspects such as sample requirements, sample preparation, and measurement techniques that
are currently employed in archaeological ceramic provenance research.

Isotope Systems
Strontium Isotopes
Strontium has four stable isotopes: 88Sr, 87 Sr, 86 Sr, and 84 Sr. 8'Sr is radiogenically produced by
radioactive decay(~·) of 87 Rb and therefore 87 Sr increases over time in geological materials.
While Sr substitutes for Cain common rock-forming minerals, Rb is a substitute forK owing
to their similar ionic radii and valence. 1be 87Sr/86Sr ratio of rocks and minerals therefore
varies significantly with the age of the rock and K (respectively Rb) content of the mineral.
Owing to radioactive decay of 87 Rb (half-life of 87 Rb is 48.8 x w' years), old rocks have pro-
duced a significant amount of 87Sr and therefore usually show a high 87 Sr/ 86 Sr ratio. Similarly,
even geologically young rocks and minerals with high Rb content (e.g. high K minerals such
asK-feldspars and mica) can produce high amounts of radiogenic 87 Sr and therefore exhibit
a high 8'Sr/86 Sr ratio. In contrast, rocks with high Ca content (e.g. marine limestone) and
Ca-bearing silicate minerals (e.g. hornblende, Ca-rich plagioclase) that also show high Sr
concentrations but low Rb contents usually have low 87Sr/86 Sr ratios. Depending on the geo-
chemical composition of rocks as a function of their genesis and provenance, Rb/Sr ratio,
 ISOTOPE ANALYSIS 309

and age, 87 $r/ 86Sr ratios are either high (e.g. in granitic rocks) or low (e.g. in basaltic rocks),
and vary depending on mineralogical composition in sedimentary rocks. 87Sr/ 86Sr ratios of
the weathering products of those rocks may vary depending on the degree of weathering, for
instance in detrital sediments, where easilyweatherable mineral fractions may be lost owing
to dissolution processes.
To date, Sr isotopes have been used in ceramic provenance studies by Knacke-Loy (1994),
Pinter (2005), Li et al. (2006), Carteret al. (2011), and Alex et al. (2012). An early study by
Knacke-Loy (1994) presented Sr isotope results for ceramic sherds and clays at Troy. Pinter
(2005) performed a comprehensive comparative Sr isotope study on knobbed ware from
locations in Greece and the Balkans. Li et al. (2oo6) used Sr isotopes to characterize and dif-
ferentiate Chinese Tang Sancai from the two production centers in Gongxian and Yaozhou.
Carter et al. (2011) analyzed pottery sherds and compared the results with available Sr iso-
tope data of potential raw materials from the Grand Canyon region of the Western United
States, and Alex et al. (2012) investigated ceramics of the Teotihuacan Valley in Mexico by Sr
isotopes.

Ndlsotopes
Neodymium has seven naturally occurring isotopes: 142Nd, 143 Nd, 14 4Nd, 145 Nd, 146 Nd, l48 Nd,
and ''0 Nd. >43Nd is produced by radioactive decay of '"Sm (half-life: 1.06 x w" years). Nd
belongs to the lanthanides, also called rare earth elements (REE), which are a group of ele-
ments with similar geochemical properties that form common trace constituents in rocks
and minerals. While high concentrations of REE occur in some heavy minerals, especially
phosphate minerals such as apatite, monazite, and xenotime, average Nd concentrations in
shale range between 30 and 40 ppm (Taylor and McLennan, 1985). The Sm-Nd system has
been used for decades to date rocks and minerals. Furthermore, the ratio of'''Nd/' 44 Nd has
often been used in combination with the 87$r/ 86 Sr ratio as a tracer of the provenance of rocks
(e.g. Faure, 1986; Dickin, 2005). Similarly, Nd isotopes alone or in combination with Sr iso-
topes may provide an important tracer in deciphering the provenance of ceramics and raw
materials.
Variation of the '43Ndf'44Nd in rocks and minerals are the result of radioactive decay of
"'Sm. 1herefore, the ' 43 Nd/' 44 Nd ratio in any geological material is dependent on the ini-
tial ' 47Sm/' 44 Nd ratio (e.g. during magma generation) and time elapsed since the forma-
tion of this magma. Sm and Nd are fractionated during magmatic processes (e.g. partial
melting, fractional crystallization); where Sm tends to enrich so-called "primitive" mafic
mantle rocks, whereas Nd is preferentially incorporated into felsic crustal rocks (e.g.
Faure, 1986; Dickin, 2005). '43Ndf'44Nd ratios in sedimentary rocks are inherited from the
original source rock that represents the provenance of the sedimentary materiaL 143Nd/
' 44 Nd ratios of geological materials usually show small variations that are expressed as

epsilon (ENd) values relative to the "'Nd/' 44 Nd ratio of achondrite standard. This standard
called CHUR (chondritic uniform reservoir) has a ' 43 Ndf'44Nd ratio of 0.512638 (DePaolo
and Wasserburg, 1976). ENd values are calculated according to the following equation:
144
wNd I Nd )
£ -
Nd- ( 143Nd/144Nd
""'''' I X 10 4
C/-/UR
310 BETTINA A. WIEGAND

Nd isotopes show generally less variability than Sr isotopes and in combination the two iso~
l
I
tope systems may provide a unique fingerprint of sedimentary raw materials used in ceramic
manufacture. Both Sr and Nd isotope signatures are commonly used by geochemists to char-
acterize and discriminate between rocks of different genesis and origin (e.g. Faure, 1986, and
references therein).
While REE concentrations and pattern have been applied in a number of studies using,
for example, neutron activation analysis or inductively coupled plasma-mass spectrometry
(ICP-MS) technique to investigate the source of ceramic objects (e.g. Kennett et al., 2002;
Li et al., 2005; Szilagyi et al., 2012; Tiequan et al., 2012), Nd isotopes have rarely been used in
archaeological research. One of the first comprehensive studies using Nd isotopes in con-
junction with Sr and Pb isotopes was conducted by Knacke- Loy (1994), who analyzed ceram-
ics and clays of Troy. A subsequent study by Pinter (2005) employed Sr and Nd isotopes to
trace the origin of knobbed ware in Troy, Turkey, and the Balkan region. Li et al. (2oo6)
used Sr and Nd isotopes to characterize Chinese 13.ng Sancai and sources of raw materials.
Furthermore, Nd isotopes have been used in glass provenance research by Henderson et aL
(2010), for example, who investigated Bronze Age glasses of the Mediterranean region, and
by Brems et al. (2013), who characterized beach sands as sources of silica in Roman glass
manufacture.

Lead Isotopes
Natural lead (Pb) has four stable isotopes: w8 Pb, w'Pb, w 6Pb, and w4 Pb. Three of them, wspb,
w'Pb, and w 6 Pb, are radiogenically produced by the decay chains of the uranium and tho-
rium series (23 2 Th, t 38 U, 235U). The half lives are 1.41 x 1010 years for t32Th, 4.47 x 109 years for
238
U, and 7.04 x 10 8 years for 235U (Faure, 1986). 204 Pb, also referred to as common lead, has
no radioactive parent nuclide, and therefore the abundance of 204 Pb does not change over
time. All Pb isotopes are assumed to have been uniform at the time of Earth's formation.
Since then, enrichment in the concentration of radiogenic Pb isotopes by radioactive decay
has changed the Pb isotope composition of the Pb reservoirs on Earth, while w 4 Pb is entirely
primordiaL
U and Ih are trace elements in common rock-forming minerals, such as feldspars, and
are particularly abundant in some heavy minerals such as zircon, sphene, apatite, and mona-
zite. Pb ores are mostly related to magmatic and hydrothermal activity associated with large
granitic intrusions. Lead is either found in primary lead sulfide ore bodies, commonly as
vein mineralizations, that mainly consist of the mineral galena (PbS). Often galena occurs in
association with other sulfidic ore minerals (e.g. Cu, Zn, Ag, Fe sulfides). In addition, galena
is found in secondary residual ore deposits that have formed by weathering and erosion pro-
cesses over time.
Lead ores that have formed throughout Earth's history are composed of a mixture of pri-
mordial Pb and different amounts of radiogenic Pb from the original source rock as a result
of radioactive decay from their parent isotopes. During formation of Pb ores, the Pb iso-
topes are essentially separated from their parent nuclides 238 U, 2>5 U and 232Th. Consequently,
there is no further radioactive decay of U and Th to alter the Pb isotope composition,
which means that Pb ores retain their isotopic composition after formation. Natural vari-
ation of Pb isotopes in Pb ores thus depends on the time of formation of those deposits.
1be abundance of radiogenic Pb isotopes in a Pb ore deposit is therefore constrained by
i¥1

ISOTOPE ANALYSIS 311

U and Th concentrations, the geological age, and the initial Pb isotope ratio of the source
rock (Faure, 1986).
1he application oflead isotopes to archaeological studies is based on the difference in iso-
topic composition of Pb ores, so that materials containing Pb of a certain geological source
can be distinguished by the ratio of the four stable Pb isotopes, commonly as '"8 Pb/w4 Pb,
20
7Pb/ 204Pb, and 206 Pbf2°4Pb. A large number of sites are known worldwide as centers of pre-
historic mining and smelting activities, and Pb isotopes have been employed to character-
ize several of the related Pb deposits, including the Taurus Mountains, Turkey (Yener et al.,
1991), the Mediterranean region (Stos-Gale et al., 1995, 1996; Gale et al., 1997), Mont Lozere,
France (Baron et al., 2006), Bulgaria (Stos-Gale et al., 1998; Kuleff et al., 2006), Germany
(Manna et al., 2000; Niederschlag et al., 2003; Durali-Mueller et al., 2007 ), and New Mexico,
USA (Habicht-Mauche et al., 2000, 2002; Huntley et al., 2007). In addition, a large collection
of data is compiled in the OXALID database (Bulgaria, Spain, Italy, Cyprus, Greece, Turkey,
and Britain) and accessible at <http://oxalid.arch.ox.ac.uk/The%2oDatabase/TbeDatabase.
htm> (Stos-Gale and Gale, 2009).
The isotopic composition oflead is an important tracer for evaluating the provenance of
archaeological artifacts. For example, lead has been used in metallurgic processes includ-
ing the production of bronzes and coinage (e.g. Stos-Gale et al., 1997; Niederschlag et al.,
2003; Kuleff et al., 2006; Weeks et al., 2009 ), but is also a constituent in the production of
glasses (e.g. Mecking, 2013) and in lead-based glazes (e.g. Habicht- Mauche et al., 2000, 2002;
Huntley et al., 2007; Walton and Tite, 2010). Experimental investigations suggest that Pb
isotope fractionation during metallurgical processes is negligible (Cui and Wu, 2011); there-
fore the provenance oflead in an archaeological object can be identified with great precision.
Despite their frequent use as an indicator of the origin of Pb from ore deposits, Pb isotopes
may be employed to decipher the provenance of minerals such as feldspars and clays in
ceramic products and their raw materials (e.g. Knacke-Loy, 1994; Renson et al., 2011, 2013).

Mass Spectrometry
Mass spectrometric methods to determine isotopic ratios of different elements have
become important in provenance studies in geoscience and related fields over the last few
decades. Isotopic analysis provides the opportunity to determine characteristic fingerprints
of geogenic materials used in archaeology and thereby provides distinct clues about raw
materials provenance and the movement of manufactured products. Throughout the past
decades different mass spectrometric methods have been developed for analysis of specific
elements and compounds. These include isotope ratio mass spectrometry (IRMS), ther-
mal ionization mass spectrometry (TIMS), and more recently multicollector inductively
coupled plasma-mass spectrometry (MC-ICP-MS) among other available techniques such
as accelerator mass spectrometry (AMS) and the sensitive high-resolution ion microprobe
(SHRIMP). Heavy isotopes, for example Sr, Nd, and Pb isotopes, have been traditionally
measured by thermal ionization mass spectrometry (TIMS). Since the development of
multicollector ICP-MS techniques, MC-ICP-MS instruments have all but replaced TIMS
instruments for the analysis of these and other heavy stable isotope systems; for example,
Fe, Ni, Mo, Zn (e.g. Aggarwal et al., 2008). However, with respect to the element to be ana-
lyzed, certain techniques are favorable over otber techniques. For example, Sr isotope ratio
312 BETTINA A. WIEGAND

measurement on TIMS usually shows better precision compared to measurement on MC~

ICP-MS owing to the complete elimination of isobaric interferences with 8'Rb. The pre-
cision for ''Sr/ 86Sr ratios on TIMS typically is less than o.oooo2 (2cr). Elemental isobaric
interferences on MC-ICP-MS are a common problem that usually requires the correction
of the measured isotopic ratio. Chemical procedures that include the separation of ele-
ments by ion-chromatographic methods to minimize isobaric interferences generally need
to be applied for both TIMS and MC-ICP- MS measurement techniques.

Sample Preparation Techniques

Ceramic material and geogenetic raw materials, such as clays and fine-grained alluvial
deposits, can be treated in similar ways concerning sample preparation for isotopic analy-
sis. However, ceramic material usually needs special pre-treatment to remove any secondary
deposits that include calcium carbonate and other precipitates related to vessel use or altera-
tion processes at the burial site, such as precipitation of solutes from infiltrating groundwa-
ter and soil solutions. Furthermore, each of the isotope systems of interest requires a special
sample preparation protocol for isotopic analysis by mass spectrometric techniques.

Sample Preparation and Isotope Measurement Using TIMS

The isotopic analysis of Sr, Nd, and Pb by thermal ionization mass spectrometry usually
requires chemical preparation and purification of the element of interest prior to mass spec-
trometric analysis. For each element certain purification steps are necessary.
Typically, so-wo mg of sample material (powder) is used for the isotopic analysis of Sr,
Nd, and Pb isotopes. For mineral analysis, usually between 10 and 20 mg of handpicked
specimen is necessary, depending on the concentration of the element of interest in the
mineral (e.g. feldspars). Feldspars, either as primary mineral inclusions in sedimentary raw
materials or as their alteration product, clay minerals, usually contain sufficiently high Sr,
Nd, and Pb concentrations for isotopic analysis. Feldspars with a high anorthite component
(Ca-rich plagioclase) incorporate several hundreds of ppm of Sr as a substitute for Ca owing
to the similar ionic radii of Sr and Ca. Likewise, clay minerals, such as kaolinite, a common
weathering product of feldspars, and montmorillonite, a weathering product of plagioclase,
Mg-rich silicates, and pyroxenes in volcanic ash, have high Ca and Sr concentrations. Nd
and Pb concentrations in those minerals are usually in the range of several tens of ppm,
which allows small quantities of samples to be analyzed with high precision on the isotopic
ratio for all three isotope systems. In addition, fractions of Sr, Nd, and Pb can be retrieved
from the same sample digest.
Usually, sample powders or mineral fractions from ceramic raw materials and pottery
sherds are dissolved in a mixture of hydrofluoric acid (40%) solution and nitric acid (65%)
solution in predeaned Teflon vials. After complete dissolution of the material, the elements
ofinterest (Sr, Nd, Pb) need to be separated from the matrix of the solution, which means that
other ions of the solution need to be removed (e.g. Wels et al. 2006). This is especially neces-
sary to avoid isobaric interferences of~ 7 Rb on 87Sr or l44Sm on 144 Nd. From a cation resin like
BIORAD AG50 x 8, Sr, Nd, and Pb can basically be isolated from the same sample solution
 ISOTOPE ANALYSIS 313

with diluted hydrochloric acid as eluent. While for Sr a single separation step is sufficient, Nd
and Pb need further treatment; a second separation step on an additional ion chromatogra-
phy column. Purification ofPb is traditionally done by using an anion resin such as BIORAD
AG1 x 8 and hydrobromic acid as eluent, whereas separation ofNd from Sm and other rare
earth elements can be performed on HDEHP (di-(2-ethylhexyl) orthophosphoric acid)
coated Teflon powder (Richard et al., 1976) or alternatively Bio-Beads resin (Darbyshire and
Sewell, 1997) with a dilute hydrochloric acid. Alternative resins such as Sr.Spec and TRU.
Spec can be used for the separation ofSr and Nd, respectively (Pin et al., 1994), while separa-
tion ofNd from other rare earth elements can also be performed on Ln.Spec resin (Pin and
Zalduegui, 1997). For Pb isotopes Pb.spec has also been used (Huelga-Suarez et al., z014).
For isotopic analysis it is generally necessary to work with ultrapure or distilled reagents to
keep blanks low.
After purification, Sr fractions are either loaded onto outgassed Ta-single filaments or on
Re-double filaments using diluted phosphoric acid for mass spectrometric measurement.
Sr is run at a temperature between 1350 and 1450°C. Nd is generally also loaded with diluted
phosphoric acid and measured by Re-double filament technique, whereas Pb is usually
measured on Re single filaments in a bed of diluted phosphoric acid and silica-gel at tem-
peratures between 1200 and 1300°C. Isotope measurements on TIMS for each of the ele-
ments usually take between 30 minutes and one hour. Common isotope standards used for
the three elements are NBS987 for Sr isotopes, La jolla for Nd isotopes, and NBS981 for Pb
isotopes. NBS standards can be purchased from the National Bureau of Standards at <www.
nist.gov>.
Traditional TIMS analysis of Sr and/or Nd isotopes of ceramic materials was carried
out by Knacke-Loy (1994), Pinter (zoo5), Li et al. (zoo6), Carteret al. (2on), and Alex et al.
(zo12). Knacke-Loy (1994) also used TIMS for the analysis ofPb isotopes in his study.

Sample Preparation for MC-ICP-MS

In general, sample dissolution and purification steps applied prior to Sr and Nd isotope
analysis by TIMS also apply for MC-ICP-MS analysis of those isotope systems. Sample
preparation procedures for measurement of Sr and Nd isotope ratios using MC-ICP-MS
in geological material were reported by Makishima et al. (zooS). Ganio et al. (2012) pub-
lished a method for Sm-Nd isotope analysis of archaeological material using MC-ICP-MS.
Furthermore, Copeland et al. (zooS) compared Sr isotope ratios measured by liquid and
solid (in situ laser ablation) MC-ICP-MS and found a variation of o.ooo3±o.oooz, which the
authors considered sufficient for distinguishing sources ofSr from different lithologies.
High-resolution magnetic sector inductively coupled plasma mass spectrometry (HR-
!CP-MS) has been applied in some cases to analyze stable Pb isotopes (Habicht-Mauche et
al., 2000, 2002; Huntley et al., 2007). However, since the development ofMC-!CP-MS (this
technique is nowadays available in many laboratories worldwide), this is the favored tech-
nique for isotopic analysis of Pb, Nd, and other heavy stable isotopes of transitional metals
such as Fe, Cr, Cu, Ni, Zn, Mo. MC-ICP-MS technique is suitable for both dissolved samples
and solid materials through laser ablation technique. Comparable to laser ablation multi-
collector inductively coupled plasma mass spectrometry (LA"MC-ICP-MS, ion microprobe
techniques (e.g. secondary ion mass spectrometry (SIMS) technique) could potentially be
314 BETTINA A. WiEGAND

applied for in situ analysis of Pb isotopes in sherds and minerals without prior digestion of
the sample. Multicollector ICP- MS equipped with a double- focusing magnetic sector mass
analyzer to deflect the masses of interest in combination with a set of Faraday cups provides
the opportunity to collect several masses simultaneously and therefore provides a greater
precision for the isotopic ratio than is possible with single-collector ICP-MS instruments.
Liquid sample analysis by MC-ICP-MS requires digestion of the sample material. For
example, for Pb isotope analysis of lead-based glazes, the sample material needs to be dis-
solved in nitric acid (e.g. Huntley et al., 2007; Cui et al., 2010 ). The analysis of Pb isotope
ratios in relatively "pure" Pb ores such as galena or Pb artifacts using MC-ICP-MS requires
only a few milligrams of sample material. Sample materials need first to be cleaned (e.g. in
distilled water) and corrosion crusts need to be removed prior to digestion in dilute hydro-
chloric or nitric acid (e.g. Niederschlag et al., 2003; Durali-Mueller et al., 2007; Renson et al.,
2011). Usually, no further chemical separation oflead is necessary. However, in some cases
if required, preconcentration and separation ofPb from matrix elements can be done by ion
chromatography using different kinds of commercially available resins (e.g. Weis et al., 2006;
Makishima et al., 2008; Weeks et al., 2009; Renson et al., 2011; Huelga-Suarez et al., 2014).
Alternatively, chemical preparation and purification steps according to the sample prepara-
tion described for TIMS analysis can be applied.
For Pb isotope measurements using MC-ICP- MS, sample solutions are usually adjusted to
a certain Pb concentration below the tolerance limit of the instrument, for example, between
200 and 500 ~-tg/L, acidified using 2% nitric add, and run in a sample-standard bracketing
sequence (e.g. White et al. 2000; Weis et al. 2006), where a Pb standard (e.g. NBS981) is
repeatedly measured for instrumental drift correction between runs of unknown samples.
Concentrations ofPb in reference standard solutions are matched with Pb concentrations in
sample solutions. For instrumental mass fractionation of the analyzed Pb isotopes, an addi-
tional thallium (Tl) standard solution (SRM997) is added to the digested sample. Usually,
10
4Pb, :wopb, 207Pb, and 208Pb isotopes are measured simultaneously. Interference ofl0 4Hg on
204
Pb is monitored by simultaneous measurement of 202Hg and is mathematically corrected
for by assuming a natural ratio of 0.230 for '"4 Hgi""Hg (Niederschlag et al., 2003; Baron
et al., 2006; Renson et al., 2011; Dorta et al., 2013). Other authors (e.g. Baker et al., 2oo6) con-
sider isobaric interferences and mass bias variations due to matrix effects on Pb isotopes
from relatively pure Pb metals to be insignificant. Analysis errors are generally o.o2% (2cr)
and less.
A procedure for in situ Pb isotope measurements using femtosecond laser coupled with
MC-ICP-MS was presented by Dorta et al. (2013). Usually, in situ measurements of isotopes
need correction of certain interferences with other isotopes present in the matrix of the ana-
lyzed sample. For Pb, the interference is ' 04Hg on '"4 Pb as outlined above. The advantage of
laser ablation techniques coupled with MC-ICP-MS techniques for Pb isotope studies, and
potentially other isotope systems, is that only small sample amounts are ablated and there-
fore destruction of archaeological material is controlled and relatively minor. In addition,
Glaus et al. (2013) recently presented a portable laser ablation sampling device for sample
collection in the field. Laser-ablated aerosols are trapped on membrane filters from the sam-
ples and subsequently analyzed by MC-ICP-MS in the laboratory.
Cui et al. (2010) and Renson et al. (2011, 2013) analyzed Pb isotopes in ceramic sherds by
MC-ICP-MS, whereas Habicht-Mauche (2ooo, 2002) and Huntley et al. (2007) used HR-
ICP- MS in their studies ofPb isotopes in lead-silica glazes and Pb ores from New Mexico.
 ISOTOPE ANALYSIS 315

CASE STUDIES

Sr and Nd Isotopes in Ceramic Provenance Studies

An early example of the combined use ofPb, Sr, and Nd isotope analysis with petrographical
and geochemical methods for ceramic provenance studies was undertaken by Knacke- Loy
(1994), who investigated Bronze Age ceramics from Troy and their potential raw material
sources. Knacke-Loy (1994) analyzed bulk powders of days, loam, and marl of variable grain
size and geochemical composition from alluvial deposits in the surroundings of Troy in
addition to locally excavated ceramic sherds. A selection of twenty-three samples was iso-
topically investigated, including some ceramics reference samples from Mykene, Tiryns,
Cyprus, and Syria. Based on the combination of isotopic and geochemical data, local and
imported ceramics could be distinguished. Raw materials used in Troian ceramic produc-
tion were locally derived and mainly mined along the two main rivers that surrounded the
ancient center of Troy. Among the three isotope systems, Knacke-Loy found that Nd iso-
topes showed the most promising results for the investigated days and ceramics. 87Sr/ 86Sr
ratios of days from Troy ranged between 0.7082 and 0.7087 and mostly overlapped with the
8'Sri 86 Sr ratios between 0.7083 and 0.7093 that were analyzed for ceramic sherds from Troy.

eNd values of the same samples (days: -3.7!0 -4-9 and ceramic sherds: -4.1 to -5.4) showed
similarly good agreement between days and sherds. The slight variation in the isotopic range
of the sherds towards higher values for both isotope systems compared to the analyzed clay
samples may reflect a certain isotopic heterogeneity in the day sources used for ceramic pro-
duction in ancient Troy. In contrast, pottery sherds from Mykene and from Aharkoy had
significantly higher 87Sr/86 Sr ratios between 0.7095 and 0.7117 and eNd values between -6.4

0.725

China
0.720
Grand Canyon (USA)

0.715
J('
Bulgaria
"'=
~
~

0.710 - Greece
Turkey

0.705 Mexico/USA (volcanic)

0.700
0 2 4 6 8 10 12 14 16 18 20
Number of ceramic samples

FIGURE 18.1 Distribution of 87Sr/ 86 Sr ratios in ceramic samples from archaeological sites
of different regions. Data are from Knacke-Loy (1994), Guzowska eta!. (2003), Pinter (zoos),
Li eta!. (zoo6), Carteret a!. (2011), and Alex eta!. (2012). High 87Sr/ 86Sr ratios (0.7689-
0.7850) of San Francisco Mountain gray ware from Carteret a!. (2011) are not included in the
diagram.
316 BETTINA A. WIEGAND

and -7-4 and were clearly distinguishable from the Troy samples. In general, Knacke-Loy
(1994) interprets the analyzed Sr isotope ratios and eNd values of the analyzed sherds and
clay samples as reflecting a considerable component of crustal-derived sediment materiaL
This is evident from the location of analyzed data along a crustal development trend in a eNd
versus 87Sr/ 86Sr diagram.
Further investigation of Early Iron Age knobbed ware of Troy and the Balkan region
using mineralogical, petrographical, geochemical, and isotopic methods, and a combina-
tion of Sr and Nd isotopes, was carried out by Pinter (zoos). Sediment and ceramic sam-
ples from several archaeological sites including Troy, North Turkish Tbrace, the Sea of
Marmara (Menelqe (,atagi), and archaeological sites of Bulgaria (Ovkarovo, Chal, Diadovo,
Pshenitsevo, Kirilovo, and Sborianovo) were investigated. The samples vary significantly in
Sr and Nd isotope ratios as a result of differences in the geological background of the various
investigation sites. Ceramic sherds from Troy are in the range of 0.7078 to 0.7103 for 87Sr/
86 Sr and -3-1 to -6.2 for eNd. A higher variability of values was found for Menekje (,atagi,
with 8'Sr1 86 Sr ratios in the range of 0.7065 and 0.7106 and eNd values ranging from 0.4 to
-8.1. The data showed partial overlapping with isotopic data from clay samples of the area.
The low Sr isotope ratios of 0.7065 and high eNd value of 0-4 of one sherd sample suggests a
volcanic source of raw materials. Sediment and ceramic sherds from North Turkish Thrace
showed excellent agreement for both 87Sr/ 86 Sr ratios (sediment: 0.7118; ceramic 0.7120) and
eNd values (sediment: -7.8; ceramic: -8.3). For the samples from Bulgarian archaeological
sites, the location Chal showed the lowest 37 Sr/ 86 Sr ratios for sediments and sherd samples
(0.7086 to 0.7119) and highest eNd values (-6.1 to -7.5), while Sborianovo showed the high-
est 87Sr/ 86 Sr ratios of 0.7152 and 0.7181 for clay and ceramic, respectively. eNd values of those
samples were low, -10.4 for clay and -10.5 for ceramic sherds. The locations Diadovo and
Pshenitsevo had intermediate 87Sr/ 86Sr ratios between 0.7084 and 0.7119, while eNd ranged
between -7.4 and -8.9.

0 Turkey

-5
~
zw
-10

-15
...
~--:>-~ -~---~\

e_ _____ j-- ra
,,_...-
_______---,)
-20
0.705 0.720

FIGURE 18.2 Distribution of 87Sr/ 86 Sr and eNd values in ceramic samples from Turkey,
Greece, Bulgaria, and China. Data plot in distinct groups along a crustal evolution trend that
indicates raw materials from sedimentary sources of different geological age and genesis.
Data are from Knacke-Loy (1994), Guzowska eta!. (2003), Pinter (2005), and Li eta!. (2006).
 ISOTOPE ANALYSIS 317

Li et al. (2oo6) investigated Chinese Tang Sancai from Gongxian and Yaozhou kilns by
combined Sr and Nd isotope analysis. Ceramic samples from the two kilns differed signifi-
cantly for both Sr and Nd isotope ratios. High 87Sr/ 86Sr ratios between 0.7222 and 0.7237 and
low eNd values between -18.0 and -18.4 were determined for Gongxian Tang Sancai, while
Yaozhou Tang Sancai showed lower 87Sr/ 86Sr ratios between 0-7177 and 0.7206 and higher
eNd values between -10-4 and -13.5. The results of the study demonstrated that clear distinc-
tion of ceramics from the two locations was possible based on their Sr and Nd isotope com-
position despite similarity in major element content and appearance.
In a recent study, Alex et al. (2012) investigated ceramics from the Teotihuacan Valley,
Mexico, using a multimethod approach including Sr isotopes. Most of the analyzed ceramic
sherds showed low Sr isotope ratios in the range 0.7044 to 0.7046, which was within range
of clay samples analyzed in the study. The results of the investigation suggested that clay
deposits used as raw materials were derived from weathered young volcanic rocks of the
Mexican volcanic belt. A single sherd showed higher 87Sr/86 Sr ratios coinciding with sedi-
ments derived from older basement rocks of the Sierra Madre Occidental.
Carteret al. (2011) used Sr isotopes to investigate gray ware ceramics of the Upper Basin
of the Coconino Plateau in the eastern Grand Canyon region, USA, and their respective
source materials. In this study, two distinct ceramic traditions, Tusayan gray ware and San
Francisco Mountain gray ware, were characterized petrographically and according to their
Sr isotope composition. For raw material investigations, sedimentary deposits such as shale,
mudstone, talus, and fine~ grained alluvium were analyzed for the inner Grand Canyon area
and the Coconino Plateau. Carteret al. (2011) were able to precisely match the majority of
San Francisco Mountain gray ware (87Sr/ 86Sr: 0.7689 to 0.7850) with a mudstone from the
inner Grand Canyon as the source of raw materials. In contrast, two samples showed raw
material compositions derived from weathered volcanic rock in the greater vicinity (8 7Sr/
86
Sr: 0.7048). The Tusayan Gray Ware (87Sr/86Sr: 0.7163 to 0.7219), on the other hand, was
made from a different raw material that was likely derived from rocks exposed on the
Coconino Plateau at the southern rim of the Grand Canyon. The findings suggested a large
diversity of geological sources used for raw materials in these ceramic traditions, including
the exploitation of more distant raw material sources (>2o to 35 km) and possible exchange
of gray wares (Carter and Sullivan, 2007).
Other studies involving the analysis of archaeological ceramics using Sr isotopes
include methological studies. Carter et al. (2011), for example, investigated the effect of
acid-leaching to remove any (secondary) calcium carbonate from the Sr isotope ratio of
sherds. Leaching with 0.3N acetic acid produced a lower Sr isotope ratio in the leachate
because of dissolution of calcium carbonate, while bulk analysis of the remaining sherd
sample consequently resulted in a higher 8'Sr/ 86 Sr. It is therefore recommended to care-
fully investigate any occurrence of calcium carbonate in sherds and raw materials to deter-
mine if alteration of ceramic material (either from food storage, groundwater interaction
during burial, or weathering processes) has occurred or if calcium carbonate was present
in the primary mineralogy of the raw material. On the other hand, analysis of multiple
samples from the same sherd produced variation in the Sr isotope results in the range of
o.ooo4, suggesting the occurrence of mineralogical heterogeneities in the material. Such
heterogeneities may pose a problem especially in the analysis of coarse wares owing to
inclusion oflarger mineral or rock fragments in the clay matrix. Using larger sample sizes
may help to avoid this problem. Furthermore, separation of coarse fractions from the fine
318 BETTINA A. WIEGAND

fraction and separate analysis of the two fractions might be an alternative for more precise
results.

Pb isotopes in Ceramic Provenance Studies

Investigations of Pb isotopes have been the focus of research for decades concerning prov-
enance studies of metal artifacts and Pb ore deposits. Therefore, Pb isotopes are one of the
best-explored lithogenic isotope systems in archaeological provenance research to date. For
ceramic provenance research, two applications have been demonstrated. The Pb isotope
ratio of bulk sherd material represents the isotopic composition of inherited rock-derived
lead that forms a trace constituent in the mineral assemblage of sedimentary raw mate-
rials and therefore can be used as an additional indicator in ceramic provenance studies.
Sedimentary deposits usually contain a mixed Pb isotope composition of the eroded bed-
rocks, and therefore need to be isotopically characterized for the location of interest. In
contrast, lead in glazes is generally derived from Pb ore deposits and therefore allows com-
parison with Pb isotope data from available databases on Pb ores.
Studies ofPb isotopes on bulk material of ceramic sherds were carried out by Knacke-Loy
(1994) and more recently by Renson et al. (2011, 2013). For ceramic sherds and some raw
materials from Troy, Knacke-Loy (1994) found significant differences in the pattern of ' 07 Pb/
w 6 Pb ratios in bulk samples that facilitated grouping of the different ceramic provinces.
Comparison of Pb isotope and Nd isotope distributions, in particular, revealed distinctive
patterns for the classification of ceramic sherds and their provenance. Renson et al. (2011)
investigated Late Bronze Age pottery and a larger number of sediment samples from south-
east Cyprus (Hala Sultan Tekke) using Pb isotopes. Various pottery sherds had Pb isotope
characteristics similar to sediment samples from the area surrounding the archaeological
site, while a number of the Canaanite sherds showed a higher variability in sediment prove-
nances interpreted as foreign raw material sources (probably from the wider Mediterranean
area) for this type of vessels. In addition, Renson et al. (2013) investigated the Pb isotopic
content in White Slip II sherds from Sanidha (Cyprus) and Minet el-Beida (Syria) by using
Pb isotopes and compared their results with sediment and rock samples from the surround-
ings of Sanidha. The authors suggested that local clay deposits from Cyprus were the source
material for ceramic sherds found in Sanidha and potentially also for sherds found in the
Syrian archaeological site Minet el-Beida.
Furthermore, Pb isotope studies oflead-based glazes were used to constrain the raw mate-
rial sources oflead in glaze production in the American southwest (e.g. Habicht-Mauche
et al., 2000, 2002; Huntley et al., 2007 ), glazes used for Chinese Tang Sancai pottery (Cui et
al., 2010), lead-glazed ceramics in the Roman empire (Walton and Tile, 2010), and in Egypt
(Wolf et al., 2013).
Habicht-Mauche et al. (2ooo, 2002) investigated pottery glazes from the Rio Grande
Valley in the American southwest (New Mexico) for the source of lead that was used as a
fluxing agent for low-fired glaze-painted surface coatings by Pueblo potters during the fif-
teenth century. The authors found that most of the ceramic glazes contained lead from a
single ore deposit in the Cerrillos Hills (south of Santa Fe), despite occurrence of other Pb
ore deposits located in the vicinity of the Pueblo. The Pb originated from surface veins of
galena, which showed distinctive stable Pb isotopic composition. In addition, Huntley et al.
 ISOTOPE ANALYSIS 319

(2007) investigated glaze-paintings of pottery from the Salinas area in Central New Mexico
by Pb isotopes and found that most ceramic glazes matched with Pb ores found in southern
New Mexico.
Based on the investigation of glazes from Tang Sancai pottery derived from the two
Chinese provinces Henan (Gongyi kiln) and Shaanxi (Hunagbao kiln) by Pb isotopes,
two independent ceramic production centers that used different Pb ores were suggested
by Cui et al. (2010). While Pb isotopes of Tang Sancai from Huangbao kiln pointed to
the Northern China province as the source for lead, similar ceramics from the Gongyi
kiln appear to have used lead ores from the Yangtze province in the production of their
glazes.
Walton and Tite (2010) investigated lead,glazed pottery from the Western Roman empire
by Pb isotopes with the goal of investigating differences in production technology. Two glaz-
ing techniques were distinguished, one using only lead oxide as coating on pottery, and a
second technique using a mixture of lead and quartz. Several regions were suggested for
lead-glazed ceramic production including Gaul, Italy, Serbia, and Romania, and a number of
ore deposits across Western Europe were suggested as potential sources for the lead used in
the production of the glazes.
Wolf et a!. (2013) investigated lead-based pottery glazes from Fustat, Egypt, from the
eighth to the fourteenth century and found that the Pb ores were probably derived from
distant sources in the Mediterranean region, including Tunisia, Sardinia, Spain, the Taurus
Mountains (Turkey), and Iran. Furthermore, the distribution of Pb isotopes suggested that
Pb ore sources used for the production of glazes in Fustat pottery changed over time. The
authors explained the preferential exploration of non-local Pb ore sources instead of local
Egyptian ore sources by the fact that Pb ores are often a byproduct of silver mining, and
therefore readily available from the respective mining areas to the north, whereas Egyptian
Pb ores were not mined at this time.

16.1
16.0
15.9
15.8 Europe

~
15.7
~

~
15.6
~ 15.5
g
15.4
New Mexico (USA)
15.3
15.2
15.1
15.0
17.0 17.5 18.0 18.5 19.0 19.5

FIGURE 18.3 Pb isotope data of lead-based glazes from New Mexico, USA (Habicht-
Mauche et al., zooo/zooz), China (Cui et al., 2010), and various European locations (Walton
and Tite, 2010 ).
320 BETTINA A, WIEGAND

Figures 18.1-18.3 present Sr, Nd, and Pb isotope data from the above~ mentioned studies
of ceramic sherds and glazes from different regions worldwide. For all three isotope sys-
tems significant variations can be observed, depending on the geological background of the
investigated archaeological site. While Sr isotopes may be sufficient to trace the origin of a
ceramic product for significantly different lithologies, the combination of Sr and Nd isotope
ratios allows more precise characterization of raw material sources. Pb isotope ratios in lead-
based glazes enable distinguishing provinces of Pb ores, and may further be helpful in the
characterization of sedimentary ceramic raw materials.

CONCLUSION AND FUTURE RESEARCH

Previous studies using lithogenic isotopes of Sr, Nd, and Pb in ceramic provenance research
demonstrate the great potential of isotopic fingerprinting methods. Based on the results of
long-term research available from the broad range of geoscientific applications in addition to
methodological and technical advances in mass spectrometry over the past decades, a large
spectrum of geochemical and isotope methods including basic concepts for the understand-
ing of provenance research is available for archaeological applications. The different authors
who have used isotope methods in their research on ceramic provenance have shown that
further research is needed, particularly concerning methodological approaches, choice
of the most promising isotope tool, and refinement of analytical procedures. In addition,
further isotope systems, such as Cu, Sn, and other metal isotopes, are likely to be the focus
of methodological exploration for archaeological provenance research in the near future.
Moreover, interpretation of the data requires a more interdisciplinary thinking, as especially
the study of ceramic provenances provides the opportunity to link between archaeological
and geological-geochemical sciences to illuminate interaction of prehistoric humans with
natural resources in a more detailed way. Therefore, isotope geochemical methods may
broaden or even reverse our understanding from the traditional course of events.

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 CHAPTER 19

X-RAY POWDER
DIFFRACTION (XRPD)

ROBERT B. HEIMANN

INTRODUCTION

ARCHAEOLOGICAL ceramics can be investigated at four levels of structure: the atomic levels
with typical dimensions of 0.1 nm (1 nm = w-9 m), the molecular/compound/unit cell levels
(groups of atoms) of typically 1 nm, the microscopic levels in the broad range of 100 nm to
1 mm, and the macroscopic level above 1 mm. This chapter deals with structural information
obtained at the unit cell level using X-rays as a probe.
The types of atoms present in a ceramic material define its elemental composition; that
is, the relative amount of each type of atom that is usually expressed in weight (mass) per-
cent. Analytical techniques typically used to characterize the bulk chemical composition
of archaeological ceramics include wet chemical analysis, atomic absorption spectroscopy
(AAS), X-ray fluorescence spectrometry (XRF), optical emission spectroscopy (OES),
neutron activation analysis (NAA), and inductively coupled plasma mass spectrometry
(ICP-MS).
Atoms in ceramics are bound together predominantly by strong covalent forces to form
either crystalline compounds or "phases:' in which the constituting atoms are arranged in a
geometrically well-ordered three-dimensional periodic array or amorphous (glassy) solids
with lost symmetry and periodicity. To determine the phase composition of ceramics, ana-
lytical techniques are required, such as X-ray diffraction (XRD) (Pawloski, 1985; jenkins and
Snyder, 2012), glancing incidence X-ray diffraction (GIXRD) (Feldman and Mayer, 1986),
electron backscatter diffraction analysis (EBSD) (Schwartz et al., 2000; Maggetti et al., 2010;
Stojakovic, 2012), and neutron diffraction analysis (NDA) (Embs et al., 2010), also called
elastic neutron scattering. The knowledge of the phase composition of ceramics can be used
to estimate firing temperature ranges, by observing the formation or decomposition of par~
ticular minerals (Isphording, 1974; Heimann and Franklin, 1979; Maggetti and Rossmanith,
1981), and establishing provenance groups based on their mineral composition.
In crystalline materials, the smallest repeatable unit of the atomic arrangement obeying
the crystallographic symmetry conditions is called a "unit cell:' 1he unit cell is characteris-
tic of a given compound and serves to identify it unambiguously. Hence, X-ray diffraction
 l
328 ROBERT B. HEIMANN

provides a "fingerprint" that can be checked against the Powder Diffraction File (PDF) of
the International Centre for Diffraction Data. Although XRD is over wo years old (first dif-
fraction experiment by Max von Laue, Walter Friedrich, and Paul Knipping in 1912; first
determination of crystal structure by Bragg father and son in 1913), it is still the most widely
applied tool for identifYing crystal structures.

GENERATION OF X-RAYS

X-rays comprise a broad part of the electromagnetic spectrum with wavelengths between 1
nm (1 nanometer~ w· 9 m) and 10 pm (1 picometer ~ ro·" m), much shorter than those of
visible light. X-rays are produced when electrons highly accelerated in an electric high-ten-
sion field hit a metallic target, the so-called anticathode (anode) made of copper, iron, chro-
mium, molybdenum, or silver. The electrons are rapidly decelerated near an atomic nucleus
and part of their kinetic energy is radiated away as X·rays offrequency (v) determined by the
equation J.).E = hv, where his Planck's constant. This equation limits the maximum energy
of X-ray photons to that of the energy of the accelerated electrons; the shortest possible X-
raywavelength can be calculated as Am;n ~ 12.390/V [A] (Duane-Hunt equation). This leads
to a potential of25 kV for the minimum X-ray wavelength of 0.4936 A (1 A~ w·8 em~ 0.1
nm). The Duane-Hunt equation is valid under the assumption that the entire energy of the
electron is instantaneously converted. However, in practice this is unlikely. The probability
is much higher that the energy is dissipated stepwise, that is, the electrons cascade gradually
from one energy niveau to the next lower one, until after several such steps they reach their
state of lowest energy, the so-called ground state. This is the reason why X-rays with a broad
spectrum of different wavelengths are generated, also called a continuous X-ray spectrum or
bremsstrahlung (from the German bremsen, to brake, and strahlung, radiation).
Superposed on the broad continuous X-ray spectrum is the sharp line spectrum of the
characteristic X-ray radiation, the wavelength of which is dependent on the atomic number
of the target (anode) material of an X-ray tube. Its origin can be explained by the classic
(Niels) Bohr model that posits that the electrons surrounding the atomic nucleus are con-
fmed to discrete shells or energy niveaus (Figure 19.1a). When the target is bombarded by
highly accelerated electrons, these electrons interact with the electrons of the metal target by
"knocking out" an electron from an inner shell, converting the atom to an excited state. The
electron vacancy in the inner shell will be quickly filled by electrons dropping down from an
outer energy niveau, thus emitting X-rays with sharply defined frequencies. These frequen-
cies correspond to the difference in energy between the inner and outer niveaus (shells) and
their orbitals or subshells s, p, respectively. The innermost shell is called the K shell, followed
outwardly by the L, M, N ... shells. An atom that has lost a K electron remains momentarily
in a K quantum state that, however, is unstable. The probability is high that an electron from
the L shell fills the vacancy and thus transforms to an L quantum state with lower energy. '!be
transition L3 -> K generates an X· ray photon of a discrete wavelength, Ka,. Similarly the tran.
sition L,.;. K leads to Ka, whereas the transition M 3 .;. K generates somewhat higher-energy
(lower-wavelength) radiation, Kp,. The photon energies depend on the atomic number of
the target material (anode). Most frequently copper is being used as a target in an X-ray tube.
Under these conditions the CuK series yields the wavelengths Ka, 1.54051 A, Ka, 1.55433 A,
 X-RAY POWDER DIFFRACTION (XRPD) 329

(a) (b)
M II/III
3p
2 Ml D
3s

llll
>
"'-
>
2'
v
c
v
3
l
""
ll
2p
2s
~
2
K
Ka2 Ka1 K~'·'
4 1s

(c) (d)

d '
~,c
d ,'

FIGURE 19.1 (a) Permitted electron transitions to generate X-rays of the K series. (b)
Interpretation of X-ray diffraction as the result of simple reflection (8 angle of incident radi-
ation, d distance among crystal lattice planes). (c) Seemann-Bohlin focusing geometry for
Debye-Scherrer and Straumanis methods. (d) Bragg-Brentano focusing configuration for
scintillation counter (powder diffractometer) method. E entrance slit of X-ray radiation, C
position of scintillation counter) D diffracted beam position.

and Kp, 1.39217 A. For an iron anode these values are FeKa, 1.93597 A, FeKa, 1.93991 A, and
FeKp, 1.75653 A.
The characteristic X- ray radiation consisting of Ka and KP lines is always superposed on
the continuous radiation (bremsstrahlung). However, for exact measurements monochromatic
X-ray radiation is required. Near monochromatic radiation can be obtained by inserting thin
metal foils as filters in the X-ray beam that absorb the bremsstrahlung and considerably weaken
the KP contribution. This is based on the fact that the adsorption edge of the metal (Ni for Cu
radiation, Mn for Fe radiation) is situated between the Ka and Kp lines of the X-ray radiation
used. However, these filters are not able to separate the Ka, from the Ka, interferences. 1his
can only be achieved by a focusing concave single-crystal monochromator employed in the
Guinier method (Guinier, 1956), for very accurate measuring oflattice constants.

fUNDAMENTAL PHYSICS OF X-RAY DIFFRACTION

The diffraction technique is based on the fact that if a thin beam of electromagnetic radia-
tion of an appropriately small wavelength (X-rays, electrons, y-rays) is incident to a crystal
330 ROBERT B. HEIMANN

lattice, the beam is scattered or "diffracted" in specific directions and angles depending on
the distances of atoms in the crystal lattice, thus forming a "diffraction pattern."
Consider, for example, a one-dimensional lattice in which the atoms are replaced by point-
like scattering centers; each point acts like the origin of a secondary wave that spreads out
spherically (Huygens' Principle). According to a simplified set of assumptions, the relation-
ship between the directions of the incident (primary) and the diffracted (secondary) rays,
scattered at a linear lattice of points with distances or "translations" (a0 ), can be expressed
by the geometrical relationship shown in Figure 19.1b. The figure shows three parallel lattice
planes of distance d. A parallel bundle of X-rays is incident to these planes at a "glancing"
angle 8. The interference condition between the rays reflected from points A0 and B, and trav-
elling along the same trajectory, requires that the path difference BA0 -BM is a whole number.
The path difference is the distance by which the ray reflected from fhe second lattice plane is
displaced backwards relative to the ray reflected from the first lattice plane at point A0 • Since
BA0 = BA, the path difference isBA,.- BM = MA, = A0 A,-cos(90°-8) = A0 A,-sin8 =2d·sin8.
An interference maximum (''constructive interference") will be observed when:

n•A = 2d•sin6 Equation 19.1

whereby n, the order of interference, is a whole number, Ais the wavelength of the X-rays in
A, dis the lattice plane spacing, and eis the glancing angle.
Equation 19.1 is the fundamental Bragg equation that governs the vast field of X-ray crys-
tallography and, in particular, provides the condition for constructive interference for
X-rays scattering from atomic planes of a crystal. It also provides the important link between
e
the measured angle and a characteristic lattice dimension d, that is, the spacing of lattice
planes parallel to a crystal face with the Miller index (hkf), also called interplanar spacing.
This index triple describes the position of a crystal plane in an appropriate coordinate system
commensurate with the symmetry of the crystal. Since the plane intercepts the coordinate
system (a,a,a3) at the three points a,/h, a,jk, and a,/f, or some multiple thereof, the Miller
indices are proportional to the inverses of the intercepts of the plane. If one of the indices is
zero, it means that the plane is parallel to an axis, that is, the intercept is at infinity. For fur-
ther details referto textbooks of geometric crystallography, such as Vainshtein (2003).

POWDER METHODS

To an analyst seeking to determine the phase composition of ancient ceramics, basically

two methods are available, the Hull-Debye-Scherrer photographic method and the scintil-
lation counter-method using a powder diffractometer. The choice between these methods
is largely determined by the amount of sample material available and the accuracy of the
results desired. Useful hints for sampling strategy and requirements can be obtained from
Kingery and Vandiver (1986).
X-rays diffracted by a single crystal are collected in a discrete spot pattern using photo-
graphic techniques such as the Laue, Weissenberg, de jong-Bouman, or precession (Buerger)
methods (Klug and Alexander, 1974). In contrast to this, X-rays diffracted by a fine powder,
in which every possible crystalline orientation is equally represented, yield smooth diffrac-
tion rings or arcs when recorded on a circularly bent film (Debye-Scherrer method).
 X-RAY POWDER DIFFRACTION (XRPD) 331

Hull-Debye-Scherrer Method
In many cases the ceramic object under investigation is unique, and thus, highly valuable so
that the amount of sample removed from the sherd must be rigorously minimized, for exam-
ple extraction of the material using a dentist's drill from a location hidden when the object is
on display. The total amount of material may be only in the micro- or low-milligram range as
frequently found in forensic samples (Kugler, 2003).

Sample Preparation
The grain size of the powdered sample should be below 10 ~m; larger particles will cause a
spotty appearance of the diffraction rings. Usually, the powder is confined to a commercially
available narrow tube called a Mark capillary (internal diameter 0.3 or 0.5 mm, wall thick-
ness o.o1 mm) made from special glasses, including vitreous silica that absorb X-ray radia-
tion only weakly. These fragile capillaries must be handled with extreme care. Very minute
amounts of a powdery material, won for example by rubbing a ceramic sherd against emery
paper, can be fixed to the outside of a glass fiber coated with glue. Even smaller microgram
amounts of material can be collected under the microscope using a small drop of resin glued
to the tip of a glass fiber. By using these sample preparation techniques, XRD becomes virtu-
ally a non -destructive analytical method.

Equipment
The sample is mounted in the center of a sealed flat metal cylinder called a Debye-Scherrer
camera of either 180 or 360 mm internal circumference (diameter 57.3 and 114.6 mm,
respectively). These dimensions ensure an exact conversion of the distances of the recorded
interference rings (in mm) into angular degrees (in "8 and 0 28, respectively). A strip of pho-
tographic film is pressed against the inner wall of the cylinder in such a way that, through
two holes punched in the strip, the conical entrance and exit apertures of the X-ray beam
can be threaded: the Straumanis configuration (Straumanis and Jevins, 1940). The entrance
aperture, diameters of 0.3 to 1.5 mm, is designed to collimate the beam to yield sharper
reflections; the exit aperture serves as a beam stop and is equipped with a fluorescent screen
to control the alignment of the sample in the center of the camera. A motorized rotatable axis
allows the mounted sample to be located exactly in the center of the camera cylinder, and
turn during exposure. 1be loaded Debye-Scherrer camera is attached to an X-ray machine
in such a way that an X- ray bundle, collimated by the circular exit window of the X-ray tube,
shines exactly through the center of the entrance aperture of the camera.

Seemann-Bohlin Configuration
The intensity and sharpness ofthe diffracted X- ray beam can be considerably improved by focus-
ing. The Seemann-Bohlin technique (Seemann, 1919; Bohlin, 1920) uses the fact that entrance
aperture E and sample are positioned on one common focusing circle (Figure 19.1C). The focus-
ing principle is based on the geometric rule that if the incident X-rays diverge from a point and
are reflected-that is, refracted to pass through another point D-these two points are required
to lie on the same circle as the (surface) of the powder spectmen as well as the slit of the entrance
aperture E.
332 ROBERT B. HEIMAN :-.I

Evaluation of Measurements
The best method for evaluating the film is to place the developed film on a light box and mea-
sure the diameters of the corresponding interference rings with a transparent ruler (o.s mm
divisions). In the Straumanis configuration (see above), the centers of the two holes punched
in the film are 90 mm apart for a small camera with 57.3 mm diameter and 180 mm for a large
camera with 114.6 mm diameter, each corresponding to 180 °28. Any deviation from this
distance, caused for example by shrinkage of the photographic film during wet processing,
can be accounted for by calculating a correction factor with which the measured distances
of the interference rings must be multiplied. For a small camera, with radius r = 57-3 mm, the
distances x between two symmetrically arranged rings measured in mm correspond directly
e
to the diffraction angles according to 8 = (18o/zm)•X. From the angles 8 the d-values can be
calculated by the Bragg equation for a given X-ray wavelength A(Equation 19.1).

Powder Diffractometer
Powder diffraction data are usually presented as a diffractogram that records the diffracted
X-ray intensity I as a function of the scattering or "glancing" angle 0 28 (Figures 19.2-19.4).
The advent of electron synchrotron sources (Courant eta!., 1952) has increased the num-
ber of available wavelengths considerably. The intensity of an X-ray beam diffracted by the
crystallites in the powdered sample is recorded by a CKf (cathode ray tube) instead of a
photographic film. Using an automated goniometer, step-by-step scattered intensities may
be measured, and stored digitally and processed by very detailed software.
The advantage of this method over the Debye-Scherrer technique is fourfold: the intensi-
ties of the interferences can be determined directly with high precision; the method is fast
and highly reliable, since frequently only a few selected reflections need to be considered;
no darkroom work is required; and equipment is easily available at virtually every university
department of chemistry, materials science, and geology/mineralogy as well as numerous
industrial and governmental research facilities. On the downside, the technique requires
expensive apparatus caused by the much higher demand in terms of constancy of the direct
current source for the X-ray tube, as well as the more complex recording and control devices.

Sample Preparation
Grain size of the powdered samples should be around 10-30 ~m to obtain maximum and
reproducible intensities of the diffracted X-ray beam. The specimens will be fiXed to a sam-
ple holder made from aluminum or a polymeric material that carries a machined, shallow
square or circular hollow into which the powder will be pressed to achieve a smooth and
planar surface. If the powder is fine enough, it will stick to the holder without any additional
binder. Care must be taken to avoid texture effects caused by the preferential orientation of
the powder particles relative to the specimen surface. This frequently happens because platy
particles, such as clay minerals, orient themselvesparallel to the sample surface when too
much pressure is applied during sample preparation. As a result the lattice planes parallel to
the surface of the platelets show highly exaggerated intensities, whereas the intensities oflat-
tice planes perpendicular to the surface will be suppressed. Several techniques exist to reduce
 X-RAY POWDER DIFFRACTION (XRPD) 333

these texture effects including mixing the sample with X-ray inert spherical particles-for
example, cork or lycopodium powders-to which the platelets may stick and thus present
their surfaces in the desired random orientation. Alternatively, the powder can be dusted
onto thin foils of poly( ethylenterephthalate) (PET; Hostaphan~, Mylar'"") or polypropylene.

Equipment
The measuring principle of a powder diffractometer is shown in Figure 19.1d. The sample
surface is positioned in the center of the measurement circle (solid circle). By slowly tilting
the sample at a constant rate, its angle towards the incident X-ray beam is varied, and con-
sequently the diffracted beam also moves. The focus of the beam inside the X -ray tube, the
entrance aperture E, the sample surface, as well as the counter Care located at the circumfer-
ence of a virtual circle, the focusing circle (dashed circle in Figure 19.1d). This is the Bragg-
Brentano configuration (Bragg, 1921; Brentano, 1923). During recording, the scintillation
counter C moves along the measurement circle with an angular velocity that is twice that
of the sample. The resolution of the diffractogram, and hence, the precision of the measure-
ment, depends upon various parameters including selection of filters, apertures, goniometer
speed, maximum signal range of the recorder, time constant, type ofX-raytube, voltage, and
proper alignment of the focusing condition.

Evaluation of Powder Diffractograms

Since the X-ray diffractograms already present the peak positions recorded as intensity ver-
sus diffraction angle plots, the angle 0 26 can be directly read from the chart and converted
to d-values by the Bragg equation (Equation 19.1). Modern X-ray diffractometers are com-
puter controlled, and with appropriate software the diffractogram can be evaluated directly
on a computer screen. Since the pattern of diffracted X-rays is unique for a particular struc-
ture type it can be used as a "fingerprint" to identify individual minerals in a ceramic mate-
rial. The PDF database of the International Centre for Diffraction Data allows searching
for unknown compounds by comparing the d-values of the lines with the highest intensi-
ties (peak height) with those of the database in which the substances are ordered after the
d-values of the strongest peaks, the so-called Hanawalt groups (Hanawalt et al., 1938). A cal-
culated example is shown in Table 19.2.

APPLICATION OF XRD
TO ARCHAEOLOGICAL CERAMICS

Investigation of an Archaeological Clay: Provincial

Roman Terra Sigillata
The clay under investigation is calcareous illitic clay sampled from the banks of the Otterbach
creek, a small tributary to the Rhine River, near jockgrim, Palatinate, Germany. This clay
has reportedly been used to manufacture provincial Roman Terra Sigillata ware in the East
334 ROBERT B, HEIMANN
l
Table 19.1 Chemical composition of calcareous illitic clay from
Otterbach, Jockgrim, Palatinate, Germany
(Heimann et al., 1980)
Oxide Si0 2 Al 20 3 Ti0 2 Fe20 3 CaO MgO Na 20 K20 P20 5

massOfo 61.7 19.3 0.8 5.5 7.0 2.7 0.8 3.5 0.1

Table 19.2 List of measured diffraction angles 0 28, d values calculated

according to the Bragg equation (Equation 19.1), referenced values
and intensities of mullite (first numbers refer to 3:1 mullite, numbers
in brackets to 2:1 mullite) obtained for comparison from the Powder
Diffraction File (# 79-1275 for 2:1 mullite; # 82-0037 for 3:1
mullite), and assignment of Miller indices (hkt). The d v~lues for quartz
were calculated from the lattice constants a0 = 4.9133 A, c0 = 5.4053
A. X-ray wavelength A= 1.5418 A(CuKo)
line# '28 (meas.) d (calc.) d (PDF) Intensity (PDF) (hkl) Assignment

1 16.50 5.372 5.386 (5.400) 530 (800) 110 3:2-mullite

2 21.00 4.230 4.255 100 quartz
3 26.50 3.363 3.386 (3.402) 1000 (1000) 210 3:2-mullite
4 26.75 3.332 3.344 101 quartz

5 30.75 2.907 2.884 (2.889) 170 (200) 001 2:1-mullite

6 33.00 2.714 2.693 (2.700) 370 (450) 220 2:1-mullite
7 35.25 2.546 2.542 (2.548) 480 (490) 111 2:1-mullite
8 36.50 2.462 2.456 120 quartz
9 39.40 2.429 2.427 (2.428) 160(150) 130 2:1-mullite
10 39.50 2.281 2.291 (2.298) 175 (560) 201 3:2-mullite
11 41.00 2.201 2.206 (2.202) 550 (340) 211 2:1-mullite
12 48.50 1.887 1.886 (1.897) 50 (60) 400 3:2-mullite
13 60.75 1.524 1.525 (1524) 380 (230) 331 2:1-mullite

Gaulish settlement Tabernae Rhenanae (today's Rheinzabern) between the second and third
centuries AD. 1his is indeed one of few fortuitous cases in which the original clay source still
exists so that through experimental firings the ancient technology can be ascertained and
reconstructed with confidence. Table 19.1 shows the chemical composition of the as-mined
clay obtained by XRF spectrometry.
The left panel of Figure 19.2 shows X-ray diffraction charts of several clay size frac-
tions from this raw material source, separated using an Atterberg cylinder. ~Ihe coarse
i
---·---·--···------------------------

X-RAY POWDER DIFFRACTION (XRPD) 335

il ml
I chi ( \jchl

I chi
I
Ji
I
I \
'V
rljJ,. ch~; lep i\)rl m~ g

I( 1 j V,} ~~chi
c ,.../ ~~ .._,.., il
pi 'lch I ~I chi i f

b J --.,.j·\·1/\ ;z J\ 1\)
qz '-.)W \.,..N
,, qz e

p! I; ch 1 ,Iii il chi il

a J~)li~v;~~'I#~W~'( d

30 20 10 30 20

FIGURE 19.2 Left panel: X-ray diffraction charts of an archaeological calcareous illitic clay
from Otterbach, Palatinate, Germany: (a) as-mined non-separated clay, fine sand frac-
tion (-420+74 ~m); (b) silt fraction (-74+5~m grain size); (c) clay fraction (-5+1 11m).
Right panel: as-mined clay fired at different temperatures and atmospheres; (d) 6oo°C in
air; (e) 8zo°C in reducing atmosphere (jO, > 10- 4 atm); (f) 1010°C in reducing atmosphere
(jO, > 10- 4 atm); (g) 1010°C in air (Heimann et al. 1980). Labelling of the peaks is as
follows: cc calcite, chl chlorite, di diopside, he haematitie, il illite, ml mixed layer mineral, pl
plagioclase, qz quartz, sa sanidine, sp spinel, tr tridymite.

granular non-clay constituents quartz, plagioclase, and calcite appear in the as-mined clay
(Figure 19.2a), whereas in the silt (-74+5 11m) (Figure 19.2b) and clay fractions (-5+111m)
(Figure 19.2c) the clay minerals illite (il), mixed layer (ml) mineral(s), and iron-rich chlorite
(chl) dominate. The finest fraction contains lepidocrocite (lep, y-FeOOH) as an important
carrier of iron. This high-illite fraction was used by the Roman potters as a slip, applied to the
leather-hard green body prior to firing.
The results of experimental firing of the clay are reported in Figure 19.2, right panel
(Heimann et al., 1980). Firing using an oxidizing environment at 6oo°C (Figure 19.2d)
reveals that the original phase content of the clay is still maintained even though chlorite
(chl) has already disappeared from the XRD record. In particular, calcite (cc) and illite (il)
appear unchanged. In contrast to this, firing using an oxidizing environment at 1010°C
(Figure 19.2g) shows neoformation of diopside (di), calcium-rich plagioclase (pl), traces of
sanidine (sa), and hematite (he), but no mullite. Diopside is a fingerprint mineral of calcare-
ous ceramics fired above about 950°C under oxidizing conditions. The iron oxide present as
the minerallepidocrocite (lep) as well as released from the illite or chlorite lattices crystal-
lizes under oxidizing conditions as hematite (a-Fe,0 3), producing the telltale rich coral red
color of air-fired Terra Sigillata pottery.
Firing under mildly reducing conditions (/0 , >10- 4 atm; Mn,O/Mnp 4 redox buffer) at
8zo°C (Figure 19.2e) reveals that decomposition of illite has already started, manifested by
the disappearance of the (ozo!t1o) and ( 003) interplanar spacings at around 21.0 and 25.3 °28,
respectively. Calcite (cc) still occurs in the phase assembly since its decomposition starts at
336 ROBERT B. HhiMANN

temperatures higher than 85o0 C. A firing temperature of 1010°C under mildly reducing con-
ditions (Figure 19.2f) produces a phase assembly consisting of calcic plagioclase (pl), tridy-
mite (tr), and spinel (magnetite). The occurrence of magnetite is responsible for the gray to
black color of the fired ceramics.

Low-Fired Earthenware Produced from Calcareous

Clays: The Gehlenite Problem
Most ancient low-fired earthenwares were produced from red-firing clays and shales, the
main clay mineral content of which is illite. The presence of feldspars and, in particular, cal-
cite provides fluxing agents that considerably lower the sintering temperature. Consequently,
it is not surprising that ancient pottery was predominantly produced from calcareous illitic
clays that, on firing to temperatures well below 1000°C, yielded a reasonably dense and
rather impervious body. Corinthian and Attic ware, Roman Terra Sigillata, and many medi-
eva! earthenware products were produced from calcareous illitic clays .. However, such clays
have non-refractory properties and thus possess a rather narrow softening interval so that
great care had to be taken not to "overfire" the vessels and thus create undesirable large-
scale melting of the clay, leading to warping, bloating, and ultimately failure (for example,
Maniatis and Tite, 1975). Evidence of such failure exists in the archaeological record; almost
all ancient pottery production sites contain copious numbers of deformed and otherwise
misfired wasters. With increasing control over the complex physicochemical parameters
existing in a pottery kiln and a judicious choice of appropriate clays, a shift to less calcare-
ous clay, and, as a result, an increase in quality occurred. This is evident, for example, in the
change from highly calcareous Neolithic pottery of Crete to much less calcareous clays dur-
ing the Middle and Late Minoan Kamares periods, achieved presumably by blending clays
from different sources with high (northern coast of Crete, Knossos) and low (southern coast,
Phaistos) lime contents to yield a consistent product (Noll, 1982; Heimann,1989). A simi-
lar blending of clays from different sources has been deduced from compositions of Italian
maiolica (Caiger-Smith, 1973; Baldi, 2003) and French faience (Maggetti, 2012).
Higher amounts of CaO in the clay result in ceramics with considerable amounts of
gehlenite, Ca,Al1v[A!Si0 7 ) when fired to 8so-woo0 C. Gehlenite persists metastably in the
ceramic and reacts at higher temperatures (>wso°C) with silica released during decomposi-
tion of meta-kaolinite or illite to anorthite+ wollastonite (or in the presence ofMgO to diop-
side, CaMgSi,06 ) according to:

J
Ca 2 Al[ AlSiO, + 2 Si0 2 ---> CaAl 2 Si 2 0 8 + CaSiO, Equation 19.2

The formation of gehlenite outside its field of thermodynamic stability, and its occurrence in
and disappearance from calcareous illitic clays has long been considered an analytical chal-
lenge as a thermodynamic problem. However, the solution to this problem has been found
in the realm of reaction kinetics. Well-processed clays utilized to make fine Roman Terra
Sigillata, with a narrow and small grain size distribution and, in particular, absence oflarger
calcite grains, do not show gehlenite, whereas coarse and low-fired utilitarian ware (Terra
Helvetica) made from identical clays contain significant amounts of gehlenite (Maggetti and
 X-RAY POWDER DIFFRACTION (XRPD) 337

KUpfer, 1978; see Figure 19.3, right panel). Evidently, the reaction rate of gehlenite formation
is a function of grain size which, in turn, is influenced by the degree of processing of the clay;
a dear measure of the technological skill of the potter.
Since ancient earthenware ceramics were almost always fired below I000°C, gehlenite
should indeed have been formed during oxidizing firing. However, this phase is rarely
detected in such ceramics with some notable exceptions; for example, when the ceramics
were buried under strongly arid conditions (Figure 19.3a-b). In contrast to this, in con-
tact with soil solutions, gehlenite transforms to zeolitic minerals. Depending on the com-
position of soil solutions there are several reaction paths; confirmed experimentally by
Heimann and Maggetti (1981) using XRD (see also Rathossi et al., 2010). Gehlenite reacts
with diluted inorganic (HCl) and organic (acetic, oxalic, citric, aspartic, tartaric) acids to
hydrogrossularite (hibschite, Ca3Al,[(Si,H)O 4 ],), under moderate humid conditions in the
presence of CO, to wairakite (Ca[AlSi,0 6 ],·zH,O), garronite (NaCa,. 5 [Al3Si 50, 6 ],·14 H,O)
(Figure 19.3c-d), scawtite (Ca7 [(CO,JSi 6 0, 8 ].2H,O), and montmorillonite, and, under very
humid conditions, in the presence of humic acids and C0 2 , to calcium carbonate modifi-
cations (aragonite, vaterite) with different stabilities with respect to the calcite that finally
remains as the thermodynamically stable phase, together with smectites. In high-fired
(>wso°C) calcareous ceramics, gehlenite reacts with silica to form anorthite that, during
burial under humid conditions and pH-values >8, very slowly decomposes to calcite and
a smectitic phase. These experiments clearly show how the sensitivity of some minerals in
low~fired ceramics to aggressive solutions. Here is a lesson to be learned: extensive cleaning
of excavated shards with acids (pH <3) to remove calcite or silicate surface deposits should
be generally avoided.

pi

40 30 20 °28 35 30 25 20

FIGURE 19.3 Left panel: X-ray diffraction charts of archaeological ceramics buried under
arid conditions, showing large amounts of gehlenite (ge) and diopside (di) as well as residual
calcite (cc) and quartz (qz). (a) Ceramics from the tomb of Intef VII, Thebes, Egypt, qth
Dynasty; (b) Nabataean sigillata, Petra, jordan, rst century AD (Heimann and Maggetti 1981).
Right panel: XRD charts of rst century AD Terra Sigillata from La Peniche (Vidy, Lausanne),
Switzerland (Maggetti and Kupfer 1978), showing zeolitic decomposition products of
gehlenite due to burial under humid conditions: (c) wairakite/Ca-analcime; (d) garronite/
Ca-harmotome.
338 ROflERT B. HEIMANN

Ceramic Reactions in High-Fired Stoneware Clays

l
I
Thai stoneware (fourteenth to fifteenth century AD) was produced from non-calcareous,
refractory, kaolinitic clays. The ceramic paste (c. so mass% clay, c.25 mass% quartz and c.25
mass% alkali feldspar) resembled that of typical porcelain. Chemical analysis by XRF of
typical Sawankhalok or Sukhothai stoneware clays yielded about 73 mass% SiO, 21 mass%
Al 20 3, 4 mass% alkalis and 2 mass% Fe 20 3 (Kilb, 1979). 1be average mineralogical composiM
tion of the stoneware was found by XRD analysis to consist of c.12 mass% mullite, c.2o mass%
quartz, and c.68 mass% glass (Figure 19-4).
The relatively high proportion of alkali oxides fosters the formation of partial melts dur-
ing high-temperature firing (1200-1250°C) of the ceramic green body (Heimann, 1989). The
ternary eutectic-that is, the composition with the lowest melting temperature of any ratio of
K2 0, Al 2 0 3, andSi0 2 -islocated at about 10 mass% K2 0, u mass% Al 2 0 3 and 79 mass% Si0 2 •
Figure 19.4, inset, shows the microstructure of typical Sawankhalok stoneware. The min-
eralogical equilibrium composition is expected to be that of the coexisting minerals mullite +
quartz + potassium feldspar. However, since the alkalis are securely locked up in the glass
phase, no feldspar is formed. Mullite is present both in its primary platy (2:1-mullite Mu I;
zA1,0 3.SiO,; eq. 3) and secondary needle-shaped (3:2-mullite Mu II; 3Al,0 3-zSiO,; Equation
19-4) modifications. A quartz grain can be seen dissolving, surrounded by a pool of glass.
Si-Al spinel, 3SiO,-zAl,0 3 formed by decomposition of kaolinite transforms to primary 2:1-
mullite and cristobalite above 1050°C (Equation 19.3). The z:J-mullite reacts with silica to
secondary 3:2-mullite beyond 1250°C (Equation 19-4).

[ 3Si0 2 • 2Al 2 0 3 J -> [ 2Al 2 0 3 • SiO, J + 2Si0, Equation 19.3

3[2Al 2 0 3 ·Si0 2 ]+Si0 2 ->2[3Al 2 0 3 ·2SiO,J Equation 19-4

qz

mu

10 15 '29

FIGURE 19.4 XRD chart (CuKa) of stoneware from Sawankhalok, Thailand (14th-15th
centuries AD), formed by firing of a refractory kaolinitic clay beyond 125o'C, showing (resid-
ual) quartz (qz) and mullite solid solution (mu) phases. The inset shows an SEM image of
the (etched) ceramic microstructure with primary platy mullite (Mu I; 2Al,03 SiO,), sec-
ondary needle-shaped mullite (Mu II; 3Al,0 3 zSiO,), and a quartz grain dissolving in glass
(Heimann 1989).
 X-RAY POWDER DIFFRACTION (XRPD) 339

The XRD chart (Figure 19-4) shows the main peaks of mullite as well as those of residual
quartz (Table 19.2). In addition, the elevated background (mottled area) centered at 22 °26
suggests the presence of a high-silica glass. If such a glass could be crystallized by long-term
tempering at sufficiently high temperature, the centroid position would narrow to the (m)
spacing of il-cristobalite at 21.93 '28 (d, = 4.128 A).
Frequently, peaks overlap so that both their angular positions and intensities cannot
clearly be resolved. The XRD chart of Sawankhalok stoneware reveals a substantial over-
lap of the strongest quartz interference at d = 3-332 A with the strongest mullite interfer-
ence at d = 3.363 A between 26.50 and 26.75 °28. To deal with such problems, the Rietveld
method (Rietveld, 1969, 2010) was introduced. This method uses a least squares approach
to refine a theoretical line profile until it matches the measured profile. Subtracting the
theoretical and measured line profiles yields information on the quality of structural
refinement.
As mentioned above, not only crystalline but also non-crystalline (amorphous or glassy)
phases occur in archaeological ceramics formed by quenching of high-siliceous melts from
high firing temperatures. During cooling in these highly viscous melts, nucleation required
for crystallization is suppressed, so that the non-crystalline state is maintained down to
room temperature. In glass formed in this way, the atomic arrangement is non-periodic
and, consequently, lacks well-defined symmetry. This leads to a distorted network of silica
tetrahedra that does not produce a sharp diffraction pattern but a diffuse pattern instead,
resulting in broad shadowy rings on the De bye-Scherrer film or an elevated background in
the diffractometer record (Figure 19.4, mottled area, 15-30 °28). Hence, normal XRD tech-
niques are not suitable for investigating amorphous materials. However, the rich structural
information contained in diffusely scattered patterns can be retrieved by high-resolution
wide-angle X-ray scattering (WAXS) using synchrotron radiation. This technique com-
prises determination of the so-called complex scattering vector S(Q), the deconvolution of
which yields information on repetitive structural units such as SiO 412 tetrahedra of differing
degree of condensation, topology, and conformation, and thus will allow determining quan-
titatively the chemical composition of a glass (Pietsch et aL, 2004; Pentinghaus et al., 2004;
Heimann et al., 2007).

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-----------·-------·······---~---

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Heimann, R. B. and Maggetti, M. (2014). Ancient and Historical Ceramics (Stuttgart:
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 CHAPTER 20

X-RAY FLUORESCENCE-
ENERGY DISPERSIVE
(ED-XRF) AND WAVELENGTH
DISPERSIVE (WD-XRF)
SPECTROMETRY

MARK E. HALL

ENERGY dispersive X-ray fluorescence (ED-XRF) spectrometry and wavelength dispersive

X-ray fluorescence (WD-XRF) spectrometry are two analytical techniques that use X-rays
to generate compositional data. Although not as popular for ceramics as neutron activation
analysis (NAA, INAA) or inductively coupled plasma-mass spectrometry (ICP-MS), X-ray
fluorescence (XRF) spectrometry can provide a low cost and fairly rapid way of determin-
ing the chemical composition of ceramic materials. In the case ofED-XRF spectrometry, it
also can be a non-destructive method for generating quantitative chemical data. The pur-
pose of this chapter, in addition to providing a review of these two analytical techniques, is
to illustrate some of the archaeological studies that have utilized one or both of these tech-
niques, and discuss some of the anthropological questions XRF spectrometry can address.
I provide a brief technical overview of XRF spectrometry and refer readers to Bacso et al.
(1998), Brouwer (2003), jenkins (1999), Janssens (2003), Lachance (1993), Rouessac and
Rouessac (2007: 263-281), Shackley (2012), Whiston (1987), and Williams (1987) for more
detailed information. Additionally, I do not focus on portable or handheld XRF spectrom-
etry of ceramics in this chapter; instead the reader is referred to Chapter 21 in this volume
and papers by Speakman et al. (2011) and Hunt and Spealanan (2015).
Whereas the focus in this chapter is X-ray spectrometry, it is emphasized that a single ana-
lytical technique is often insufficient for addressing the question(s) at hand. Consequently
additional analytical techniques are employed to facilitate a better understanding of the
chemistry from both materials science and cultural perspectives. For example, Buxeda i
Garrig6s et al. (2001) used not only XRF, but also X-ray diffraction (XRD) and scanning
electron microscopy (SEM) to understand chemical patterns observed at the Late Bronze
Age kiln at Kommos, Crete. Other examples of ceramic research incorporating XRF and
instrument-based analytical techniques include, but are not limited to, Baxter et al. (2008),
 X-RAY ED~XRF AND WD~XRF SPECTROMETRY 343

Day and Kilikoglou (2001), Fortina eta!. (zooS), Hall and Nishida (2oos), Inanez eta!. (2007,
2008), and Knappe! et al. (zoos).

ANTHROPOLOGICAL AND ARCHAEOLOGICAL

ASSUMPTIONS AND ISSUES

The provenance of ceramics can often be determined by comparing the concentrations and
relative amounts of the major, minor, and trace elements contained within them. A pri~
mary assumption behind this approach is that a relationship exists between the chemical
composition of the pottery and the clay(s) and temper(s) used to manufacture the pottery
(Wilson, 1978: 220, 221; Harbottle and Bishop, 1992: 27; Steponaitis et a!., 1996: sss-s6o;
Hein eta!., 2004: 245-246). Furthermore, for prehistoric pottery, the chemistry of the clay
and tempers used in the pottery are seen as being a reflection of local geological materials
(Bishop eta!., 1982; Bishop and Neff, 1989; Harbottle and Bishop, 1992; Hein eta!., 2004).
Although human behavior may alter the chemical signature and prevent sourcing to a
specific clay deposit (e.g. the addition of temper(s) and the refining of clay(s)), it does not
prevent the analyst from identifying unique, statistically significant compositional groups
(Neff et a!., 1988; Arnold et a!., 1991). Distinct compositional groups of ceramics can be
viewed as having originated from different "sources:' These "sources" could correspond to
specific clay deposits, regional clay deposits, and/or "production workshops" (Arnold eta!.,
1991; Costin, 1991). A final corollary, particularly for prehistoric sites lacking evidence for
a kiln or other production features, is that the dominant chemical group found at a site is
often presumed to represent local production, whereas other chemical groups of ceram*
ics found at the site are presumed to represent trade or exchange (Tile, 1999). This prin-
ciple, often referred to as the criterion of abundance, can be highly problematic especially
in areas where there is substantial movement of pottery and/or when sample sizes are small,
and/or when there is limited/no knowledge of the chemical signature(s) of pottery from
other sites.
The conceptual framework described above is only a useful starting point for chemical
analyses of ceramics, and not a set of axioms. Research has shown that reality is often more
complex. Hein eta!. (2004) have illustrated the variability that can exist in local and regional
clay deposits. Even within a single clay deposit, when normality is assumed, individual clay
samples from deposits appeared as outliers when compared to the majority of the samples.
When human behavior gets added to this chemical variability in the clay, links to the raw
material can be further obscured or even non-existent. Buxeda i Garrig6s et al. (2003), in an
ethnoarchaeological study of pottery production in a single village in Spain, illustrate how
human preparation of the local clays increased the chemical variability, and there was not a
single chemical group that could be considered characteristic of the village as a whole.
Additionally, it is important to mention that ceramics are also subject to post-depositional
alteration (see Chapter 11, this volume). A number of factors, such as the firing temperature
of the ceramics, how the ceramic was used (e.g. crucibles, storage of salts, etc.), porosity,
burial environment, and the pH of the groundwater, can lead to chemical alteration (Hedges
and McLellan, 1976; Buxeda i Garrig6s et al., 2001; Schwed! eta!., 2006). Depending on the
344 MARK E. HALL

extent of the alteration, this could alter the bulk chemical composition of the pottery and
ultimately affect the ability of the analyst to identify reliable compositional groups.
It is with this conceptual framework (and its caveats), combined with archaeological
knowledge, that one can begin to use chemical analyses of ceramics to address the cultural
aspects of ceramic manufacture and production.

PHYSICS OF X-RAY FLUORESCENCE

Although X-rays have long been used to image the skeletal structures, or to examine the
contents of bags and packages at security checkpoints, our interest herein is the secondary
(or fluoresced) X-rays that occur when an object is subjected to X-ray radiation. Photons
from the primary or incident X-ray beam, with an energy between 5 and 100 keV (Rouessac
and Rouessac, 2007: 263), displace electrons in the K, L, and M orbitals of atoms forming the
surface of the sample. Secondary X-rays are formed when electrons from the higher orbitals
release energy to fill voids in the lower orbitals (i.e. L orbital electrons drop to the K orbit,
while M orbital electrons drop to the L orbit, etc.). An L orbital electron drops to the K orbit
and loses energy; the energy loss is measured as Ka and K~ X-rays. The La and L~ X-rays are
produced when an M orbital electron drops down to the. L orbital. As the atomic number
(Z) increases, the number of resulting secondary X-rays (such as!(,., K~, La, L,, etc.) and
their intensity increases.
Not all the incident X-ray photons produce secondary X-rays. Depending on the energy
of the incident X-ray, a certain percentage of the photons can end up producing Auger elec-
trons instead of secondary X-rays, and another percentage of them can be coherently and
incoherently scattered. Alternatively, if too powerful, incident photons can pass through the
sample's atoms and not produce any secondary X-rays or be scattered. Efficient production
of secondary X-rays occurs when the incident photons have energy just slightly greater than
the binding energy (also known as the absorption edge) of the K orbitals.' For example, Ca,
which has a binding energy of 4.03 keV, has a cross-section of 6r6 cm'/gm at 5 keV, but at 30
keV has a cross-section of only 4 cm'/gm.' At 5 keV, Rb has a high cross-section at 386 em'/
gm, but its binding energy is 15.2 keV-thus, an incident photon with an energy of 5 keV
would not have enough energy to displace an electron in the K orbital of aRb atom. Despite
having a lower cross-section of 20.2 cm2 /g at 30 keV, the incident energy is more than suf-
ficient to produce secondary X-rays. It is for this reason that different tube voltages are com-
monly used to detect elements of interest and multiple runs are needed. As noted by Janssen
(2003: 371): "An element can therefore be determined with high sensitivity by means ofXRF
when the exciting radiation has its maximum intensity at an energy just above an absorption
edge of that element:'
Coherent X-ray scattering is the basis for X-ray diffraction (see van der Veen and Pfeiffer,
2004). Incoherent scattering, also known as Compton scattering, is where the photon strikes
an electron in the orbital of the atom, and loses part of its energy and is deflected in a dif-
ferent direction. For non-destructive ED-XRF and WD-XRF, this incoherent scattering is
important since it is a function of the size and thickness of the sample. By ratioing the peak
heights to the Compton scattering peaks, size and shape effects are accounted for in non-
destructive ED-XRF (Shackley, 2012: 23).
 X~RAY ED-XRfl AND WD-XRF SPECTROMETRY 345

The secondary X-rays emitted by the sample are what the XRF detector measures. ED-
XRF spectrometry measures the energy and intensity of the secondary X-rays, primarily the
K and LX-ray lines. It is best suited for elements with an atomic number (Z) between 20 and
41, though with the proper excitation voltage, filters, and sample preparation, this method
can measure elements from about Z ~ 11 through about Z ~ 92 depending on the instrument.
WD-XRF spectrometry measures the wavelengths of the secondary X-rays and it can readily
measure fluoresced X-rays from the lighter elements (e.g. Na, Ca) given their longer wave-
lengths (Lachance, 1993: 158).
While in principle straightforward, there are complications to account for when it comes
to measuring and quantifying the secondary X-rays. First, the generation of secondary
X-rays occurs on the order of10-' 6 seconds, and all elements present have the potential of
fluorescing. One must have a detection system in place that can record this flood of sig-
nals. Second, there are elements that have overlapping X-ray lines; two common examples
include the Rb K' line overlapping with the Y Ka line, and the Pb La line overlapping with
the As Ka line. In addition, mass absorption effects, also called inter-element effects, need
to be accounted for. Some of the secondary X-rays that are produced can be absorbed by the
sample and generate Auger electrons, whereas others can excite other atoms present in the
sample and enhance their production of secondary X-rays. Generally speaking, higher Z
elements have the potential for enhancing lower Z elements, particularly when the higher
Z elements are present in much greater concentrations than the lower Z elements
(Wobrauschek eta!., 2010: 4). Inter-element effects and overlapping peaks can generally be
dealt with in the calibration software in newer ED-XRF and WD-XRF spectrometers.
In terms of absorption, it must be emphasized that although the primary X-ray beam
often penetrate deep into the sample, the fluoresced X-rays essentially come from the sur-
face of the sample. Low Z elements produce lower energy X-rays and generally originate
from within 10-20 microns of the surface. Higher Z elements, such as Cu, Ag, Au, and Hg,
can produce (depending on the sample matrix) higher-energy X-rays from as deep as 100
microns.

SAMPLE SELECTION AND PREPARATION

A variety of factors need to be accounted for in the selection of ceramic samples for analy-
sis. Obviously, the samples should potentially provide answers to the research question(s) at
hand. Keep in mind, though, that without a prior study to reference to, chemical analyses of
ceramics are often exploratory in nature. That is to say that although ceramics are being ana-
lyzed, the lack of a reference database makes determining the source of the ceramics inher-
ently challenging. One approach is to measure as many samples of a given ceramic type or
style as possible from a single site to see the potential variation in that single type or style.
'The condition of the ceramic samples is also important; samples that are extremely friable or
encrusted with salts have the potential of being altered by post-depositional processes (see
the end of this section). Given that most researchers use some form of multivariate statistics
to identify groups in their chemical data, larger numbers of samples helps prevent singulari-
ties from occurring in the calculations. As a general rule of thumb, the number of samples
analyzed should be a minimum of two to three times the number of elements being analyzed
346 MARK E. HALL

for. Tims, if twenty-seven elements are being measured, ideally more than fifty-four samples
should be analyzed.
One of the most important steps in preparing the sample for XRF analysis is cleaning the
surface of the sample. Soil and other substances (e.g. soluble salts), not originally part of the
pottery, need to be removed. As a minimum, pottery should be subjected to repeated wash-
ings with distilled/deionized water and scrubbing with a light nylon brush (Habu and Hall,
2001; Hall, zou; Ravisankar et al., 2011). Washing with ethyl alcohol in the final stages is also
possible. Ideally, mechanical cleaning of the surface with an abrasive rotary-type tool is nec-
essary to remove pigments> glazes, slips, and any other non-ceramic deposits that occur in
and on the outer surface of the sherd.
For qualitative analyses, both ED-XRF and WD-XRF require minimal sample prepara-
tion after cleaning. The sample can be a solid ceramic surface, a pressed pellet, a fused glass
bead, or an unconsolidated powder. Although less desirable, the main requirement for ana-
lyzing solid surfaces is that the surface is relatively flat, sufficiently cleaned from soil or other
foreign substances (see above), and homogeneous.
Pressed pellets can be used for both quantitative ED-XRF and WD-XRF measurement of
trace elements. Pellets are made by grinding several grams (2-15g depending on the labora-
toryprotocol) of precleaned pottery sample into a fine powder (200-300 mesh).' Care must
be used to avoid contamination. Most earthenwares can be ground in an agate or porcelain
mortar by hand without too much risk of contamination. For hard ceramics) such as por-
celains, it may be necessary to use silicon carbide or a tungsten carbide mill. 4 Alternatively,
some laboratories routinely obtain samples by drilling into the ceramic and then collecting
the resulting powder. Once the ceramic is powdered, it is typically mixed with a binder, such
as polyvinyl alcohol or crystalline cellulose, and pressed into a pellet using a hydraulic press
at 10-30 tons/in' (0.15-0.45 gigapascals). Pellets are often encased in a shell of aluminum or
boric acid.
Major elements with lower Z, such as Na, Mg, P, AI, and Si, are best measured using WD-
XRF spectrometry on a fused glass disk. As with pressed pellets, the pottery sample is finely
powdered and mixed with low melting flux such as lithium tetraborate or lithium metabo-
rate, and heated above 1ooo"C (Bennett and Oliver, 1976). 'The flux melts and the powdered
pottery sample is dissolved. Upon cooling the molten mixture, a glassy disk is formed. A
key aspect of fused disks is that matrix effects between samples and standards are negated
given that everything is converted to a similar glass matrix. Specific procedures for pro-
ducing fused discs of ceramic and refractory samples are detailed in the American Society
for Testing and Materials (ASTM) standard ASTM Cl6o5-04(2009) and International
Standards Organization (ISO) standard ISO 12677:2011. These two standards also specify
operating conditions for WD-XRF spectrometers.'
Fused discs with large dilutions (e.g. flux:sample ratio of 9:1) are not suitable for mea-
suring most trace elements. In some cases, success has been obtained using low dilutions
on the order of 2:1 to 5:1 (flux:sample). Eastell and Willis (1990), Hutton and Elliot (1980),
johnson eta!. (1999), and Mori and Mashima (2005) have all developed protocols that pro-
duce fused discs that can be utilized for measuring both the major, minor, and select trace
elements.
Recently, De Vleeschouwer et al. (2011) and Ichikawa et al. (2o12b) have published meth-
ods for using 100 to 300 mg of unconsolidated powders in WD-XRF studies. However, mea-
surements of unconsolidated powder are not common practice, and experimental protocols
 X-RAY ED-XRF AND WD-XRF SPECTROMETRY 347

should be rigorously studied prior to attempting to generate reliable and valid quantitative
data. This is especially true for measurements of major elements.
Quantitative non-destructive ED-XRF and WD-XRF can also be performed on ceram-
ics.' Once again, it is important that the sample surface be thoroughly cleaned. To minimize
shape effects, it is also important that the area to be analyzed is relatively flat. Some research-
ers compensate tor shape effects by using tightly focused (e.g. collimated) X-ray beams a few
millimeters in diameter or smaller to irradiate the sample. Smaller beams are particularly
useful when studying paints, glazes, or some other unique feature on a ceramic, but are not
ideal for bulk measurements. A larger beam size of 0.5 to 1.0 em in diameter is preferred for
ceramic analysis as this permits irradiation of a larger area, thereby reducing variability in
the measurement. Smaller diameter X-ray beams have been shown to produce highly vari-
able measurements in ceramics, even in cases where the sample is relatively homogeneous
(e.g. Speakman et al., 2011).
Since non-destructive quantitative XRF spectrometry is a technique that only analyzes
the surfaces of the pottery, post-depositional chemical alteration is a major concern. Studies
by Buxeda i Garrig6s et al. (2001), Hedges and McLellan (1976), and Ichikawa (2012a) on
post-depositional alteration have demonstrated that the alkali metals Ca, Mn, and P can
be altered by a variety of post-depositional processes and skew the results of any analyti-
cal method. Several of the elements measured in ED- XRF studies of pottery, such as Ga,
Nb, Th, Ti, Y, and Zr are only mobile in extreme metamorphic ;:onditions (Winchester and
Floyd, 1977; Bishop et al., 1982), which are not typical of most archaeological sites. A few
studies have demonstrated, with proper surface preparation, that non-destructive ED-XRF
produces similar results to other analytical methods (Romano et al., 2oo6; Bonizzoni et al.,
2010; Barone et aL, 2011).?

ED-XRF

As noted above, ED-XRF spectrometry measures the intensity and energy of the fluo-
resced X-rays. 11re most important elements in an ED-XRF system are: (1) the X-ray source;
(z) the detector; and (3) spectrometer geometry (Wobrauschek et al., 2010: 6-ro; Shackley,
2012: 26-33;).

X-Ray Sources
X-rays can be generated from either a radioisotope or an X-ray tube. Radioisotopes com-
monly used for XRF spectrometry include ' 4 'Am, "Co, '"9 Cd, and "Fe, which as part of
their radioactive decay emit either gamma rays or other photons. While useful for measur-
ing select elements, radioisotopes have disadvantages as an X-ray source (Whiston, 1987: 3ll;
Szal6ki et al., 2001): (1) they have a set energy level; (2) their intensity is often low and decays
with time; (3) conventional semiconductor detector efficiencies are often low for the high
energy ranges produced by the radioisotopes. Additionally, radioisotope sources are highly
regulated. With technological advances in miniaturized X-ray tubes, XRF spectrometers
using radioisotope sources have become increasingly scarce over the past ten years.
348 MARK E. HALL

Currently, X-ray tubes are the most common X-ray sources used in laboratory-based ED-
XRF spectrometers. Two types of X-rays are generated when high-voltage electrons travel
from the cathode to the anode of the tube. The bremsstrahlung radiation is produced from
the loss of kinetic energy when the electrons strike the anode; it ranges in energy from o keV
to just a few ke V over the tube voltage. It defines the background signal. The anode produces
X-rays characteristic of its composition. Anodes are typically made of higher melting point
metals (e.g. Mo, Pd, Rh, W) that have a high photon flux.
The spectrum produced by the X-ray tube can be optimized for elements of interest by
varying the operating voltage and current. Further llexibility can be obtained by using
primary filters and secondary target. Primary filters are inserted between the X-ray tube
and the sample. Filters, when made of metal sheets, can fluoresce and generate Ka and K'
X-rays that can enhance the lluorescence of elements in the sample. Filters also help reduce
the background near the absorbing edge energy, and increase the detection limits of ele-
ments in the background "trough:' For example, Pd filters with a Rh tube can enhance detec-
tion of elements with a Z between 37 and 42 (Shackley, 2012: 28), whereas Ag filters with a
Rh tube enhance detection of elements with a Z between 38 and 43 (Rose, 1990: table 5b ).
In contrast to primary filters, a secondary target is a material that is excited by the primary
X-rays. This material then emits secondary X-rays characteristic of the elemental composi-
tion of the target. These secondary X-rays are then what irradiate the sample. The use of
secondary targets results in lower backgrounds and better excitation than primary filters,
but requires a much higher initial X-ray energy. Tbe major advantage of secondary targets,
however, is lower detection limits for Na and Mg (elements very challenging to measure by
ED-XRF) and better detection limits for many other higher Z elements that occur in the low
ppm range.

X-Ray Detectors
For ED-XRF units, lifhium drifted silicon (Si(Li)) detectors are commonly used to measure
X-rays with energies between 1 and 50 keV Si(Li) detectors can process between 40,000 to
roo,ooo counts/second/mm' (cps/mm'), 8 and resolve 120 to 150 eV at 5-9 keV (Janssens,
2003: 386-387). Efficient operation ofSi(Li) detectors is obtained when they operate at tempera-
tures below 250 Kelvin (K); one way to do this is by using liquid nitrogen. Another way of cooling
the detectors is by using Peltier elements (i.e. a thermoelectric cooler) attached to fhe detector.
Two common Peltier-cooled detectors are Si-PIN (silicon-p-type semiconductor-
intrinsic semiconductor-n-type semiconductor) diodes and SDD (silicon drift detectors).
Si-PJN detectors are photodiodes used to detect X-ray and gamma ray photons. Beginnings
in the early 2000s Si-PIN detectors were widely adopted by XRF instrument manufactur-
ers as compact and inexpensive replacements for conventional liquid nitrogen cooled Si(Li)
detectors. Si-PIN detectors typically have resolutions of 170-230 eVat 5.9 keV and can pro-
cess count rates of about 40,000 cps. SDD detectors have typical resolutions of c.125-150 eV
at 5·9 keV at and can process in excess of roo,ooo cps. The primary advantage ofSDD is that
these sensors are capable of delivering lower electronic noise and higher count rates than
their Si-PIN counterparts. 1beir primary drawbacks of SDD detectors are that their detec-
tion efficiency is lower than conventional Si(Li) detectors for X-ray energies greater than 10
 X--RAY Fm-XRF AND WD-XRF SPECTROMETRY 349

keV (Potts eta!., 2004: 1399; Kenik, 2011: 40) and they typically cost twice as much as their
Si-P IN counterparts.
Other materials used for X-ray detectors include high purity germanium (HPGe), cad-
mium zinc telluride (CZT), and mercury iodide (Hgl,). HPGe detectors are suitable for
measuring X-ray energies over 30 keV CZT detectors can operate at room temperature
with a resolution of 250 eV at 5.9 keV and are also designed to handle high-energy X-rays
(Janssens, 2003: 387). 11rese detectors can handle up to 15 x 10 6 cps/mm' (Szeles eta!., 2008).
Detectors made from Hgl 2 can also operate at room temperature, deal with energies up to
150 keV, and when operating at 273 K, they have a resolution of2oo eV at 5.9 keV
While commercial ED-XRF units have focused on using semiconductor detectors,
research is still ongoing on high-resolution cryogenic detectors (Potts eta!., 2004; West eta!.,
2010). Most of the research is focusing on superconducting tunnel junction detectors (S)T)
which can achieve resolutions of 26-52 eV at 5·9 keV

Spectrometer Geometry
'!he layout and arrangement of the X-ray source, sample, and detector dictate the size of
an ED-XRF spectrometer and have an influence on the background. The simplest arrange-
ment, known as a direct excitation system, is when theX-rays strike the sample at a 45° angle
and the detector is placed at 45" to the sample surface. The sample is excited by both the
X-ray tube anode lines and the bremsstrahlung radiation. '!his arrangement takes a mini-
mum amount of space, and collimators and filters can be used to home in on specific areas
of the sample and reduce the background. In a secondary excitation system, the primary
X-ray beam strikes a secondary target whose X-rays are then reflected onto the sample. The
fluoresced X- rays strike the detector at an angle of 45". By using filters, a secondary excita-
tion system can have lower detection limits than a direct excitation system. The final geom-
etry creates a polarized X-ray beam, which strikes the sample. In this configuration, the
primary X-rays strike a polarizer at 90", which reflects the X-ray beam to the sample at a 90"
angle. The fluoresced X-rays are collimated and directed to the detector at a 90" angle. While
requiring more space, the background is decreased and lower elemental concentrations can
be measured.

Quantification
While there are a variety of computer programs available for the quantification ofED-XRF
spectra, they all depend on either a fundamental parameters (FP) algorithm or an influ-
ence coefficients method (Janssens, 2003: 401-415; Thomsen, 2007; Brouwer, 2010: 48-56;
Markowicz, 2011). FP methods are based on the theoretical X-ray production. For a given
current and voltage setting, pure element samples are analyzed. These spectra of fhe pure ele-
ments are then used to iteratively calculate the concentration of the sample (run at the same
current and voltage setting) .9 FP methods assume that one knows the matrix of the sample
and has a good idea of the elements one needs to analyze for. Many FP programs require the
chemical composition to be normalized to wo%.
350 MARK E. HALL

Influence coefficients methods are based on a regression of elemental concentrations in

standards of known concentration. For each element of interest, a calibration curve is cre-
ated that links the X-ray intensity to a known concentration. This method can account for
Compton scattering and inter-element effects. The standards used to create the calibration
curves should be of similar composition as the samples; for ceramic studies, clay and sedi-
ment standards are available from the US Geological Survey, the US National Institute of
Standards and Technology, and elsewhere that cover the relevant major, minor, and trace
elements (see Hunt and Speakman, 2015).
The calibration curve that is created should be checked against the known standards to
determine accuracy. To monitor the calibration of the ED-XRF unit and determine the
precision, known standards should be analyzed with each batch of unknown samples.
Finally, it needs to be realized that the calibration curve is only valid for a given element
between the highest and lowest concentrations in the standards used to create the lin-
ear calibration. Extrapolation of the regression line is not valid since inter-element effects
at concentrations outside the range can cause the concentration versus intensity line to
become non-linear.

WD-XRF

As the name implies, WD-XRF spectroscopy measures the wavelengths of the fluoresced
X-rays. A typical WD-XRF unit consists of an X-ray tube, a collimator, a diffracting crystal( s ),
and an X-ray detector. X-ray tube technology for WD-XRF spectrometers is very similar to
that discussed above for ED- XRF spectrometers. Collimators are optional for ED-XRF spec-
troscopy, but they are necessary in WD-XRF spectrometers. The polychromatic X-rays that
are fluoresced from the sample are directed and channeled to the diffracting crystal(s) by the
collimator. Collimators can improve the resolution by restricting the angles that the fluo-
resced X- rays strike the crystal.

Diffracting Crystals
The crystals in a WD-XRF spectrometer diffract X-rays with different wavelengths, like a
prism. When the Bragg equation is satisfied for a particular wavelength, the crystal reflects
the X-rays into a detector instead of diffracting the X-rays. The detector then converts the
X-rays of a specific wavelength into intensities for the given element.
Individual crystals are used in WD-XRF spectrometers. Lithium fluoride (LiF) is com-
monly used since it can resolve the K-lines for Ti to U, and the L-lines for the rare earth
elements (REEs). Pentaerythritol, also called PET, are used to resolve the K-lines of the ele-
ments between AI and K. Layered synthetic multilayers (LSM) are synthetic crystals manu-
factured using thin films. LSM crystals can be designed to measure the K lines of elements
between Be and F.
 PLATES

EXPERIMENTAL
CLAYTEST -PIECES

Leather~hard state Color by After firing 900 °C Color by

(moisture content Munsell (oxidizing atmosphere) Munsell
15-20 weight) code code

2.5Y 6/4 10R 5/6

'' 2.5Y 6/3 2.5YR 5/8

I
,I
!
'l
'i

I 5Y 5/2 10R 5/8

iI
Ij
5Y 6/4 10R 6/8

2.5Y 5/3 10R 5/8

2.5Y 5/2 10R 5/8

PLATE 1 Experimental firings of different clay raw materials (Sicily, Italy).

 (c) (d)

PLATE 2 Photomicrograph of thin sections of medium-high fired sherds with calcite: (a)
homogeneously distributed secondary calcite from recarbonatization after gehlenite in cal-
careous pottery (sigillata from Arezzo); (b) secondary calcite in calcareous pottery (Eastern
Sigilata A) is dissolved at the surface where environmental acid solutions had access, as, for
example, on the upper right site where the protective gloss is missing; (c) precipitated calcite
in non-calcareous North Mesopotamian metallic ware; (d) calcite scale below the red gloss
of a sherd of Tripolitanian sigillata from Carthage. (Photomicrographs by G. Schneider;
incompletely crossed polarizers, width of field 0.7 mm.)

1,1

(c)

PLATE 3 (a) Late Bronze Age pottery sample 133, hand specimen of the fabric in fresh break,
width of field is 15 mm (photograph I. K. Whitbread); (b) Late Bronze Age pottery sample
133, photomicrograph of the fabric in plane polarized light, width of field is 4.65 mm (pho-
tograph I. K. Whitbread); (c) Late Bronze Age pottery sample 133, photomicrograph of the
fabric under crossed polars, width of field is 4.65 mm (photograph I. K. Whitbread).
---------------~~--

PLATE 4 Photomicrographs of thin sections with a basalt-andesitic volcanic rock fragment

under plane polarized light (a) and crossed polarized light (b); (c) pale green pleochroic col-
ors of a pyroxene mineral in plane polarized light (field is 1.8mm); (d) moderate (low second
order) interference colors of an amphibole (field is 1.2mm); (e) secondary calcite formation
in pore space; (f) test-fired ceramic with grog under crossed polarizers. A clear demarcation
can be detected between grog and the matrix (field is 1.8mm).
PLATE 5 Some microstructural changes with increasing firing temperature involving
inclusions, pores, and groundmass. Photomicrographs in polarized transmitted light, paral-
lel polars of: a-d) mollusk shells with still preserved (a) and completely obliterated (b) inter-
nal structure, pores with irregular (vughs, c) and spherical (vesicles, d) shape, and optically
active (a, c) and inactive (b, d) groundmass, as a consequence of the firing temperature of
the same base clay material; e-f) micritic limestone grains with still-preserved crystalline
optical behavior (a) and completely obliterated (b) from the firing. Scanning electron micro-
scope back scattered images of an illitic-chloritic clay in which the groundmass is still com-
posed of well-defined grains at 1050°C (g), whereas at uoo°C it is partially melted, forming
an amorphous phase, which determines bridging between grains.
 Sample after refiring
Original
sample 400 °C 600 oc 700 °C 800 oc 900 oc

PLATE 6 MGR-analysis of six ceramic sherds, carried out to determine original firing tem-
peratures. (For explanations see text in Chapter 27.)
(a)

(b)

PLATE 7 Structural MGR-analysis of two ceramic samples. A= pottery fragment originally

fired at Teq < 70o'C; B =pottery waste, fragment over-fired at 1100-1150'C. (Photographs
taken under a reflected light microscope.)
 Sample after refiring
Original
sample 800 "C 900 oc 1200"C

PLATE 8 MGR-analysis (8oo•c, 9oo•C,12oo•C) of five samples belonging to two MGR-

groups-a fact which only becomes apparent after re-firing at 12oo•c.
8

SN
l
ovf

ovM

sMLT

MLT

fl

sovM
(temper MLT)

PLATE 9 Examples of matrix types (samples re-fired at 12oo'C) of non-calcareous sherds

(iron-rich red-firing or iron-poor whitish-firing) and of calcareous pottery (yellowish-
greenish firing). (Photographs by M. Baranowski.)
 X-RAY ED-XRF AND \VD-XRF SPECTROMETRY 351

WD-XRF Detectors
WD-XRF spectrometers can use proportional counters, scintillation detectors, or gas scin-
tillation detectors to measure the intensity of the fluoresced X-rays (of a given wavelength).
Proportional counters are essentially a sealed glass tube containing a wire and are filled with
an inert gas. 10 The wire leads out of the tube and is connected to a resistor and capacitor in
parallel. A high-voltage charge is placed across the wire. When an X-ray strikes the tube, the
gas is ionized and the negative ions are drawn towards the wire. The voltage pulse across the
capacitor is proportional to the energy of the fluoresced X-ray beam. Proportional counters,
depending on the gas/gases they are filled with, can handle over 1 million cps. Their resolu-
tion ranges from soo to woo eV.
Scintillation detectors are better at measuring X-rays with wavelengths less than 1.5A
(jenkins, 1999: 97). These detectors are made of sodium iodide doped with thallium, or cae-
sium iodide doped with thallium or sodium. This material is then connected to a photomul-
tiplier. When X-rays strike the scintillator, light is produced that has intensity proportional
to the energy of the X-ray. The photomultiplier converts the light to an electron pulse. The
resolution of these detectors is quite poor; they are on the order of 1 ke V Scintillation detec-
tors can also handle over 1 million cps.
Gas scintillation detectors combine elements of both the proportional counter and scin-
tillation detector. A gas filled tube holds two wire mesh electrodes, similar to a proportio"nal
counter; a photon enters in the tube and ionizes the gas. A charge is placed across the two
electrodes. Ultraviolet radiation is emitted when the ions collide with the electrodes. A pho-
tomultiplier measures the ultraviolet radiation that is produced. The resolution of these
detectors is around 300-500 eV.
When the detectors are mounted on a goniometer and they rotate at an angle of 26
degrees as the crystal rotates e degrees, the intensities of the wavelengths are sequentially
measured. This classifies the spectrometer as a sequential spectrometer. When there are a
series of detectors mounted at fixed angles with a fixed series of crystals, then the intensity
of several wavelengths can be measured simultaneously. WD-XRF spectrometers with this
arrangement are known as simultaneous spectrometers.

COMPARISONS BETWEEN ED-XRF

AND WD-XRF SPECTROMETERS

Both ED-XRF and WD-XRF spectrometers can be used to measure elements of inter-
est for studies of technology and provenance. 1he advantages and disadvantages inherent
to both spectrometers may influence the ability to answer the research questions, though.
In theory, both types of spectrometers can measure elements with Z >8, but light ele-
ment measurements are more challenging by ED-XRF. WD-XRF spectrometers measure
the light elements with better precision and resolution. WD-XRF spectrometers can also
more readily measure some of the REEs (rare earth elements). In terms of detection limits,
while there are associated issues of sample preparation, backgrounds, and counting times,
352 MARK E. HALL

WD-XRF spectrometers generally have superior detection limits over ED-XRF spectrom-
eters (Jenkins, 1999: 117-119; Janssen, 2003: 418).
With respect to acquisition costs, WD-XRF spectrometers, generally, are expensive
(>$zooK) and require dedicated laboratory space. ED-XRF spectrometers have a lower cost
( <s8oK) and generally occupy a much smaller footprint. jenkins (1999: 113) has noted that
despite the cost, sequential WD-XRF spectrometers offer a high level of flexibility, whereas
simultaneous WD-XRF spectrometers can process large numbers of samples quickly.

DATA ANALYSIS

Elemental data obtained from XRF spectroscopy is multivariate data. Useful books and
articles on multivariate statistics, written with the anthropologist and archaeologist in
mind, include Baxter (1994, 2003, zooS), Baxter and Buck (2ooo), Buxeda i Garrig6s and
Kilikoglou (2003), Neff(2ooz), and Shennan (1997).
Although the emphasis here is on XRF data, the following discussion applies to treatment
of most compositional data. Multivariate statistics programs are not the beginning and end
point-some data grooming needs to be done. Examination of box-plots and histograms of
each element analyzed for should be examined. Questions that need to be considered include:

(1) Are there zeroes in the data?"

(2) Are all values within the calibration range?
(3) Are all values greater than the detection limit?
(4) Are there any potential outliers?
(5) Is the histogram of the elemental values heavily skewed?

If zeroes exist in the data, or data is below the detection limit, or outside the calibration
range, then some methodology must be developed to deal with this situation. If there are
only a few values missing, it is possible to use an approach suggested by Sanford et aL (1993)
and replace zeroes and values below the detection limit, with half the detection limit for the
given element. Alternatives to this approach are using some form of multiple imputation to
calculate the missing values (e.g. Neff, 2002), or dropping the element from the statistical
analysis (Sanford et al., 1993; Palarea-Albaladejo et al., 2007).
Before any multivariate analysis is undertaken, the decision needs to be made on whether
the data should be transformed in any way. At a minimum all data should be in the same
units; if a combination of major, minor, and trace elements have been measured, then the
statistical analyses should be done on all the elemental data either in weight percent or parts
per million (ppm, or alternatively micrograms/gram)."
A debate exists in the literature on whether to logarithmically or log-ratio transform
unsealed chemical data. Based on the work of Ahrens (1954), many researchers feel that loga-
rithmic transforms normalize and scale the data (Papageorgiou, Baxter, and Cau, 2001: 572;
Baxter and Freestone, 2006). The log-ratio transform involves taking the logarithm of the
ratio of the elemental value divided by its geometric mean (Aitchison, 1982, 1986; Aitchison
et al., 2002). Variations of the log-ratio transformation are explored in Baxter (2001: 140-144).
 X-RAY ED-XRF AND WD-XRF SPECTROMETRY 353

In all situations, the transfOrmed data is used in further statistical calculations. Baxter
and Freestone (2006: 523) have noted that both transformations have the means of finding
archaeologically interpretable patterns in the data, but that patterns in log-ratio analysis
can be obscured by non-important variables, and absolute differences in the data, which are
obscured by a log-ratio transformation, can m~rkdifferent compositional "recipes:'
One commonly used multivariate technique to find groups in the transformed data is
hierarchical cluster analysis. Dissimilarity coefficients are calculated for all pairs of the data.
Then an algorithm (e.g. Ward's Method, Single Link) in hierarchical fashion groups the data
and presents it in the form of a dendrogram. The data used in cluster analysis can be the raw
chemical data, transformed data, or principal component (PC) scores (see later in this sec-
tion). Unless a statistic such as the bi-serial coefficient is used (see Hallet al., 1999), or group
membership is verified using Mahalanobis distance probabilities or some other measure,
group membership is somewhat subjectively defined.
Two other forms of cluster analysis that have seen limited use in chemical studies of
ceramics are model based clustering (Baxter, 2001; Papageorgiou et al., 2001) and mixed-
mode clustering (Baxter et al., 2008). Model-based clustering encompasses a variety of
methods, but the approach involves fitting the chemical data to a multivariate normal distri-
bution or some other pre-specified distribution. Unlike conventional clustering algorithms,
this approach has set criteria for assessing the number of clusters and can deal with overlap-
ping clusters. The disadvantages to this statistical method are: (1) it is computationally inten-
sive; (2) outliers can cause problems with group determinations; and (3) the groups can be
meaningless if the data is not multivariate normaL Despite open source software implement-
ing model-based clustering, the method has not been used much in archaeometry (see Hall,
2001,2004, 2011; Papageorgiou et al., 2001; Hall and Minyaev, 2002).
Mixed-mode clustering allows petrographic information in the form ofbinarydata to be
incorporated into the analysis of the quantitative chemical data (Baxter et al., 2008). Like
model-based clustering, it is easily influenced by outliers and requires an iterative approach
to search for groups. Unlike other examples of mixed-mode clustering, Baxter et al. (2oo8)
do not use a clustering algorithm to find groups, but use ordination methods such as prin-
cipal component analysis (PCA) or correspondence analysis (CA) and visually search for
groupings in ordinate plots.
PCA is a multivariate ordination technique that is also commonly used in ceramic com-
positional studies. 1l1e technique transforms a series of correlated variables into linearly
uncorrelated variables known as principal components (PC). The transformation is such
that the bulk of the variance is contained in the first PC, while the second PC contains the
second greatest amount of variation. Details on the method and its associated mathematics
can be found in Baxter (1991, 1994: 48-99) and Shennan (1997: 265-307).'3 Structure or pat-
terns in the PCs is sought by visual examination ofbi-plots of the PCs, or by using some form
of cluster analysis or kernel density estimates.
CA is another ordination technique that is sometimes used to look for patterning in the
chemical data. It is not as widely used as PCA. CA looks at the relationship between the rows
and columns of the data matrix and aids in detecting relationships between the individual
samples and the chemical elements (see Baxter, 1991; Shennan, 1997: 308-327). jacobson et al.
(2002) and Pillay et al. (2000) are two case studies that use CA to find patterns in the ceramic
chemical data.
354 MARK E. HALL

BACK TO THE BIG QUESTION(S)

It needs to be underscored that good archaeological science does not end with the discovery
and statistical setoff of compositional groups. The next step, and perhaps the most impor-
tant step, involves incorporating anthropological and/or archaeological to aid in inter-
preting the empirical patterns observed in your chemical data. As Baxter (2oo8: 972) has
emphasized: "It is the archaeological interpretation that is paramount, unless a study is a
purely methodological one:'
Archaeological and anthropological interpretations of ceramic chemical data are tied to
how one views technology. 14 In ceramic studies, the "Archaeological Science" I "Behavioral" I
"Processual" I "Technofunctionalist" school typically has dominated much of the discussion.
This school of thought sees culture as a neutral agent in ceramic production, limited to decora-
tion and ornamentation. Functional properties and environmental factors are what are seen as
driving ceramic manufacture.'' In contrast to this school of thought is the "Cultural''/ "Post-
Processual" school which arose in the mid-198os. It essentially sees technology as a cultural
product that is influenced by human choice and can convey identity and symbolic meaning.
Only in the last fifteen years or so has a middle ground been grudgingly acknowledged
that sees a dynamic relationship between technology and culture, each of which responds
to the other (see Sillar and Tite, 2ooo; Griffiths, 2001; Jones, 2004). Cultures can accept or
reject certain technologies, while technology can force unintended social changes in a cul-
ture. Material properties can often give an object social value and meaning in a culture (see
Tite et al., 2001), while cultural behaviors and beliefs can dictate the materials that are used
in manufacture and how those materials are processed.
Evolutionary archaeology has also come into the fray to address the causes of techno-
logical change, technological choices, and historical processes. While some of their theo-
retical adherents can admit that their definition of selection can be exceedingly narrow
(Neff, 2001: 28o), collaborations with the "Cultural" school of thought are seen as meth-
ods in which to resolve some of their epistemological angst-particularly when it comes to
addressing the issues around why cultures choose certain technological variants and how
they succeed or fail.

Getting at the Big Question( s)

The underlying purpose ofX-rayfluorescence spectrometry and other analytical techniques
is to provide empirical data that ultimately sheds light on human behavior.'' In this section
we examine a few issues that ceramic compositional data can address. The following exam-
ples are not intended as a comprehensive list or review, but instead serve to highlight various
ways in which compositional data can be used to address cultural issues. Numerous other
examples are provided elsewhere throughout this book.
Provenance studies of ceramics aid in the study of trade and exchange in archaeological
cultures. Manufacturing facilities-such as clay mines, pottery wheels, or kilns-present at
or in the vicinity of a site are one of the chief pieces of archaeological evidence that aid in the
interpretation of chemical groups (see Buxeda i Garrigos et al., 2001; Day and Kilikoglou,
 X-RAY ED-XRF AND WD-XRF SPECTROMETRY 355

2001). This archaeological data, combined with the chemical data, whether it be derived
from X-ray fluorescence spectrometry or some other analytical method, can lead to verify-
ing that one or more of the chemical groups found at a site were actually produced there.
Further interpretations can be obtained when one looks at how the manufacturing facili-
ties are placed at the site-examining whether they are associated with households, a single
household, or a single, non-domestic structure.
For complex societies with a written record, archaeologists and historians can strive to
write a "narrative" or "archaeoethnography" that examines: (r) continuity and change
within the ceramic technology; (z) the economics of trade and exchange of ceramics;
(3) how ceramic technology relates to other technologies; 4) the interrelationship between
technology and political and economic structures; and s) how the society uses ceramics
(Cumberpatch, zoor). As an example of this, Skoglund et al:s (zoo6) study of ceramics at
the periphery of the Aztec empire draws on several lines of evidence to examine how differ-
ent segments of postclassic society in Veracruz used Late Aztec wares, copies of Late Aztec
wares, and locally produced wares. While not fully capturing Cumberpatclis "narrative:' the
study by Knappett et al. (zoo5) on Late Bronze Age Red Lustrous ware is a solid illustration of
how provenance studies can address socioeconomic issues.
For small-scale societies, while the ceramic chemical data can indicate trade and exchange,
one must keep in mind that other factors can drive the movement of pottery across the
landscape. Eerkens, Neff, and Glascock's (zoor) work on pottery made by the Paiutes and
Shoshone indicates that these hunter-gatherer groups exploited a number of clay sources
throughout their seasonal range. For the most part, pottery was used locally and the small
amount of non-local pottery at sites is seen as being due to seasonal movements versus trade
or exchange. This is in contrast to the Middle jomon foragers ofJapan who developed an elab-
orately decorated, mica-tempered ware called Atamadai pottery. While the production zone
for this pottery appears to have been concentrated in the eastern Kanto region, its distribution
covers over 6o,ooo square kilometers in the Kanto and southern Cubu regions of)apan (Hall,
zon). Given that the Middle jomon foragers of japan exhibit no evidence of a hierarchal social
system, the spread of this pottery is seen as being because it was used to carry shellfish or some
other traded commodity from the coast, or redistributed on the basis of household ties.
Chemical data from ceramic studies is one piece of evidence when looking at standardiza-
tion and uniformity Standardization can be viewed as similarity through time, while uniformity
focuses on a distinct temporal period (Arnold, zooo: uo-m). While one may expect standard-
ization and uniformity in complex, state-level societies, it can also be seen in other levels ofsocio-
economic complexity. Hall et aL (zooz) is just one example illustrating the continuity of paste
recipes used to mal<e pottery. In this study ofEpi-jomon and Okhotsk pottery on Rishiri Island,
the paste recipe may have been dictated by geological factors, the possibility could not be dis-
counted that the Okhotsk pottery tradition was descended from the Epi-jomon pottery tradition.
joyce et al. (zoo6) is another case study illustrating uniformity in a paste recipe through time.
Chemical homogeneity in ceramic assemblages, in addition to being an indicator of uni-
formity, can also reflect political realities. Neupert's (zooo) ethnoarchaeological study of
Luzon potters illustrated how elite alliances can influence access to clay resources. Similarly,
drawing on multiple lines of evidence, Fowles et al. (2007) posits that the chemical homoge-
neity in Coalition Period (c. AD 1050-1260) ceramics in New Mexico is the result of interre-
gional conflict blocking access to clay sources.
 ,
I
356 MARK E. HALL

ACKNOWLEDGMENTS AND DISCLAIMER

Thanks must be given to Robert DeAngelis, john Donovan, Mineo Imamura, Steve Shackley,
and Tim Teague. Over the years, they patiently taught me the ins and outs of X-ray fluores-
cence spectrometry. Thanks also are in order for Alice Hunt's and jeff Speakman's assistance
with this chapter.
All views and opinions expressed here are those of the author and do not represent those
of the Bureau of Land Management nor the Department of the Interior.

NOTES

1. Open-source software programs such as MUCAL (Bandyopadhyay and Serge, n.d.) exist
to calculate the binding energies and cross-sections for the elements. The binding energy is
one reason why multiple XRF runs at different tube operating conditions may be needed.
2. The higher the cross-section, the higher the probability of producing a fluoresced X -ray.
3· Pressed pellets should not be confused with fused glass beads. Smaller samples can be
used for WD-XRF fused glass pellets; see Nakayama et al. (2012). Ceramics are a hetero-
geneous material, though; a small sample may not capture the full scope of compositional
variability in the shard (see Ichikawa et al., 2012a).
4. johnson et al. (1997: 884) note that carbide milling equipment can cause Co, Nb, and W
contamination.
s. Academic and research work often ignores the ASTM and ISO standards. While these
standards are developed and designed for commercial materials and emphasize consistent
repeatability, there is useful information to be garnered from them in terms of developing
procedures and methods for academic laboratories.
6. While non-destructive WD-XRF is routinely done on lithic materials, one study was
I
found where this was done on ceramic materials (seeXie et al., 2007).
7· For mid-Z elements, Romano et al. (2oo6) found that the mean concentration values
(n ~ w) from the surface and powdered samples, differed from 6% to 28%. The other stud-
I
!:
ies referenced do not explicitly look at the variation between each element.
8. It is generally recommended that the current and voltage be set so that an Si(Li) detector I
'I
has a dead time of approximately so%. II
9. For the mathematics behind the FP method, see Janssens (2003: 414) or Thomsen (2007). II
I
10. K or Xe gas is used to measure X-rays with energies above 15keV. Ar is used for measuring I'
X-rays with energies betvveen 5 and 15 keV. A mixture of Ar and methane is used to mea- ~
sure lower energies. See Bacso et al. (1998: 177).
n. Under the best conditions, ED-XRF can generally measure down to 5-10 ppm, while WD-
XRF can measure some elements down to 1-5 ppm. Depending on how the software deals
with the background and the detection limit, zeroes may appear in the chemical data. If
one decides to transform the data, zeroes are undefined on the logarithmic scale.
12. When dealing with chemical data covering a broad scale, to weight the variables equally;
scaling is suggested. This involves subtracting the mean of the variable from each variable
and dividing by the standard deviation.
13. Baxter (1995) is an informative look at the effects of transforming one's data in PCA.
 X-RAY .ED-XRF AND WD-XRF SPECTROMETRY 357

14. This brief section is drawn from the works of Jones (2004) and Livingstone Smith (2ooo).
This is a very broad topic and the discussion here does not do it full justice.
15. What is sometimes forgotten by this school of thought is that the physical proper·
ties of the ceramics may account for how the culture responds to the finished product.
"Consumer choice" can have a profound impact on how a technology develops or does
not develop.
16. The case studies mentioned in this section are just a small sample of ceramic studies illus-
trating the utility of compositional studies to address anthropological questions. While
many of the studies determined the chemical composition of the pottery using XRF spec-
trometry, some studies used other methods of analysis.

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 CHAPTER 21

HANDHELD PORTABLE
ENERGY -DISPERSIVE
X-RAY FLUORESCENCE
SPECTROMETRY (pXRF)

ELISABETH HOLMQVIST

INTRODUCTION

THE scope of this chapter is the application ofhandheld portable energy-dispersive X-rayflu-
orescence spectrometers (commonly referred to as portable XRF (pXRF; p-ED-XRF), hand-
held XRF (HH-XRF) or field-portable XRF (FPXRF); henceforth pXRF) in non-destructive
elemental analysis of archaeological ceramics. In archaeometric ceramic studies, handheld
pXRF is a fairly new, post-2005, application, a compact variant oflaboratory-based energy-
dispersive X-rayfluorescence (ED-XRF) spectrometers; it is increasingly applied in ceramic
provenance studies. Controversially, however, non-destructive XRF analysis of ceramics in
archaeometry is generally considered as a qualitative or semi-quantitative method, with lim-
ited analytical capacity for source determination (Picon et aL, 1971; Bailie and Stern, 1984;
Schwalbe and Culbert, 1988; Anders et aL, 1992; Hall, 2004; Padilla et aL, 2006; Pappalardo et
aL, 2006).
For fully quantitative XRF analysis (Jenkins et aL, 1995: 283-287; jenkins, 1999:141-145;
Moens et aL, 2000; Schmeling and Van Grieken, 2002; Van Grieken and Markowicz, 2002;
Beckhotf et aL, 2oo6; Shackley, 2011), ceramic samples are powdered and prepared as pressed
pellets or fused glass beads, prior to analysis under vacuum, to compensate for material het-
erogeneity (particle size, mineralogy, porosity) and to ensure that the analytical specimen is
representative of the sample bulk composition. In principle, this protocol allows for quan-
tification of 20-30 major, minor, and trace constituents, from Z = 11 (Na) to Z = 92 (U) in
laboratory ED-XRF. The handheld instruments, however, are employed almost exclusively
on unprepared samples. In addition, they are designed for rapid tests in mining and metal
recycling industries, and thus lack fundamental facilities for quantitative research: proper
vacuum facilities and matrix-matched calibration software (Pessanha et al., 2009; Forster
364 ELISABETH HOLMQVIST
······················-··················································································

et al., 2on: 390; Speakman et aL, 2011: 3484; Goodale et al., 2012: 882-883; Speakman and
Shackley, 2013: 1437-1438; Hunt and Speakman, 2015).
As a result, the sensitivity and, subsequently, the elemental range of pXRF in non-destruc-
tive ceramic analysis are reduced; although manufacturers may claim that elements Mg- U
can be detected, their quantification is problematic. Crucially, low Z elements are excluded
because they cannot be accurately detected without vacuum and flat, homogenized samples
(Potts et al., 1997a; Williams-Thorpe et al., 1999: 217; Spealanan et al., 20n: 3484; Shugar,
2013; johnson, 2014; Hunt and Speakman, 2015: 627-630). Therefore, information about
major elemental constituents in ceramic pastes, important for fabric characterization (e.g.
temper~indicative Si and Ca), is unavailable. However, semi~quantitative relative values-
for example, net peak area values-for a limited range of high Z elements can be generated
under common pXRF analytical conditions (Gigante et aL, 2005; Forster et al., 2011; Liritzis
and Zacharias, 2011: 134). "There is also a risk that measured concentrations merely represent
the outer layer of the object, a coating, or surface contamination (Moens et al., 2ooo: 56).
In recent studies, the analytical performance of pXRF has been examined in comparison to
high-sensitivity techniques, such as neutron activation analysis (NAA) and inductively cou-
pled plasma-mass spectrometry (ICP-MS), with encouraging results: non-destructive pXRF
can distinguish geochemically different ceramic pastes and identify groups that closely cor-
relate to those indicated by these methods (Forster et al., 2on; Goren et al., 2on; Speakman et
al., 2on; Mitchell et al., 2012; johnson. 2014; Hunt and Speakman. 2015). However, these stud-
ies report a discrepancy between the absolute elemental concentrations generated with pXRF
compared to other methods, a tendency also found in obsidian studies (Craig et al., 2007:
Nazaroff et al., 2010; Millhauser et al., 20n; Goodale et al., 2012). To quote johnson (2014:
564), pXRF provides "inaccurate elemental concentrations which pattern in accurate ways:'
Naturally glassy and homogeneous obsidian can be successfully geochemically sourced
by non-destructive pXRF (Cecil et al., 2007; Craig et al., 2007; Phillips and Speakman,
2009; Craig et al., 2010; Sheppard et al., 2on; Frahm et al., 2014). In stark contrast, the entire

FIGURE 21.1 SEM-BSE micrographs of heterogeneous ceramic matrices showing sand-

temper (large grains) adding to the natural mineralogical and particle size variation and the
bulk chemistry of the clay used in Neolithic Scandinavian pottery manufacture. A 30 ~m
thick postHdepositional soil accumulation layer can be seen on surface of the sherd illus~
!rated on the right, preventing accurate surface analysis of the sherd without removal of the
surface layer.
-----------------------"·~~"""

HANDHELD PXRF 365

concept of ceramic provenance is far more complex: ceramic composition is not purely inor-
ganic chemistry but a combination of geological raw materials and culturally evolved craft
traditions (inter alia Rice, 1996: 169-17z)" The addition of non-plastic tempers, porosity, and
chemical and mineralogical heterogeneity of natural clays (Figure zr.1) contribute to the
reduced sensitivity, precision, and accuracy that characterize non-destructive pXRF studies
of unprepared archaeological ceramic samples.

SURFACE EFFECTS

In pXRF, the analytical signal comes from a surface layer, the thickness of which depends
on element-specific critical penetration depth, varying between c.0.03 and 1 mm. Thus, any
surface layering or irregularity directly affects the results (Williams-Thorpe et al., 1999: z19;
Cesareo et al., zooS: 52-53). Therefore, for accurate paste analysis, any surface coatings, slips,
or glazes need to be removed to avoid mixed analysis (liiafiez et al., 2007: 3So). ltmayalso be
necessary to remove the sherd surface to exclude interference of surface contamination; that
is, soil accumulation or post-depositional chemical alteration of the sherd surface (Figure
zr.1) (Heimann and Maggetti, 1981; Freestone, 2001; Schwed! et al., zoo4; Casaletto et al.,
zooS).
Surface irregularity and even a small analyzer-to-sample distance cause air attenuation,
a "shielding effect" that blocks the fluorescent X-ray path to the detector, and reduces the
intensity of the measured X-rays, particularly affecting the low Z elements. This creates false
elemental ratios and notable errors in quantitative analysis (Potts et al., 1997a; Markowicz,
zooS: 2z; Forster et al., zon: 392-393). Elements that have greater penetration depths (e.g.
Rb, Sr, Zr, Ba) are less sensitive to surface effects (Williams-Thorpe et al., 1999: 2z5). Use of
helium flow (available for some pXRF intrumentations) can decrease air attenuation for low
Z element measurements, but it does not equal the benefits of full vacuum conditions offered
by bench-top ED-XRF instruments (Hunt and Speakman, 2015: 636-637). A study by Forster
et al. (2011) found that a convex sample surface provided the highest intensity detection,
whereas concave surface most drastically decreased the intensity detected for both light and
heavy elements. Rough and etched surface topography also had a negative effect on intensity,
but to a lesser extent. Heavy elements (Z ~26, Fe) in general were less sensitive to surface
irregularities (Forster et al., zon: 390-397). Correspondingly, lower than expected concen-
trations were measured on concave obsidian surfaces (Millhauser et al., 2on: 3148-3149 ).

PARTICLE SIZE AND MINERALOGY EFFECTS

The volume of the analyzed sample is a product of the active detection area coverage and
the penetration depth of incident X-rays, and the distribution of the elements in this space
affects their representation in the analytical results (Markowicz, 2ooS: z1-23; Forster
et al., 2011: 394-395). The particle size affects particularly the light element X-ray intensi-
ties: for samples with the same elemental concentration, higher value is measured for the
366 ELISABETH HOLMQVIST

fine~grained variant compared to the coarse-grained comparanda-this is normally over-

l
I
come by powdering granular samples (Markowicz, 2008: 21; Markowicz, 20u: 321-324). The
effect of powdering on different elements ( Ca, Fe, and Rb) was tested by examining the cor-
relation between semi-quantitative pXRF of powdered and unprepared samples and quan- I
titative NAA data (Figure 21.2). High correlation between non-destructive pXRF and NAA
was found for Fe and Rb regardless of the sample format, whereas the lightest element Ca
showed significantly poorer results (Forster et al., 2011: 395-396). In contrast, another study
reported good correlation between ICP-MS and non-destructive pXRF values forK and Ca,
but less successful results for Fe (Johnson, 2014). Trace elemental concentrations may also
vary relative to sample treatment (Romano et al., 2006: 5-6).
Unprepared samples need to be very fine grained; otherwise the results are likely to vary
across different parts of the sample. Repeated measurements, depending on the grain size
of the analyzed material, are required to ensure acceptable precision (a standard deviation
of the mean of 10% or better) and a result representative of sample bulk composition and

(a) (d)
3000 3000
Ca (powder)
2500- 2500

2000 2000

1500 1500

1000 1000
y"' 244.18x -132.91 500
y"' 186.49x +702.58
500
R2 "'0.9136 R2 "" 0.4945
0 0
0 4 10 12 0 4 12

(b) (e)
60000-,----------------, 60000-,--------------,
Fe (powder) Fe (non-destructive)
50000 50000

40000 40000

30000 30000

20000 20000

10000- 10000 y"' 5118x +5094.6

R2 "' 0.9638
10 0 10

(c) (f)
3000-,-------------, 3000 , - - - - - - - - - - - - - - - ,
Rb (powder) Rb (non-destructive)
2500 2500

2000

1500

1000

500 Y"' 16.366x-147.18

2
R "" 0.8879
o+-----.------r-----.-----~
0 50 100 150 200

NAA (%/ppm)

FIGURE 21.2 Correlation of pXRF net peak area values to quantitative NAA data. Linear
regressions illustrate correlation for Ca, Fe and Rb for powdered (a-c) and non-destructive
(d-f) sample treatments. (Reprinted with permission from Forster et al., 2011:395, Fig. 4.)
 HANDHEL-D PXRF 367
~~~-

matrix heterogeneities, grain size, and mineralogy (Potts et al., 1997b; Forster et al., 2011;
Goren, 2011: 688). Especially for coarse ceramics (Figure 21.1), the analytical window size
(c.5-10 mm' depending on the brand) may be inadequate, and multiple analyses of different
sample regions are necessary to increase the analytical volume and to achieve a larger and
more representative sample. Three measurements for relatively fine grained materials, and
five for medium to coarse matrices may be adequate, but certain elements (e.g. Nb, Sr) in
coarse matrices may require substantially higher number of analyses to achieve acceptable
precision, which may significantly increase the time invested in the analysis and spectra pro-
cessing (Williams-Thorpe et al., 1999; Forster et al., 2011: 395). In addition, varying intensity
detection across the window was also encountered (elements positioned near the center of
the window giving higher fluorescence signal compared to the marginal areas), further add-
ing to low precision caused by material heterogeneity (Forster et al., 2011: 389-396). Hunt
and Speakman (2015) found that pXRF was not able to accurately quantify Na, P, V, Cr, Co,
Ni, and Ba (L-lines), even when the ceramic samples were prepared to pressed pellets and
analyzed using matrix-matched calibration and He flow.

DATA STANDARDIZATION

In order to quantify the measured X-ray fluorescence intensities into weight fractions, the
instrumentation needs to be calibrated with standard reference materials of known com-
position. It is essential that the calibration standards possess similar matrix characteris-
tics (porosity, granularity, mineralogy) and, hence, similar matrix effects, as the unknown
samples to be analyzed (Bishop et al., 1990; Jenkins et al., 1995: 271-273, 338-387; Rousseau
et al., 1996; Feret and Jenkins, 1998: 35; Markowicz, 2oo8: 18-19). Chemical matrix effects
(absorption and enhancement; inter-element effects) can be resolved using influence coef-
ficients and fundamental parameters; that is, measured relative intensities are transformed
to calculated relative intensities to provide a straight calibration line in the calibration pro-
cess (Jenkins et al., 1995: 344-387: van Sprang, 20oo; Rousseau, 2006: 759-776; Thomsen,
2007; Markowicz, 2008: 27-36). Physical matrix effects caused by material and surface het-
erogeneity (e.g. lower intensities are detected for irregular sample surfaces compared to flat
samples of the same concentration, if flat calibration samples were used) can be corrected
using the Compton and Rayleigh method (Rousseau et al., 1996: 184-188; Potts et al., 1997a;
Markowicz, 2008: 16-17; Markowicz, 2011: 324-327; Shu gar, 2013: 178-182).
Speakman et al. (2011: 3484) recommend that pXRF users create their own calibrations
that match the matrix properties of their unknown archaeological samples, as the factory-
installed calibrations, based on flat, homogeneous samples, do not provide acceptable pre-
cision and accuracy for quantification and data reproduction purposes in archaeological
cases. Factory calibrations may also not include all elements of interest for chemical char-
acterization of archaeological ceramics (Hunt and Speakman, 2015). In practice, creating a
matrix-matched calibration can be highly problematic because it requires access to more
sensitive techniques (e.g. NAA) to gain calibration data, and again the potential heterogene-
ity of unprepared ceramics (variation in particle size, temper) may mean that the created
calibration and experimental standards are suitable for a very limited range of cerainic mate-
rials. Acquiring commercial calibration standards suitable for unprepared archaeological
368 ELISABETH HOLMQVIST

ceramics can be impossible, which is largely why recent attempts to create ceramic calibra~
lions have faced problems (Aimers et al., 2013: 423-42+ johnson, 2014).
In addition to intermethod inconsistencies, pXRFs also seem to have inter-instrument
accuracy issues; separate instruments report varying "true values" using the same factory
calibration (Nazaroff eta!., 2010: 893-894: Goodale et al., 2012: 880-882; Frahm et al., 2014:
236: see also Hein et al., 2002). Relatively good intra-instrument precision is reported, but
periodically reanalyzed control samples are recommended to ensure intra-instrument pre~
cision over long periods (Bishop et al., 1990: 542-543; Shackley, 2010: 18-19: Glascock, zon:
172-173; Markowicz, 2011: 327).

DEFINING ANALYTICAL PROTOCOLS

Based on the above-mentioned factors, the following parameters have been suggested as a
scientific protocol to control the sources of error, deriving from inhomogeneous ceramic
samples, and to facilitate non~destructive geochemical discrimination of cer·amic materials:

(I) Matrix-dependent number of repeated analyses to obtain acceptable analytical preci-

sion and a result representative of the material heterogeneity (particle size, mineral~
ogy) and bulk composition of the sample (Potts et al., 1997b; Williams-Thorpe et al.,
1999: 219: Forster et al., 2011; Speakman et al., 2011; Grave et al., 2012).
(2) Focusing on high Z (;,26) elements in geochemical discrimination, to avoid preci-
sion and accuracy issues related to light element detection in non-destructive in-air
ceramic analysis (Forster et al., 2011; Speakman et al., 2011: Grave et al., 2012; Hunt
and Speakman, 2015).
(3) Elements prone to surface post-depositional alteration (e.g. S, Cl, P, Ba) and concen-
trations near the LOD (limit of detection) should be excluded from the data analy-
sis owing to high background noise in relation to peaks of interest in pXRF spectra
(Gigante et al., 2005; Pessanha et al., 2009; Forster et al., 2011: 390; Goren et al.,
2011: 689: Liritzis and Zacharias, 2011: 134; Frankel and Webb, 2012: 1380-1386).
(4) Use of relative, semi-quantitative net peak area values instead of quantitative units
(parts per million; ppm) in circumstance where suitable calibration is unavailable
(Gigante et al., 2005: Forster et al., 2011; Liritzis and Zacharias, 2011: 134) to avoid
generating "untrue" absolute concentration values (Shackley, 2010: 18; Forster et al.,
2011: 393; Liritzis and Zacharias, 2011: 132-134; Speakman eta!., 2011).
(5) Minimal sample requirements are that the sample is clean, dry, preferably flat or at
least non~concave surfaced, has no surface layering or treatments, covers the entire
analytical window, and is at least 6 mm thick to allow "infinite thickness" (Potts et al.,
1997a; Ge eta!., 1998; Moioli and Seccaroni, 2000: 48; Romano et al., 2006: 4-5;
Goren et al., 2011:687-688: Liritzis and Zacharias, 2011: 112: Markowicz, 2011: 322;
johnson, 2014: 563).
(6) Combined invasive sampling, for at least part of the sample set, should be consid-
ered. Prior knowledge of the expected group structure and chemical variability can
be helpful (Speakman eta!., 2011: 3494), and data obtained by methods with higher
analytical sensitivity can help exclude precision- and accuracy-related issues in the
 HANDHELD PXRF 369
---~,,--~-~-~--,-~~~,~~~~-~,,-,-~~,-------

chemical grouping. Microscopically (scanning electron microscopy with energy

dispersive spectrometry (SEM-EDS) or petrography) examined control samples
(e,g,, per chemical group) can help to exclude temper- and mineral-related variation
(Figure 21.1) and to evaluate various technological aspects to strengthen the archaeo-
logical interpretation,

RECENT APPLICATIONS
IN CERAMIC PROVENANCING
AND GEOCHEMICAL DISCRIMINATION

Portable XRF spectrometers have been used in archaeological materials science since the
early 1970s (Cesareo et al., 1973), but were fairly recently introduced in the field of ceramic
studies (Morgenstein and Redmount, 2005; Emery and Morgenstein, 2007) 0 TI1e sensitiv-
ity, resolution, count rates, and the LODs of the handheld instruments have significantly
improved during recent years, particularly since the advent of silicon drift detector (SDD)
technology, which replaced the earlier silicon pin detectors (Si-PIN) (Piorek, 1997; Potts,
2008: 9; Pantazis et al., 2010; Forster et al., 2011: 389-390; Goren et aL, 2011: 685; Liritzis and
Zacharias, 2011: n6; Speakman et al., 2011; Mitchell et al., 2012), As a result, the use of pXRF
in archaeology has increased massively, but generally accepted scientific protocols for its use
and data processing are still being formulated (Shackley, 2010; Liritzis and Zacharias, 2011;
Speakman and Shackley, 2013),
The following case studies highlight that the highest resolution in chemical grouping by
pXRF is achievable when there is prior knowledge of the data structure; that is, the same
sample set is analyzed by another, high-sensitivity technique, Accordingly, many of the stud-
ies that employ pXRF as the only method are disadvantaged by reduced resolution and more
ambiguous clustering, subsequently decreasing the specificity of data interpretation from an
archaeological perspective.
Speakman et al. (2011) examined the capacity of non-destructive pXRF to distin-
guish compositional groups in pottery samples representing varying grain sizes from the
American southwest, previously analyzed by instrumental neutron activation analysis
(INAA). For pXRF, the surface was flattened, layers removed, washed, and dried (Speakman
et al., 2ou: 3490). The pXRF analytical conditions were as follows: resolution of c.qoeV
FWHM for 5·9 keV X-rays, area 7 mm', spot size diameter c.4mm; first analysis at 40 kV/
15~A with Cu and Al filters, live-time count 2oos, peak intensities for the Ka peaks of Mn,
Fe, Rb, Sr, Y, Zr, Nb, and La forTh were converted to parts per million (ppm) by using the
Compton peak of rhodium and linear regressions from fifteen obsidian samples (Phillips
and Speakman, 2009; Speakman et aL, 2ou: 3493); for the second analysis 12 kV/ 15 ~A;
zoos live-time count, Ka peaks for Al, K, Ti, and Kp for Ca converted to ppm by a quadratic
regression model based on pressed powder standards (Glascock et al., 2007; Speakman et
al., 2011: 3495).
The results highlighted a similar group structure in both datasets, and relative correlation
between elements measurable by both pXRF and INAA (Al, K, Ca, Ti, Mn, Fe, Rb, Sr, Zr, and
Th), Rb, Sr, and Fe showing the closest correlation (Figure 21.3) (Speakman et al., 2011: 3494).
370 ELISABETH HOLMQVIST

(a) 0.22
Mo
PXRF
0.18

0.14

0
0.10
"
0
0

if
u 0.06
0

jj_
B 0.02
3::
-0.02 ·-- Th

-0.10
-0.3 -0.2
Prindpa! Component 1

(b) -0.30
INAA Mo

-0.22

N
0
"0g_ -0.14
E
0
u
jj_
·o -0.06
0
3::
Rb

0.02

0.10 Th M8 M4a M2a

0.15 0.10 0.05 -0.00 -0.05 -0.10 -0.15 -0.20 -0.25 -0.30
Principal Component 1

FIGURE 21.3 PCA biplots of the variance-covariance matrix of the pottery samples mea-
sured by pXRF and INAA, elements common to both techniques (Al, K, Ca, Ti, Mn, Fe, Rb,
Sr, Zr, Th) used, ellipses represent 90% confidence level for group membership. (Reprinted
with permission from Speakman et al., 2011: 3494; Fig. 4 A and B.)

The authors concluded that under these parameters, pXRF provided relatively similar ana-
lytical precision and accuracy for the elements comparable with INAA, but other, method-
specific elements provided higher resolution in group discrimination; namely, Th, Nb, Sr,
and Rb for pXRF (Speakman eta!., 2011: 3495).
Forster et al. (2011) compared the effects of sample preparation procedures (unprepared,
cut surfaced, powdered) on pXRF and NAA correlation by analyzing a set of handmade
ceramics from Turkey known to display a clear group structure and distinctive geochemical
signature by previous NAA. The reported pXRF analytical conditions were: 40 ke V!13 ~A;
 HANDHELD PXRF 371
----
070 eV FHWM at Mn Ka peak at 5-9 keV at 1000 counts/s; Cu, Ti, AI filter; analytical area
7 mm 2 ; five replicate analyses, analysis time 30os.
Net peak area values of Fe, Th, Rb, Sr, Y, Zr, and Nb processed by principal component
analysis (PCA) illustrate that heavy elements can provide accurate group discrimination
comparable to NAA data, regardless of the manner of sample preparation, subject to follow-
ing an adequate protocol to control measurement errors; in this case, five repeated analyses
to achieve a standard deviation error of ±10% (Forster et al., 2011).
Compared to coarse ceramics, vitrified, glass-like stoneware bodies are unaffected by het-
erogeneity and particle size issues in non-destructive analysis. Mitchell et aL (2012) reported
the following pXRF analytical conditions for their comparative pXRF, NAA, and ICP-OES
study of high-fired Asian stoneware: 070 eV FHWM resolution for 5-9 keV at 1000 counts/
s; 40 kV/15 rnA, Cu-Ti-Al-filter; analyzed area 7 mm'; measuring time 300s, and five repli-
cate analysis (in pursuit of coefficient of variation <10% ).
Semi-quantitative pXRF net peak area values of Ti, Fe, Rb, Sr, Y, Zr, and Nb allowed
for groupings that "directly correspond" to those indicated by significantly higher-
dimensional NAA and ICP-OES datasets (23 and 19 elements respectively) (Figure 21.4)
(Mitchell et aL, 2012: 2921-2932). Goren et aL (zou) investigated non-destructive pXRF
group assignments of a sample set of very fine-grained cuneiform tablets, part of which
were previously analyzed by NAA and petrography using the following pXRF analyti-
cal conditions: sokV; Cu and Zn filters; analyzed area diameter 8 mm; factory preset

PXRF 7 ICP-OES 19 NAA23

----~-"
4-
3.5 <:>SK 20
3 <:>Sii9 4
2.5~
2
N 1.5· • Sf('tt!-o~.•- .- o N

~
N
ii¢1"o ~
j 05
1
• ••
5 0
~ 0

.
~ 0 § -2
g g
u
-0.5
-1 • •• ~ -4 u -2
_,
-1.5 •• u

-2.5
-3
_,.j
-6 oSH 20
oSH9
-4
oSH9
oSH 20
-3.5 -10.
25
''1--:::-:-:--------1
SH 9
•SH 18 0
o. 4 0 SH 20
1.5 8 SillS
1 '\ M 2 M
E 1
j 0.5
•
0
00 ~\ g •
8e 0
-0.5- •••'• 0
0
0
r I
~

~
0
eo
8
/
-1
• -2 -2
-1.5
-2
•• of!SH20
-2.5 "" -4 -4

-4 -3
_, -1 0 2 3 -5 -2.5 2.5 -2.5 0 2.5 7.5
Component 1 Component 1 Component 1
Cluster
.. 3.7
3.8

FIGURE 21.4 PCA biplots with density ellipses for clusters indicated by low-dimensional
pXRF data (Ti, Fe, Rb, Sr, Y, Zr, and Nb) and high-dimensional ICP-OES and NAA datasets
(19 and 23 elements, respectively) of Asian stoneware pottery. (Reprinted with permission
from Mitchell et aL, 2012: 2931; Fig. 7-l
372 ELISABETH HOLMQVIST

"mining" matrix; measuring time 18os; three replicate analysis. In this analysis, Fe, K,
Rb, Ti, and Zr values showed the best correlation with INAA clusters (Goren et aL, 2011:
684-689).
It appears that case-specific heavy elements are the most useful for group discrimina-
tion in non-destructive pXRF data. Accordingly, the same strategy is followed in other
studies; for instance, Rb, Sr, Y, Zr, and Nb concentrations indicated site-specific groups
for prehistoric pottery samples from Florida (Tykot et aL, 2013); Ti, Mn, Fe, Cr, Rb, and Zr
were used to cluster amphorae from Sicily in two groups interpreted as products of differ-
ent manufacturing areas (Barone et aL, 2011); and Rb, Sr, Y, Zr, Nb, Ba, and Th were used
to characterize pottery from the Arabian Gulf (Ashkanani and Tykot, 2013). Previously
established or suspected group structures can be confirmed by pXRF, and it can serve as a
sampling method for invasive techniques. In addition, it can provide chemical confirma-
tion for petrographic groups (Burley and Dickinson, 2010; Daszkiewicz and Schneider,
2011; Papmehl-Dufay et aL, 2013). By the same token, combined mineralogical evidence
and understanding of relevant geological environs can also guide "correct use of compar-
ative geochemical data'': Sr, Rb, and Fe ratios, analyzed by pXRF, discriminated pottery
originating from the Nile Valley (marls and silts) from marine, desert, or volcanic terrain
environs (Morgenstein and Redrnount, 2005: 1618-1623; Emery and Morgenstein, 2007:
113-118).
Non-destructive pXRF may be the only analytical option when in situ analysis is required
or invasive sampling is strictly prohibited. It is often praised for its role in these situations,
but published in situ ceramic analyses, in the field, or at museum sites (Morgenstein and
Redmount, zoos; Bonizzoni et aL, 2013) are rare. In fact, the typical pXRF analysis environ-
ment in archaeology is a laboratory (Goodale et al., 2012: 882-883; Frahm and Doonan,
2013), and undoubtedly, optional invasive sampling (and higher analytical sensitivity) is
often discarded in favor of the accessible, fast, and low-cost elemental analysis offered by
pXRF. However, taking into account that pXRF has limited sensitivity, dimensionality,
and discriminating power in non-destructive application, increased resolution in group
discrimination is dependent upon: (a) prior knowledge of the data structures, and (b)
geochemically distinctive samples; that is, adequate compositional variation is presented
between different compositional groups (see Speakman et al., 2011). Otherwise, it is ques-
tionable whether pXRF analysis alone can provide adequate analytical resolution to iden-
tify archaeologically meaningful ceramic populations (e.g. geologically related, yet distinct
II
day sources in a given region) in relatively homogeneous datasets (see, e.g., Forouzan et al., ,,[!
2012: 3536-3540; Panich and Wilken-Robertson, 2012), an issue that relates to project plan-
ning and sampling strategy, and the need for combined microscopic and higher-sensitivity
techniques.

GLAZES, COATINGS, AND PIGMENTS

Individual phase analysis of multilayered structures, such as glazed ceramics, is impossi-

ble with non-destructive pXRF (li\ai\ez et al., 2007; Bonizzoni et al., 2011), because these
thin layers and microstructures require a beam that can be focused down to a few microns
 HANDHELD PXRF 373

in diameter to allow microanalysis; for example, SEM-EDS or j.LXRF (Charalambous eta!.,

2010; Bezur and Casadio, 2012).1herefore, surface analysis of glazed ceramics is a bulk anal-
ysis of the glaze, its pigments, and the ceramic body. Quantification of these distinct layers is
impossible and identification of pigment elements can also be challenging (Perez-Arentegui
eta!., zooS: 1274-1z79 ). Glaze constituents can disturb the analysis of ceramic body concen-
trations in nbn-destructive analysis even in unglazed areas. Especially in Pb-glazed pottery,
where lead absorption into the ceramic body hinders the detection of other elemental con-
centrations in the measured spectrum, a specific calibration may be needed to extract lead
attenuation effects to Fe, Rb, Sr, Zr, and Nb peaks (Ifiafiez et al., 2007: 383; Forster and Grave,
2013).
Non-destructive pXRF can be a qualitative tool tor pigments or coating analysis: the red
coating of Neolithic pottery from Israel was determined to be Fe-enriched (Biton et a!.,
2014: 744-745); elevated Fe, Sr, Mn, Ti, and Zn levels of Brazilian pottery were interpreted
as indicative of engobe coatings (lkeoka et al., 2012); a variation in Fe and Mn pigments sug-
gested technological change in Cyprian ceramics (Karydas eta!., zoos); and cobalt pigments
were identified in the decoration ofValencian ceramics (Perez-Arentegui et aL, 2008: 1274-
1279).Invasive sampling of complex polychrome structures, for example on terracotta, can
be guided by in situ pXRF tests, although there is still a risk of mixed analysis (Uda et a!.,
2002; Bonizzoni et al., 2011; Colombo et al., 2011).

INTERPRETING DATA

Glascock (zon: 161-172) determined that an analytical method employed in provenance

studies of archaeological materials should facilitate minimum invasive sampling to preserve
maximum artifact integrity, provide fast, accurate, and reproducible data to serve large sam-
ple series, enable analysis of various samples sizes and morphologies, and be sensitive to a
large number of major, minor, and trace elements. While non-destructive pXRF in ceramic
analysis fulfills some of these criteria, it is also limited in many ways. In pXRF, group dis-
crimination is typically based on semi-quantitative values of about five heavy elements, in
contrast to 10-20 major, minor, and trace elements more conventionally preferred in prov-
enance studies. However, non-diagnostic elements in high-dimensional datasets can some-
times blur data structures, and reduced variables may enhance the resolution and pattern
identification (Baxter and jackson, 2001: zs4; Baxter and Freestone, 2006: 524-525; Michelaki
and Hancock, 2011: 1268). Nevertheless, "not all individual elements will have equal value"
in geochemical grouping (Arnold et al., 1991: 295), and although low-dimensional datasets
can indicate production clusters subject to "element specificity;' that is, the selected elements
represent the greatest variability in the dataset, there is a risk that case-specif1c critical provM
enancing elements are not determinable by pXRF (Mitchell et al., zo1z: 2921-z93z). Non-
destructive pXRF may not provide analytical resolution adequate for site-specific sourcing
or to investigate other detailed provenance-related questions, compared with methods with
higher discrimination power, and therefore, research goals and expectations should be for-
mulated accordingly (Speakman et al., 2011: 3495). It is also vital to understand which ele-
ments act as "geochemical signals" of the geological environment when sourcing ceramics
374 ELISABETH HOLMQVIST

(Morgenstcin and Redmount, 2005), especially in non-destructive analysis dependent solely

I
upon chemical data.

II
It is apparent from recent case studies that large sample series, for example, 400-500
specimens, are being analyzed by pXRF (Frankel and Webb, 2012; Tykot et al., 2013). Such
a sample size is normally unattainable in ceramic provenancing, owing to sample prepa~
ration, analysis costs, and antiquities regulations restricting invasive sampling per assem-
blage. More extensive sampling may, in well-justified cases, allow for wider research
perspectives, for example, chronological or intersite comparisons. This requires, neverthe-
~
less, a carefully planned sampling strategy and an analytical method with adequate dis- I
criminating power (Hein et al., 2002: 542) to identify compositionally related, yet different,
ceramics in a large dataset. The purpose of sampling is to provide results that represent
wider populations and phenomena, and this also applies to non-destructive analysis (Smith
I
et al., 2007: 446-447; Millhauser et al., 20n: 3150). In order to formulate archaeologically
meaningful interpretative models of ceramic production, and exchange and related socio-
economic systems, painstaking sample-by-sample evaluation of the compositional, con-
textual, and typochronological datasets is required, and this may not be realistic for these
extensive sample series.
Under-interpretation of ceramics as products of craft technologies and sociocultural
markers is a threat related to non-destructive strategies. Archaeologically speaking, geo-
chemical grouping is a rather narrow thematic perspective that does not consider technolog-
ical details and production characterization, for example, chaine operatoire, specialization,
adaptation, and variation (Rye, 1981; Rice, 1991; Rands and Bargielski Weimer, 1992; Stoltman
et al., 1992; Tite, 1999 ). These concepts, together with source determination, form the archae-
ological core of ceramic provenance studies, and call for a combined approach. At least a
portion of samples analyzed by pXRF should also be microscopically investigated for micro-
structural, mineralogical, and technological characterization (SEM-EDS, petrography), not
least to identify temper-derived elemental concentrations in ceramic fabrics at worst leading
to misinterpretation of data (Bishop et al., 1982: 288; Rice, 1996: 169; Buxeda i Garrig6s et al.,
2001; Buxeda i Garrig6s et al., 2003).
Although writing during the pre-handheld pXRF era, Bishop (1982: 297-289) states that
"as long as the limitations of a particular technique or method are borne in mind in the inter-
pretation of one's data, information that will make a positive contribution can be obtained
from a variety of instrumental procedures;' and it is in this spirit that non-destructive pXRF
is a valuable tool in ceramic compositional studies.

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 CHAPTER 22

PARTICLE INDUCED X-RAY

EMISSION (PIXE) AND ITS
APPLICATIONS FOR
CERAMIC ANALYSIS

MARCIA A. RIZZUTTO AND

MANFREDO H. TABACNIKS

INTRODUCTION

PARTICLE induced X-ray emission (PIXE) is widely used to determine the elemental com-
position of different art, archaeological, and historical objects, characterizing pigments,
ceramics, metals, jewelry, and so on. The analytical results provide information about the
cultural and technological development of the related societies. PIXE analysis can also pro-
vide information of changes due to environmental exposure. In particular, PIXE analysis has
been used to better understand the ceramics discussed in this chapter.
Ceramics are archaeological objects frequently found in large quantities in excavations
and archaeological sites. They represent the accumulation of human experience and knowl-
edge, and therefore ceramics are intensively studied (Childe, 1956; Hayashida, 2003; jones,
2004). Archeometry is the quantitative branch of archaeology. Its major focus, since its
beginning in about 1950 until today, has been the physical and chemical characterization of
ceramics (Swann, 1999; Felicissirno, 2006; Roumie, 2010). The investigations are always very
complex, because ceramics vary in composition, abundance, and manufacturing technol-
ogy. The analytical results help to support the study and archaeological investigations at a site
or in a region, the study of related materials, and the chronology of the archaeological site.

THE PIXE METHOD

The particle induced X-ray emission (PIXE) method was first suggested in 1970 by Johansson
and Johansson (Johansson, 1970, 1976), exploring the energy dispersive analytical capability
 PIXE AND 'iTS APPLICATIONS FOR CERAMIC ANALYSIS 383

of the just released Si(Li) X-ray solid-state detector by analyzing the dust outside the labora-
tory window collected on a thin plastic sheet (Johansson, 1970, 1988, 1995; Woldseth, 1973).
The PIXE method measures the characteristic X-rays emitted by a sample being irradiated by
an ion beam of a few MeV/amu of energy (usually protons or alphas). The PIXE analysis is
very similar to an X-ray fluorescence (XRF) analysis, both measuring cbaracteristic X- rays, but
replacing the primary X-ray excitation of the XRF by an energetic ion beam in the PIXE setup.
While striking an atom, an energetic ion can remove an inner shell electron, leaving the atom
electronically excited. Hence, during de-excitation, the atom can emit characteristic X- rays
(also Auger electrons) revealing the elements within the sample. The characteristic X-rays are
measured by a highly sensitive energy dispersive detector that is able to resolve the X radiation
in its components. The tiny electric pulses at the detector, generated by the detected X-rays, are
amplified, electronically processed, and stored in a multichannel memory, generating a histo-
gram (usually with 512 or 1024+ bins or channels) of the detected radiation, called spectrum.
Owing to the absorption of the X-rays in the entrance window of the detector, PIXE analysis
is usually capable of measuring only elements above Na (Z>n).' The detection limits of the
PIXE technique are very low, of the order of~g/g (ppm), or ro' 4 at/em', which is of the order of
one atomic monolayer. Owing to the high yield of the X-rays in the energy range ofr to 20 keV
produced by ion impact (Johansson, 1970 ),'small samples, to the lower limit of approximately
1 ~tg/cm 2 , can still generate enough X-rays, allowing acceptable minute-long measurements.
For this reason, PIXE is also known for its speed. Broad beam PIXE analysis is used to measure
sample areas of about or lower than o.s cm2 • Nowadays microbeams (with a lower limit of a few
nm in diameter) are used to analyze micrometer-sized samples (Legge, 1997; Salamanca, 2001;
Mesjasz-Przybylowicz, 2002; Calligaro, 2004; Salomon, 2008).
Samples can be analyzed either in vacuum or in atmosphere. Former PIXE analysis took
place in-vacuum setups, but with the developmentofhighly resistant and very thin (less than
1 ~m) exit windows, external beam PIXE analysis is becoming more popular. This allows the
analysis of samples that cannot be placed in vacuum, either because of size limitations, beam
heating sensitivity, or the presence of volatile compounds. In external beam PIXE analysis,
the beam is extracted through an exit window, necessary to separate the ultra-high vacuum
environment of the accelerator from the outer atmosphere where the sample is placed.
Objects of cultural heritage such as paintings, ceramics, bones, and wood samples have been
successfully analyzed on external beam PIXE systems (Grassi, 2004; Constantinescu, 2014).

PIXETheory
The atomic de-excitation of an atom and the subsequent emission of characteristic X- rays
follow a set of quantum mechanical selection rules, resulting in a group of X-ray lines uni-
vocally tied to the emitting chemical element. Moreover, the Moseley law found in 1913
(Moseley, 1914) produced a simple mathematical relationship between the energy of a given
X-ray line and the atomic number of the emitting atom. This enabled a practical method for
the identification of all chemical elements.
To quantitatively relate the number of detected X-ray photons of a given line and the cor-
responding number of atoms in the sample, several experimental parameters have to be
taken into account. The quantitative formulation of the PIXE method is usually undertaken
with the following steps (Johansson, 1970,1976, 1988, 1995).
384 MARCIA A. RIZZUTTO AND MANFREDO H. TABACNIKS

Taking the geometry and parameters described in the drawings of Figure 22.1, the
incidence of n(x,y) ions in a sample will create N X-ray photons of a specific i line, pro-
portional to the number of incident ions and the atomic (or mass) density of the chemi-
cal element j present in the sample. The proportionality factor is called X-ray production
cross-section, axi·
The complete differential PIXE formula is:

Equation 22.1

Q
where - is the fraction of the solid angle seen by the detector, e is its detection efficiency
4n
(including fllters), Pi is the elemental mass density of atoms of kind j in the sample and sup-
posed to be homogeneously distributed in the sample, T(z) is the transmission efficiency (or
attenuation) of the X-ray photons on their path d to the detector, and dxdydz is the elemen-
taryvolume to be integrated over the whole sample.
Referring to Figure 22.1, the output path, d, can be written as a function of the x-coordinate
along the beam direction:

do cos a= x o cos<p Equation 22.2

The transmission efficiency of the X-ray photons inside the sample is given by the exponen-
tial attenuation law (ICRU, 1980 ):

T = : exp(f1,d) Equation 22.3

0

where 11, is the mass attenuation coefficient of the i X-ray line, due to all the elements in the
sample. Since the ions lose energy along their incoming path in the sample, it is necessary
to compute the X-ray production cross-section that depends explicitly on the ion energy,
and also the self-absorption of the X-rays, which depends on the absorption distance, d.

Detector
e filtro

filt~ ,,/1~-- .........../t

/n
sample

L .
FIGURE 22.1 Parameters and coordinates of the experimental PIXE geometry. (Reprinted
with permission Tabacniks, 2005.)
 PlX.E AND lTS APPLICATIONS l'OR CERAMIC ANALYSIS 385

The stopping power, S(E), is used to convert the x coordinate into an "ion energy coordinate"
(Ziegler, 1985):

S(E)~ dE Equation 22-4

dx

With the appropriate substitutions, the PJXE Equation 22.5 is obtained:

-~~o:;gf· K "
pcosa S(E")
[l Q p 1 N.0 IE (5 (E')•e ,,
N.~-e
1 1
"' dE' Equation 22.5
47t qoeocOSlp p Aj Eo S(E')

where E0 is the initial energy of the beam, e is the elementary charge, and QI q • e measures
the number of incident ions of charge state q once its integrated charge Q is given.

In Equation 22.5, the termexp

-11 ' cos cps" -(
dE" )
-) is derived from the exponential attenuation
( P cosa E, S E"
law due to self-absorption of the X-rays in the sample. It can be neglected if the sample is
thin enough, usually with a mass density lower than 1 mg/cm' (Tabacniks, 1983). In this case,
the energy change of the incoming beam can also be neglected, and the integral turns into a
simple multiplication, with the cross~ section taken at the initial beam energy, £ 0 •

1
N - [l e a (E0 ) · p h
~- 4n; q·e·coscpAi x, i Equation 22.6

Equation (22.6) can be simplified once more, grouping all experimental and geometrical
parameters, and defining the thin target yield y,1 of a particular PIXE setup:

y.~-e.
[l 1 N0 a (
E0 )
' 4n 1
qoeacosq>A. x, Equation 22.7
I

Equation 22.7 describes the sensitivity of a specific PIXE setup. Combining Equations 22.6
and 22.7, the resulting equation (Equation 22.8) is the working equation of a PIXE setup:

N, ~ Y;; •Q•(P, ·h) Equation 22.8

Equation 22.8 reduces Equation 22.6 into a simple multiplication proportionality formula
that relates the number of detected X-ray photons with the chemical element surface mass
density p1h usually in [ng/cm'], and the integrated charge of the ion beam Q.
Figure 22.2 shows a typical thin film yield curve of the Sao Paulo PIXE system, using
a Si(Li) X-ray detector with a 55 ~m thick be filter. The thin film yield can be calcu-
lated from first principles, for example Equation 22.7, or obtained experimentally (the
circles in the plot), analyzing thin film standards of selected elements and inverting
Equation 22.8.
386 MARCIA A. RIZZUTTO AND MANf1REDO H. TABACNIKS
----·•w••··~•••W•~·-

l
High
+
energy
"'
0

~
E
0
+
s
>- 0.1
0

Low energy
0

10 20 30 40 50
Atomic number

FIGURE 22.2 Typical thin fihn yield curve of the Sao Paulo PIXE system with a Si(Li) XRay
detector and a 55 ~m thick beryllium X· ray filter. (Reprinted with permission Tabacniks, 2005.)

In thick target analysis, both the beam energy loss and the X-ray self-absorption must be
computed. Taking the PIXE Equation 22.5, the thick target PIXE yield now looks like:

-·jjCOSipJE' c/1!"
Q a '(E')
Y~-£
N
'J
E
x.
' 4n 'q·e·cosrp A e, O'x;(e,)
e
S(E')
pcoso:' lioS(£7)
dE' Equation 22.9

where, as before, S(E) is the ion stopping power in the sample, ~' is the matrix absorption
coefficient for a particular X wray, both calculated using Bragg's rule (Leighton, 1959) and the
angles a and 'Pare defined in Figure 22.1. The thick target yield Y, as defined by Equation 22.9
is a function of the stopping power and the mass absorption coefficient, which ultimately
depend on the target composition which is unknown. Therefore, an interactive optimization
routine is needed to calculate target composition, and the elements not detected by PIXE
must be guessed or measured in some other way.
Thick target PIXE analysis is done by integrating explicitly Equation 22.5 with the aid of
dedicated computer programs such as Clara (Aburaya, 2005, 2006) or by using the renowned
GUPIXWIN software, used around the world to fit and calculate PIXE spectra from thin,
thick, intermediate, and layered specimens (Campbell, 1984, 2010).

THE LAMFI-USP LABORATORY

The Laboratory for Material Analysis with Ion Beams of the University of Sao Paulo (LAMFI·
USP) (LAMFI, 2014) was set up in 1989 with the objective to develop, implement, and make ion
beam analysis techniques available to the USP community, similar to other laboratories around
the world (Chiari, 2002; Abraham, 2004; Dran, 2004; Salomon, 2008). LAMFIWUSP includes a
pelletron tandem electrostatic accelerator (National Electrostatic Company US, model5SD H)
 PIXE AND ITS APPLICATIONS FOR CERAMIC ANALYSIS 387

FIGURE 22.3 Top left: General view ofLAMFI with the ion sources on the right and the
sSDH accelerator tank in the center. Top right: Close view of the three analytical setups at
LAMPI, with the external beam setup in the foreground. Bottom left: Detailed view of the
in-vacuum PIXE analysis setup. The vertical cylinders are the liquid nitrogen containers to
refrigerate the Si(Li) detectors to -196°C. Bottom right: External beam setup being adjusted
by Dr. Rizzutto on a test pattern with different color pigments.

that can reach voltages up to 1.7 MV. Attached to the accelerator on one side are two negative
ion sources: a SNICS II mainly for proton beams, and an Alphatross source for alpha beams,
and on the other side three experimental setups, two for in-vacuum PIXE, Rutherford back-
scattering (RBS), elastic recoil detection analysis (ERDA), and nuclear reaction analysis (NRA)
(Tesmer, 1995), and one external beam setup for in-air ion beam analysis. In the current config-
uration the accelerator can provide proton beams and alpha particles, respectively, with ener-
gies between o.6 and 3-4 MeV and o.6 and 5.1 MeV. The maximum beam current on the sample
is of the order of a few hundred nA. Figure 22.3 shows a general view of the LAMFI with the ion
sources on the right, the accelerator in the center, and the analytical stations in the back.

THE ExTERNAL BEAM SETUP AT LAMFI

The increasing need for the analysis of vacuum-incompatible or oversized samples of paint-
ings, archaeological objects, and ceramic samples led to the development and installation
 .,
Mr\RCfA A. HJZZUTTO AND MANFREDO H. TABACNIKS
I
of an external beam setup at LAMPI, where the ion beam is extracted through a thin exit
I
window and driven to the sample in air (Rizzutto, 2005; Lima, 2011). The beam exit window
at LAMFI is presently a zmm diameter, 7~m thick AI foil. Thinner foils, such as zoo nm thick
SiN or Si3N 4 , can also be used (Calligaro, 2002, 2oo8; Mesjasz-Przybylowicz, 2002). Since a
3 MeV alpha or proton beams can survive only a few centimeters in air, the setup needs to be
tight, keeping all ion and X-ray travelling distances as short as possible. In spite of its thick-
ness, the AI window is of advantage, since it emits characteristic gamma rays that can be used
to measure indirectly the beam current used to normalize the spectra.
Besides the X-ray emission, several other processes can take place during the sample irra-
diation, and can be used to better characterize the sample under analysis. Ion back-scatter-
ing, also known as Rutherford backscattering (RBS) can be used to measure light elements
unseen by PIXE. Visible light emission can be used to obtain chemical information of the
target. Gamma-ray detection can extend the analysis to sub-ppm levels on selected ele-
ments. These complementary data require using detectors that are more suited to detect the
different signals emitted by the sample. Each detector has its specific use: particle detectors
for RBS measurements, HPGe and Nal detectors for gamma rays, optical spectrometers for
visible light (ion beam luminescence) (Homman, 1994; Pie], 1996; Yang, 1997; Brooks, 2002;
Quaranta, zooS; Ruvalcaba-Sil, 2oo8; No una et al., 2013).
A sample positioning system using lasers or a webcam completes the assembly, and is used
to point the spot under analysis on a sample. The external beam setup of LAMPI is shown in
Figure 22-4 with all the detectors used to do the complementary IBA analysis.

FIGURE 22.4 The external beam setup at the LAMFI with the different detectors assem-
bled. The lower part of the figure shows in detail the assembly of the coupled detectors.
 PIXE AND ITS APPLICATIONS FOR CERAMIC ANALYSTS 389

THE CERAMIC OBJECTS

The archeometrical and archaeological studies of ceramics are always very complex because
of the variation of the composition and the very high abundance of fragments of ceramic
objects that are found in archaeological sites and manufacture. All this information assists in
the interpretation of the studies of a site, region, and chronology.
The physical-chemical characterizations of the ceramic objects allow us to highlight
aspects of culture, livelihood, trade, and technological development of the human groups
who previously inhabited· a region. The macroscopic characteristics of ceramics, such as
their shape and decoration, are often used as chronological and cultural indicators. However,
the determination of microscopic factors such as the chemical and mineralogical composi-
tion can be applied to the provenance study of these materials, as well as the technology used
in its manufacture (Bao- Ping, 2009 ).
The main purpose of the physics applications to the study of ancient ceramics is to con-
tribute to the reconstruction of their life-cycle from production to distribution and use.
And thus it helps in interpreting the reconstruction of the characteristics of the people
involved.
Reconstructing ceramic production technology involves firstly determining the prepara-
tion of basic materials and how they were used. Finally, questions relate to how the ceramics
were formed, as well as how the surfaces were treated, decorated, and fired. Scientific investi-
gations into the use of a particular ceramic vase primarily involve the examination of surface
fouling, pigments, and organic waste, both on the surface and absorbed into the body of the
object.
Distribution studies or sources of the ceramics try to establish, through the basis of their
chemical composition, where the objects were produced or imported from, and if possible,
to identify the center of production and/or determine the source of the basic material used.
The subsequent interpretation of the life-cycle of ceramics involves consideration of issues
such as the mode of production, possible reasons for the technological choices used in pro-
duction, and sale or exchange.
In order to answer these questions, it is necessary to take into account the archaeologi-
cal context in which the ceramics were produced, distributed, and used. More than that, an
ethnoarchaeological study of ceramics is needed, involving direct observation and studies
of archaeologists to discover the variability in production, distribution, and use of ceramics
among societies.
Thus, the ceramics are related to specific groups of production, which, in turn, are cor-
related with their respective origins, and with these objectives in mind we study a specific set
of ceramics belonging to the collection of the Museum of Archaeology and Ethnology of the
University of Sao Paulo (MAE-USP) (MAE, 2014).

The Chimu Collection of the MAE-USP

The pre-Hispanic cultures were very productive in the arts through the production of metal
and ceramic artifacts. The pre-Hispanic Andean culture is divided into four periods: initial
390 MARCIA A. RIZZUTTO AND MANFREDO H. TABACNIKS

(1800-900 BC), primary (120 BC-550 AD), medium (550-900 AD) and late (900-1532 AD),
and is found in various regions in South America.
The Chimu culture (800-1476 AD), located in northern Peru, developed during the late
period in the same territory as the Moche (or Mochica) culture (100-750 AD) and possi-
bly before the Cupinisque culture (10oo-zoo AD) was established. 1he main cultural city
was Chan Chan, covering an area of over 20 km 2 located in the Meche River located near
the coast ofTumbes in northern Huarmey valley near the Andes. During the Chimu period
there was great social and political development with two distinct phases: the first related to
a small group located in the Moche Valley and surroundings, the second related to an exten-
sive dominion called "Kingdom ofChimor" (Keatinge, 1973: Moseley, 1990).
What is known today about the lifestyle of the Chimu culture is related to what has been
assigned by the discoveries of objects of art, architecture, and ceramic vessels excavated
in archaeological sites. The Chimu ceramics express the level of technical development
and production of this culture and are a witness of this rich culture. The typical ceramic
objects of this culture exhibits a very dark color that is obtained by heating in a reducing
atmosphere combined with polish, probably done by hand, fingers, and stone. These ceram-
ics are equivalent to those found in the Moche culture (Swann, 1999) and the Sican culture
(Lambayeque-750-1350 AD), which show ancient symbols of the Moche and Cupinisque
cultures but with new elements. The Chimu ceramics were produced in large quantities from
molds with different finishing levels and polish, and also with an engobe material in the sur-
face. They have different functions, such as daily use (domestic) and ceremonial. The Chimu
culture introduced the use of specialized or vertical molds, with the body and neck of the
ceramics mounted and the stirrup-spout bottle type decorated with anthropomorphic fig-
ures representing characters and/or animals such as monkeys, birds, and so on, molded in

FIGURE 22.5 Chimu ceramics at the Museum of Archaeology and Ethnology of the
University of Sao Paulo (MAE-USP) collection. (Photograph: W. Souza Silva)
i'f

PIXE AND ~TS APPLICATIONS FOR CERAMIC ANALYSIS 391

one body. The most common ceramics of this culture are bottles with whistling chambers, as
shown in Figure 22.5.
The main raw material of ceramics is clay with its specific properties, such as plasticity,
color, and porosity. Some cultures, aiming at modifying the strength or weight of ceramic
vases, mix the clay with some spices (tempers) of different materials such as mineral or
organic elements (sand, calcium carbonate, vegetable matter, and even the ceramics them-
selves ground into thinner pieces).
The PIXE technique was used in order to identify major and minor chemical elements of
the set of 36 ceramic vessels from the pre-Hispanic Chimu Culture Collection at the MAE-
USP (Lima, 2010, 2011) '!be analysis supported the determination of the correlation between
them and their separation into groups.

The PIXE Measurements of the Chimu Ceramics Collection

The PIXE measurements were performed with the LAMFI-USP arrangement of an exter-
nal beam with a Kaptono of 25~m as a window to the outside atmosphere. '!be spectra were

(a) Energy (MeV} Energy (MeV)

0 002 0 004 0006 0 008 ,_,0.010 ~~2

I~ ~
3.0
8 ' 3601
~ 2.5
~
·o 2.0
<
~

.~
1.5 ~
1
~

"6 ~

<~
z 1.0

6
0.5

0.0
~~~ A:I
400 500 600 100 200 300 400 500 600
Channel Channel

3635 3601

--sup.l
(b) AI --sup.l
sup.2 AI sup.2
--inner
- - inner1
- - inner2

Cc s Cc s

FIGURE 22.6 (a) PIXEspectra oftwo ceramic vessels (3635 and 3601) of the Chimu culture;
(b) comparison of the concentrations values obtained by PIXE at different points, analyzed
in the two ceramic pieces.
392 MARCIA A. RIZZUTTO AND MANFREDO H. TABACNIKS

obtained with a proton beam of ~2.2Me V approximately and o.snA current for 6oo seconds
of irradiation. Two Si-PIN detectors were used in this outdoor setting: one with 16oeV@
MnKa was used to record the X-rayfrom the sample analyzed, and the second one for moni-
toring the beam dose.
With the PIXE analysis it was possible to measure the concentrations of elements Al, Si, P,
S, Cl, K, Ca, Ti, Cr, Mn, Fe, Cu, and Zn in the ceramic objects. Typical PIXE spectra obtained
for two vessels (3635 and 3601) are shown as examples in Figure 22.6a.
PIXE measurements were performed at various points of the vessels to identify the
elements in the ceramic paste (inner) and outer surface (suf). The elemental concentra-
tions were obtained using charge beam correction and the thin target yield obtained to the
external beam setup. These concentrations can be affected by inhomogeneity of the clay,
but the values obtained for the different points in each sample show a strong similarity
(Figure zz.6b).

(a) 2.0

1.5

1,0

~.,
0.5

i-i o.o
il
& -0,5 \
3589
-1,0 3590
3591
3592
3620
3621
0 3629 4
104c
36Hl
3631
3635
:J637
(b) 2.5

2,0

1.5

1,0

~
,;
0.5

;.; 0,0
£
J.<! -0,5 • ~ 104-c
35$9
-1,0 3590
3591
3592
-1,5 3618
3620
3621
3629
3631
0 3 3635
3637

FIGURE 22.7 (a) Graph of the correlation between Al, Si, K, Ti and Fe elements giving rise
to 4large groups; (b) graph of the correlation between Al, Si, K and Ti elements, suggesting
the origin of three major groups.
 PIXE AND ITS APPLICATIONS FOR CERAMIC ANALYSIS 393

Group A
,~~CC'

itJ/d~
j,,~,.

'

3629

PIXO JSJl

PiXE 3627
no AI

3562 X277

PIX£ JS26 PIXE !04b

'" " "

FIGURE 22.8 Sun ray plots of the elements Al, Si, K, and Ti showing the correlations in the
groups and the respective vessels in each group.
 l
394 MARCIA A. RIZZUTTO AND MANFREDO H. TABACNIKS

The PIXE concentrations ~g/cm') were obtained for the 13 elements AI, Si, P, S, Cl, K, Ca,
Ti, Cr, Mn, Fe, Cu, and Zn of the surface (suf) and the inner part (inner) of the points ana-
I
lyzed for each ceramics examined. The elementary standard deviation is ±10% for Al, Si, Ti,
and Fe in surface and ±45% and ±6o% for Cu and Zn in the inner parts, respectively. For the
other elements the uncertainty varied on average ±20% in the surface and± 30% in the inner
part. It was clearly observed that the standard deviations are greater in the inside than on the
surface.
The elemental concentrations obtained with the PIXE technique were used in two mul-
tivariate statistical methods, principal component analysis (PCA) and hierarchical cluster
analysis (HCA), which are often used to examine clusters and determine similarities and
correlations among samples (Yap, 1990; Zhua, 2004; Papachristodoulou, 2006). The PCA
analysis showed that Sand Ca are correlated. There is also a correlation between Al, Si, K, Ti,
and Fe, thus it is possible to separate the pieces into four groups (Figure 22.7a). Considering
the elements Al, Si, K, and Ti in the PCA analyses (Figure 22.7b), the coupling between the
vessels can be better seen.
The dendrogram for hierarchical clustering obtained for these samples shows a strong
correlation among the elements K, Fe, Ti, Si, and Al, confirming the above discussion. Ca
and S have the same correlation in the PCA and HCA analysis. The grouping analysis by
dendrogram applied to all samples divides them into two groups: A and B. Group A has the
correlation of the elements K, Fe, Ti, Si, and Al where the B group can be subdivided into two
subgroups: B1 (Zn, Cu, Mn, and Cr) and B2 (Ca, S, Cl, and P). The group Bz also has the sub-
division BzA (Ca and S) and B2B (Cl and P).
1be elemental composition multivariate statistical analysis using PCA and HCA showed
the statistical correlations and similarities between samples. PCA showed a high correlation
among the elements AI, Si, K, Ti, and Fe, and allowed assignation of the samples to different
groups. The same robust correlation among these elements was also observed in the HCA
analysis applied to these samples. The vessels belonging to each group are also represented
by the sun ray plots of the elements AI, Si, K, and Ti in Figure 22.8.

CoNCLUSION

Non-destructive elemental characterization methods, such as PIXE, cover a set of analyti-

cal techniques that can be very useful in the interface between physics and cultural heritage,
being capable of assisting the social scientist, the archaeologist, or curators better character-
izing historical and artistical objects. 1bese methodologies are also an important subject of
research by themselves, being continuously improved to better support and aid the social
scientist to study and understand modern questions in cultural heritage research. Physical
methods for the characterization of ancient or artistical objects can bring new informations to
aid the comprehension of common problems in museum collections ranging from the effect
of storage conditions and environmental contamination to guiding restoration works or the
comprehension of the creation process and its comprised technology. The fruitfull collabora-
tion of scientists from different areas and the need of mutually understanding different sci-
entific languages also offer exciting opportunities for the development ofhuman knowledge.
 PIXE AND ITS APPLICATIONS FOR CERAMIC ANALYSIS 395

ACKNOWLEDGMENTS

This research is supported by the State of Sao Paulo Research Foundation (FAPESP) and
the Brazilian National Counsel of Technological and Scientific Development (CNPq). The
authors are indebted to the Museu de Arqueologia e Etnologia MAE-USP for providing
access to the Chimu vessels collection, Fernando Meloni for the statistics, and Silvia Cunha
Lima on interpreting the PIXE analysis. The LAMFI-USP technical team is acknowledged
for experimental support during analysis.

NOTES

1. There are detectors with ultra-thin windows, or windowless, that are able to measure ele-
ments with Z<n, mostly used in special applications.
2. The sensitive region of solid-state X-ray detectors.

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 CHAPTER 23

INDUCTIVELY COUPLED
PLASMA-MASS
SPECTROMETRY
(ICP-MS) AND LASER
ABLATION INDUCTIVELY
COUPLED PLASMA-MASS
SPECTROMETRY (LA-ICP-MS)

MARK GOLITKO AND LAURE DUSSUBIEUX

INTRODUCTION

CERAMIC provenance studies are, in effect, cultural/technological and geological studies.

Rarely can the actual geographical boundaries of a "source" be delimited with precision.
Instead, pronouncing a sherd "local" or "non-local" is a probabilistic statement reflecting a
variety of potential criteria, including: knowledge oflocal geochemistry and mineralogy; the
likelihood of observing a similar compositional profile in sherds produced elsewhere; how
far from a particular location people are likely to travel to obtain their raw materials (e.g.
Arnold's (1985) "primary exploitation threshold"); how frequently represented particular
ware types or chemical types are at a given location versus elsewhere (the "criterion of abun-
dance"); cultural-technological choices such as clay preparation and vessel use; and post-
burial changes that may impact observed sherd composition.
Many ceramic provenance studies rely on techniques such as instrumental neutron acti-
vation analysis (INAA) or X-ray fluorescence (XRF) to generate bulk compositional data.
Inductively coupled plasma-mass spectrometry (ICP-MS) was first used by archaeologists
interested in finding a lower cost, more widely available alternative to INAA during the early
to mid-1990s (e.g. Burton and Simon, 1993: Tykot and Young, 1996). However, the major
contribution of ICP-MS to archaeological ceramic analysis is more recent; the use oflaser
ablation (LA) sample introduction to produce spatially resolved chemical information to
400 MARK GOLITKO AND LAURE DUSSUBIEUX

supplement mineralogical or bulk chemical analysis. Elemental "mapping" and phase analy-
sis by LA-ICP- MS facilitates identification of the underlying chemical structure and miner-
alogy of a ceramic and which geological, cultural, technological, and/or post-depositional
processes account for the variation observed in bulk chemical studies. Several other analyti-
cal techniques offer spatially resolved imaging and analysis-electron probe microanalysis
(EPMA) and scanning electron microscopy with energy dispersive spectrometry (SEM-
EDS) for example-but these techniques have relatively high detection limits and cannot
typically measure elements present at very low concentrations that are often of interest in
ceramic compositional studies. LA-ICP-MS has consequently emerged as the preferred
technique for targeted analysis of archaeological ceramics owing to the wide range of ele-
ments it can measure, low detection limits, and minimal destructiveness.
In this chapter, we review the basics ofiCP-MS, liquid and solid sample introduction,
mass spectrometer types, and discuss data quantification appropriate for ceramic analysis.
Next, we examine applications and advantages of!CP-MS for archaeological ceramic stud-
ies, including a critical review of paste characterization by laser sampling, and conclude with
a case study from the Sepik coast of Papua New Guinea that highlights some of the potential
advantages of the technique. We emphasize that ICP- MS analysis is most valuable as part of a
combined study incorporating bulk chemical and mineralogical characterization in concert
with targeted analysis by LA-ICP- MS.

BASICS OF INDUCTIVELY COUPLED PLASMA-MASS

SPECTROMETRY (ICP-MS)

An inductively coupled plasma-mass spectrometer measures ions separated by an arrange-

ment of powerful magnets according to their mass to charge ratio (m/Z) (Thomas, 2013). The
ions are generated (i.e. the sample is ionized) by preparing the sample as an aerosol, a colloid
suspension in gas, and passing that aerosol through a superheated plasma that strips elec-
trons from the atoms (Figure 23.1).
For the purposes of ICP-MS, a plasma can be understood as a super-heated ionized gas
consisting of positive ions and free electrons in proportions creating a roughly neutral elec-
trical charge. Plasmas used in spectrochemical analyses should be formed from an elemen-
tal gas that has a high ionization energy but is minimally reactive, enabling it to efficiently
ionize most other elements while at the same time preventing the formation of oxides or
poly atomic species that can interfere with the detection/quantification ofions with identical
masses. Argon (15.76 eV) is typically the gas used to create plasmas for ICP-MS, reaching a
temperature of about 10,ooo K. Only four elements, H, He, F, and Ne, have higher ionization
energies than Ar and, while these cannot be measured using an Ar plasma, some of these
elements (Fin particular) are of analyticalutilityin archaeological studies (Ammann, 2007).
Ne plasmas have been tested, but their use results in lower sensitivity than when using Ar
(Petibon et al., 2002), while He is substantially more expensive than Ar.
To create the plasma, Ar gas is introduced into a torch consisting of three concentric
quartz tubes, surrounded by an induction coil linked to a radio-frequency (RF) generator
that produces an alternating current in the gas. A spark is applied to introduce free electrons,
----------------

ICP-MS AND LA-ICP-MS 401

Nd:YAG laser
He canister and focusing
camera
Liquid
··~·-·
Mass spectrometer
auto-sampler
laser control de'.!
software

FIGURE 23.1 An ICP-MS laboratory, with both laser ablation and liquid sampling equip-
ment visible. (Photograph: Photo by Laure Dussubieux.)

which are rapidly accelerated via the electromagnetic field induced by the RF generator and
coiL These electrons collide with Ar atoms, ionizing a small percentage of them to form the
plasma (Figure 23.2). When the sample aerosol is introduced into the plasma, it collides with
electrons removed from Ar atoms in the plasma and is ionized into positive elemental ions
and more free electrons.
The resulting ion beam is then passed through a series of cones with narrow apertures that
facilitate coupling between the relatively low-vacuum ( -IXw' Pa) high-temperature condi-
tions in the plasma chamber and the very-high-vacuum conditions (~1x10- 4 Pa) in the mass
spectrometer. The ion beam then passes through positively charged electrostatic ion lenses
situated just past the cones, which focus the beam and remove photons and electrons that
would otherwise generate background noise if they reached the detector. Some instruments
also feature collision cells or other optics that remove polyatomic species or other unwanted
constituents from the ion beam, reducing background noise, although at the loss of signal
strength (Ammann, 2007; Thomas, 2013). After passing through the mass spectrometer (see
the section "Mass Spectrometer Types"), ions collide with a detector, usually a Faraday cup,
and are measured as electrical current.
Plasma-ion sources have existed for decades; however, previous generations of ICP
instruments used atomic emission or optical emission spectroscopy, ICP-AES and ICP-OES
respectively, to measure the characteristic light emitted by atoms excited by the plasma rather
than directly measuring the ions themselves. The benefits of using mass spectrometry over
AES and OES instruments, particularly for cultural materials studies, include lower limits of
402 MARK GOUTKO AND LAURE DUSSUBIEUX

(a) Detector

------·------I
(b) (c)

···---~-----. ----~agnets

~~"
Skimmer and
sampler cones
Plasma torch Plasma j -~
·····-u------------------···.······flt'fl.
tt
Argon Gas
Rf coil
1 II!' Exit slit

Detectors
Detector
(d)
Detector
·····t············--·---:c==
Q\=
rn'
\,/
=
=
= \/~
=
FIGURE 23.2 Schematic diagram of plasma-ion source and common mass spectrometer
types: (a) quadrupole; (b) single-collector magnetic sector; (c) multicollector magnetic sec-
tor; (d) time-of-flight. Dashed lines represent the path of the sample aerosol or ion beam.
( © Mark Golitko.)

detection, a broader range of detectable elements, and perhaps most importantly, the abil-
ity to more rapidly generate usable signal measurements. This last characteristic means that
ICP- MS instruments can generate data reliably using smaller sample volumes, reducing
potential damage to objects while also allowing measurement of very small sample areas.
Commercial ICP-MS units were first marketed in 1983 and have become fairly standard
instrumentation in geological> chemical, and environmental testing laboratories since then
(Ammann, 2007). ICP-MS was first used for archaeological material studies during the 1990s
to study elemental concentrations in obsidian (e.g. Tykot and Young, 1996) and archaeologi-
cal ceramics (e.g. Burton and Simon, 1993).

SAMPLE INTRODUCTION

Samples must be introduced into the ICP- MS in the form of a fine aerosol, ideally with par-
ticles less than wo nanometers (Guillong et al., 2003). The two principal methods for creat-
ing an aerosol from the sample material are by dissolving it in liquid or by removing a small
portion of the sample with a laser to produce fine particulate matter.
 ICP-MS AND LA~ICP-MS 403

Liquid Sample Introduction

Liquid sample introduction involves powdering solid samples, dissolving them in an acid,
and introducing the resulting solution into the ICP-MS, via a nebulizer, as a constant con-
trolled stream of aerosol. Two of the major advantages ofliquid sample introduction are pre-
cise control of input volume and flow, and the ability to produce a truly representative bulk
characterization of a sample by powdering a relatively large volume of material. However,
liquid sample introduction has a serious disadvantage; the sample must be readily soluble
in acids. Ceramics, like most aluminosilicates, are very difficult to put into solution, often
requiring the use of caustic and expensive acids to achieve full dissolution. Early attempts
at weak acid dissolution of archaeological ceramics using 1-molar hydrochloric acid (HCl)
(Burtoh and Simon, 1993; Nieves Zedei\o, 1994) proved problematic because the acid bath
differentially extracted elements depending on initial composition, firing temperature,
temper type and abundance, and post-depositional mineralogical alteration of the ceramic
material. Consequently, it proved difficult to ensure that weak acid extraction of ceram-
ics was consistent and reproducible for a single sample, let alone across an assemblage or
between laboratories. As a result, the chemical composition of ceramics determined by weak
acid extraction ICP-MS was difficult to interpret and unhelpful with regard to provenance
determination (Neff eta!., 1996; Triadan eta!., 1997; cf., Burton and Simon 1996), precluding
the establishment of weak acid extraction as a reliable technique for analysis of archaeologi-
cal ceramics by ICP-MS.
More aggressive acid dissolution regimes can consistently extract the elemental composi-
tion of archaeological ceramics and have been demonstrated to be effective and reproduc-
ible for their bulk chemical characterization (e.g. Clark and Kennett, 2009). Tsolakidou eta!.
(2002) evaluate several approaches for archaeological ceramics in their study, such as diges-
tion in open vessels using hydrofluoric and hydrochloric acid, alkali fusion, and microwave
digestion. While they achieved good recovery rates for most elements, their experiments
indicated low recovery rates for important trace elements, including zircon and most rare
earth elements (REEs), which are often contained in acid-resistant mineral phases included
in the ceramic fabric. By adding boric acid to the microwave digestion routine described by
Tsolakidou eta!., Kennett eta!. (2002) were able to improve recovery rates for many elements
including the REEs, and this method has proven effective for bulk chemical characterization
of ceramic materials.

Laser Ablation
Laser ablation sample introduction was first developed by geologists interested in
analyzing mineral phases that were small and difficult to dissolve into solution (Gray,
1985; Fryer et a!., 1995), and is now the most widely used sample introduction method
for archaeological studies. In laser ablation ICP-MS, a beam of coherent light is used to
remove small particles of sample which are then swept along in a carrier gas, typically He.
The beam width can be varied to between about 5-100 microns, and penetration depth
can be controlled by ablating for different durations depending upon the composition of
the sample or phase of interest. For instance, analysis of surface treatments such as glazes
or slips can be achieved by rapidly scanning the laser. LA-ICP-MS is often considered
404 MARK GOT.TTKO AND LAURE DUSSUBIEUX

quasi-non-destructive because, while the sample is being ablated, the damage is invisible
to the naked eye.
A variety of laser types can be used for LA-ICP-MS, most commonly 266 or 213 nm
neodymium doped-yttrium aluminum garnet (Nd:YAG) lasers; although newer argon
fluoride (ArF) excimer and solid-state lasers operate at 193 nm wavelength. Shorter-
wavelength lasers are desirable because they help reduce fractionation, an effect noted
during early applications oflaser ablation when longer wavelength lasers (~woo nm) were
employed. In ICP-MS, fractionation refers to any process that results in differential effi-
ciency of ablation, transport, and/or detection of elements, usually because of differen-
tial elemental volatility during melting, and is principally an effect of aerosol particle size
(Chen, 1999; Eggins et aL, 1998). Shorter-wavelength lasers produce smaller, more uni-
formly sized particles during ablation than longer-wavelength lasers and, as a result, result
in lower fractionation (Gonzalez et aL, 2002; Guillong et aL, 2003). Shorter-wavelength
lasers are also less affected by differences in sample density and opacity and, therefore,
are more consistent in ablation efficiency across different matrix types, which is a criti-
cal component of matching standards to archaeological materials for calibration purposes
(Gaboardi and Humayun, 2009 ).
Commercially available LA-ICP-MS spectrometers used in archaeology are similar to
those first developed and reported by jackson et aL (1992), combining a laser for ablation
with a magnifying microscope or camera that allows targeted focusing of the laser on areas
as small as a few microns. A motorized stage also facilitates precise positioning of the laser,
and sampling either creates craters ablated downwards through the material or lines ablated
across the surface of a sample. Consequently, laser ablation can be effectively used for either
depth-profiling; for instance, by drilling down through a multilayer surface treatment, or to
sample only the first few microns of glaze, slip, or paint
Although laser ablation can be described as quasi-non-destructive, most ablation units
require that the sample fit in a chamber that can be purged of ambient air, which can induce
fractionation if present (Kasler et aL, 2002). Consequently, even laser ablation sampling
requires that samples be relatively small, on the order of a few em in maximal dimension.
For ceramic sherds recovered from active excavations this may not be an issue; however, for
analyses of complete vessels and/or sherds in museum collections, for instance, it may be a
problem (Giussani et aL, 2009). Large ablation cells have been developed by some laborato-
ries, as well as "open~cell" designs to accommodate the special needs of cultural history and
archaeological applications. Open-celllaser units either use a small volume cell that is sealed
onto the sample surface, or an annular argon gas flow to remove ambient atmosphere with-
out requiring physical contact with the sample surface. This latter method has been used
for archaeological ceramic studies, facilitating analysis of complete vessels; however, sample
throughput is typically much slower using an open-cell unit than with conventional closed-
cell designs (e.g. Wagner and j~dral2on).

MASS SPECTROMETER TYPE§

Several types of mass spectrometers may be used to sort ions according to mass and charge.
The most common spectrometer used for archaeological applications is the quadrupole
 ICP-MS AND LA-ICP-MS 405

mass spectrometer (Figure 23.2a), which consists of four parallel rods connected to vari-
able currents generating an adjustable magnetic field that allows only one m/Z ratio through
to the detector at a time. Quadrupoles sweep through the complete mass/charge range in a
matter of seconds in order to measure the widest range of elements in the sample, but con-
sequently, measurements on individual elements do not reflect simultaneous ablation at the
sample surface. When very small features are analyzed (which are thus rapidly vaporized by
the laser), measurements on loW'~ and high- mass elements may not correspond to the same
feature of interest.
Quadrupoles also have relatively low mass resolution (ability to resolve small dif!erences
in m/Z ratios), and can suffer from mass-spectral interference for isotopes of different ele-
ments with similar m/Z ratios and because of the formation of polyatomic ions. For instance,
6
4o Ar' 0 interferes with the detection and quantification of 56Fe, the most abundant isotope

of Fe, because of their similar mass (55-9349 u vs. 55-9573 u) (May and Wiedmeyer 1998).
However, most quadrupole instruments are able to overcome these weaknesses by generat-
ing high signal strengths for elemental isotopes that suffer from less interference (e.g. 57 Fe).
Quadrupoles are of great utility for chemical characterization of ceramic pastes, glazes, slips,
paints, and individual inclusions/phases because they are able to measure a wide range of
elements quickly and efficiently.
Another common spectrometer is the magnetic sector field ICP-MS. 1bese instruments
use a magnetic field to bend ions through a curved path with a different radius for each m/
Z ratio/ion of interest. One ion at a time is directed toward the appropriately positioned exit
slit placed before the detector, determined by the force of the magnetic field. Sector field
instruments can be either single collectors for non-simultaneous measurement of ions of
different masses (Figure 23.2b) or multicollectors (Figure 23-2c), in which several detec-
tors allow simultaneous measurement of ions of different masses. Magnetic sector ICP- MS
(MC-ICP-MS) is also referred to as high-resolution ICP-MS (HR-ICP-MS) because it has
superior resolving power compared with quadrupole instruments. The high mass-resolu~
tion achievable with these detectors eliminates many isotopic interferences, making them
ideal for isotopic measurements (White et al., 2ooo; Vanhaecke et al., 2009). As a result,
MC/HR-ICP-MS has gradually replaced thermal ionization mass spectrometry (TIMS) as
the method of choice for isotope measurements in geological and archaeological studies
(White et al., zooo). However, MC/HR-ICP-MS instruments are very expensive, particu-
larly multicollectors, compared with TIMS and quadrupole ICP-MS instruments, and are,
consequently, less widely available. That said, HR-ICP-MS has been successfully used to
study lead isotopes in ceramic glazes for provenance determination by both liquid sampling
(e.g. Habicht-Mauche et al., 2002; Cui et al., 2010) and laser ablation (Habicht-Mauche et al.,
2002; Ifiaftez et al., 2010 ).
The third spectrometer used for archaeological applications is the time-of-flight
(TOF) mass spectrometer (Figure 23.2d). Rather than using differential m/Z ratios to
sort ions in a magnetic field, as quadrupole and magnetic sector instruments do, TOPs
use the time of flight after application of a uniform accelerating voltage to sort ions
by mass by forcing ions through a curved path of particular length. TOF spectrome-
ters can measure the entire mass range simultaneously, and integrate that mass range
about three times faster than quadrupole instruments. Consequently, TOF spectrom-
eters are of particular utility in applications where short signal integration time is neces-
sary (Leach and Hieftje, 2ooo; Thomas, 2013); for example, the analysis of microfeatures
406 MARK GOLITKO ANO LAURE DUSSUBIEUX

such as pore boundaries, small grain inclusions, and very thin slips or glazes. Although
less resolved than I-IC-ICP-MS instruments, TOF spectrometers generally achieve bet-
ter mass-resolution than quadrupole instruments, and thus in principal represent a rel-
atively cheap means of isotopic analysis. However, TOFs have low sensitivity (ability to
detect signal above background), and Dudgeon et al. (2007) were only able to achieve
sufficiently high signal counts for low-abundance isotopes by generating several hun-
dred readings per sample, removing "noisy" readings resulting from low concentrations
in some areas of the analyzed samples, and averaging the remaining measurements to
generate isotopic ratios.

QUANTIFICATION

Quantitative results are obtained by comparing the signal intensity measured for a given ele-
ment in a sample to the signal intensity for the same element in a standard solution or a
certified reference material (CRM), also called an external standard in the literature. ICP-
MS instruments exhibit cyclical patterns of drift over time, meaning that the relationship
between signal strength and sample elemental concentration changes between analyses.
Consequently, quantification requires repeated analysis of external standards across the
course of analysis to ensure that values are comparable. In addition, an internal standard is
required to correct for potential changes in sampling rate-how much material enters the
plasma per unit time. For liquid sampling, quantification is relatively straightforward; the
internal standard is an element absent in the sample material, and each sample and stan-
dard solution is spiked with a known concentration of the element. External standards are
typically produced by diluting commercially available elemental solutions with ultra-pure
water and nitric acid to produce standards at varying concentration levels (see, for example,
Kennett et al., 2002).
Generating quantitative results for LA-ICP-MS analysis is more challenging. For solid
samples, the internal standard has to be an element already present in the material because
it is not possible to add elements/material to the sample. The control element must have a
relatively high concentration in each sample and external standard so that its measurement
is as accurate as possible (Gratuze et al., 2001). In most archaeological ceramic studies, Si is
the internal standard used; however, Al or another major element could, in principle, serve
just as well.
In order to obtain absolute concentrations for analyzed elements, the concentration of
the internal standard has to be known. Some studies measure major element concentrations
using an independent method, such as SEM-EDS or EPMA (e.g. jackson et al., 1992). Most
archaeological studies use the method employed by Gratuze et al. (2001), in which values
for all elements measured by LA-ICP-MS are converted to oxide weights and summed to
100% to recover the concentration of the internal standard. This approach assumes that all
elements are present as their most common oxides, that nearly all of the elemental content
of the analyzed portion of a sample has been measured, and that any elements missing from
the total elemental composition, therefore, represent only an insignificant percentage of the
total content. For ceramics, measuring more than fifty elements at a time with LA-ICP-MS
if·

ICP-MS AND LA-ICP-MS 407

makes it likely that both assumptions are applicable enough to minimally impact the result-
ing calibration.
Gratuze et a!. (2001) quantified their results by repeated measurements of several
standards, averaging these values to calculate a "response coefficient" from which sam~
ple concentrations were derived. Alternatively, these multiple standards can be used
to generate a linear regression line for each element, as done by Speakman and Neff
(zoos). A number of different standard materials have been used in ceramic analyses
to produce calibration slopes, most commonly NIST61x glasses, New Ohio Red Clay
(NORC), NIST679 ("brick clay"), Corning synthetic glasses (matching the composi-
tions of ancient glasses), and fused USGS rock standards such as BHV0-1 (Giussani
eta!., 2009). It is desirable to use standards that are closely matrix-matched to sam-
ples; however, clay standard materials tend to be heterogeneous at the scale sampled by
laser ablation (Robertson et al., 2002), producing variability of 20% or more between
readings on some elements, while variability in NIST glasses is typically less than 5%
between readings.
With shorter-wavelength lasers (213 and 193 nm lasers), fractionation and issues oflaser
coupling related to differing sample opacity are reduced to the point where a combination of
both homogeneous glass standards and matrix-matched clay standards can produce a reli-
able calibration slope for archaeological ceramics (Figure 23-3).

0.4 r 0.0016
'

0.0012
c
0
z
0.001 ~
u 0.2
g
-~ 8
0.0008 -~
"0
E
0.15
11
T I l3
Qi . 0.0006 'f
"=
u
0.1 0 ,,
0.

"
D
~
0.05
0
o Rb
Pr
0.0004
- - -Linear (Fe)
··~-··Linear (Pr) 0.0002
0
········Linear (Rb)

Si-normalized signal

FIGURE 23.3 Examples of calibration lines (Si-normalized signal versus Si-normalized

concentration) for Fe, Rb, and Pr using NIST610, 612, and 679 as SRMs, with NORC (sym-
bols in circles) as a quality assurance standard.(© Mark Golitko.)
408 MARK GOLiTKO AND LAURE DUSSUBIEUX

APPLICATION IN ARCHAEOLOGICAL CERAMIC

PROVENANCE STUDIES

Liquid Sample Introduction

ICP-MS was first used in archaeological materials studies in an attempt to find a lower-cost
and more widely available alternative to INAA (Kennett et al., 2001), particularly given fears
that activation reactors would increasingly be shut down because of environmental concerns.
Consequently, many early ICP-MS ceramic studies used liquid sampling for bulk chemical
characterization. After initial attempts using weak-acid extraction proved problematic, more
aggressive acid-digestion routines were applied in studies by Mallory-Greenough et al. (1998),
Bentley (2ooo ), and Hall (2002). More recent studies have used microwave digestion of pow-
dered ceramic for bulk characterization. For example, Kennett et al:s studies of Lapita and
post-Lapita ware from the western Pacific (Kennettet al., 2004; Clark and Kennett, 2009) and
Little et al. (2004), whose work on Mayan ceramics from Belize, demonstrated the compara-
bility ofMD-ICP-MS and INAA for bulk compositional analysis.
However, MD-ICP-MS has not supplanted INAA as the "gold standard" ofbulkceramic char-
acterization. In part, this is because INAA reactors, although fewer in number, remain active,
and INAA not only achieves excellent precision for most elements of interest for ceramic prov-
enance studies but the huge databases of comparable ceramic data that have been built using
the technique facilitate the identification/ determination of fabric groups across large regions.
Acid dissolution is time-consuming and requires the use of expensive and caustic acids; acid
dissolution in open vessels can take upwards of twenty-four hours, while fusion and microwave
digestion take several hours prior to analysis as several evaporation sequences are required to
fully digest the sample and remove acids that might be harmful to the instrumentation. The
cost associated with purchasing ultra-pure acids for trace element analysis also drive the cost
of MD-ICP- MS into the range available for subsidized INAA (Little et al., 2004). However, bulk
characterization by acid dissolution ICP-MS can generate quantitative data for more than fifty
elements in principle, an advantage over the thirty-two elements typically measured by INAA.

LA-ICP-MS for Spatially Resolved Analysis

Laser ablation was first applied to archaeological ceramic analysis during the 1990s as an
alternative and less destructive method for characterizing ceramic glazes than SEM-EDS or
EMPA (Gratuze et al., 2001). These early studies focused on the unique abilityofl.A-ICP-MS
to produce spatially targeted chemical information providing valuable insight into produc-
tion techniques and raw-material provenance determination of surface treatments, either as
a primary means of reconstructing intercommunity and interregional ties or as a comple-
mentary line of evidence to supplement bulk paste analysis.
For instance, in his study of Plumbate ware from the Pacific coast of Guatemala, Neff
(2003) compared slip composition, determined by LA-ICP-MS, to paste composition, previ-
ously determined by INAA, and concluded that the same raw-material resources were used
for both the vessels themselves and the surface treatments. Oka et al. (2009) analyzed the
 ICP-MS AND LA-ICP-MS 409

composition ofblue and white and celadon glazes to differentiate between true Chinese-pro-
duced wares and Middle Eastern imitations recovered at archaeological sites in East Africa
and Western India. Speakman (zoos) used LA-ICP-MS to map composition of paints on
Mesa Verde and Mancos black-on-white pottery from the American southwest. His results
established refined characterization subdivisions of styles, previously defined by paint color
and design, and demonstrated that interregional connections inferred from style alone can
gloss over the finer distinctions revealed by the use of distinctive paint compositions to pro-
duce the same designs.
These studies all used quadrupole ICP-MS instruments to generate elemental concentra-
tions; however, MC-ICP-MS studies oflead isotopes in ceramic glazes have also been suc-
cessful in determining raw-material provenance. Habicht-Mauche et al. (2002) were able to
match glaze paints on Rio Grande style vessels to lead sources in the American southwest,
both by LA-MC-ICP-MS and by acid dissolution MC-ICP-MS. Ii\aiiez et al. (zow) were sim-
ilarly able to link the lead glazes on colonial period Romita pottery from central Mexico to
Mexican ore sources using LA-MC-ICP-MS.
In other studies, the spatial resolving power of LA-ICP- MS is used to study mineral inclu-
sions in ceramics for provenance purposes. Cogswell et al. (zoos) used LA-ICP-MS to char-
acterize schist temper in l-Iohokam ceramics from the Gila River area, but it proved difficult
to assign sherd inclusions to particular sources because of the large amount of natural vari-
ability in the geological sources. In a study of tephra temper in Mesoamerican ceramics by
Neff and Sheets (2005), researchers were able to conclusively link tephra grains in ceramic
vessels back to particular volcanic ash deposits. Palumbi et al. (2014) studied the compo-
sition of obsidian temper in Chalcolithic Caucasian pottery, and were able to combine
unequivocal source assignments for obsidian temper grains with data on paste chemistry
and suggest possible production locations for pottery from the site of Aratashen, Armenia.
'!he latter two studies in particular highlight how LA-ICP-MS analysis of temper can both
supplement analyses of ceramic paste and complement mineralogical data determined by
petrography, identifying variability within temper types that would likely not be identified
using optical microscopy alone.
A third research area in which the spatial resolving power of LA-ICP-MS has been used
for archaeological ceramic analysis is in the identification of chemical alteration resulting
from firing, use, and/or burial. In the aforementioned study of Plumbate ware, Neff (2003)
noted systematic evolution of slip composition by depth, which he attributes to firing
induced migration of particular constituent elements. Golitko et al. (2012) were able to iden-
tify a pattern of barium enrichment in sherds from northern Papua New Guinea, consistent
with post-depositional alteration processes, using raster mapping of sherd cross-sections by
LA-TOF-ICP-MS. Spatially resolved analysis by LA could also, in principle, be used to map
chemical enrichment or depletion along pore boundaries, fractures, and voids, where post-
burial uptake, leaching, or redeposition may potentially leave characteristic traces.

LA-ICP-MS FOR PASTE ANALYSIS

LA-ICP- MS is also increasingly used to generate an averaged composition for the fine paste
fraction of archaeological ceramics (e.g. Cochrane and Neff, 2oo6; Golitko and Terrell,
410 MARK GOLITKO AND LAURE DUSSUBIEUX

2012). Compositional analysis of the matrix material has two benefits over bulk composi-
tional studies; the chemical signature of the temper, which might obscure patterns or groups
of the matrix material, is eliminated (e.g. Cochrane and Neff, 2006); and, as a result, it is pos-
sible to more closely match archaeological ceramics with the composition oflocally available
raw material resources/clays (e.g. Sharratt et al., 2009). In some cases these studies build
on or are complemented by petrographic analysis (e.g. Fitzpatrick et al., 2006; Golitko and
Terrell, 2012), or bulk characterization by INAA (e.g. Vaughn et al., 2011), or acid dissolution
ICP- MS (e.g. Cochrane and Neff, zoo6).
The effectiveness of a spot analysis technique for characterizing heterogeneous ceramic
paste might be questioned; however, comparative studies of both clay standard reference
materials and archaeological ceramics suggest that LA-ICP-MS can provide reliable compo-
sitional data for many archaeological ceramic pastes, although variability should be assessed
on a case-by-case basis. Comparison at two laboratories of averaged compositional analysis
by LA-ICP-MS with MD-ICP-MS and INAA for NIST679 (Table 23.1) and New Ohio Red
Clay (Table 23.2) suggests that the precision and accuracy achieved by repeated analysis is
comparable to that achieved by other techniques for the majority of elements (data from
Glascock and Anderson, 1993; Kuleff and Djingova, 1998; Meloni et al., 2000; Grave et a!.,
2005; Wallis and Kamenov, 2013). For some elements in each standard, there are discrep-
ancies in measured concentrations relative to bulk characterization, particularly major ele-
ments Si and AI, and trace elements Zr, Hf, and some of the REEs. Enrichment and dilution
patterns for major elements Si and AI in NORC can be explained by the high percentage of
quartz in that standard compared to NIST679. As Si is typically used as an internal standard,
the variable ablation of quartz and other Si-rich inclusions is an issue relative to calibration,
and likely introduces some error to both standard and sample measurements as a result. It is
possible a less variably distributed major element such as K might serve better as an internal
standard. Alternatively, Si can be calibrated using signal strengths only for homogeneous
glass standards, and a dilution correction factor (e.g. Mommsen and Sjoberg, 2007) then
applied to measured samples to constrain error resulting from variable Si content. Zr and
Hf, which occur in ceramics primarily as zircon inclusions, and some REEs (Ce, La), which
also commonly occur in ceramics as discrete mineral phases, such as monazite-xenotime,
exhibit high levels of measurement error when sampled by LA-ICP-MS (Neff, 2003; Wallis
and Kamenov, 2012).
Precision and accuracy may be impacted, therefore, by how many ablation spots or lines
are sampled per ceramic, and whether data are "despiked" to remove anomalous measure~
ments that might result from ablation of a variable numbers of small mineral grains. The
data from the Field Museum Elemental Analysis Facility (EAF) reported in Tables 23.1 and
23.2 were generated by measuring ten 100 micron ablation craters, and removing up to three
outlier values (for elements with %RSD between measurements of more than 20%) to gen~
erate a final averaged value. In comparison to the values reported by Wallis and Kamenov
(2012), for instance, values for Zr, Hf, and most REEs in the EAF measurements are much
closer to published consensus values. In their study, Wallis and Kamenov also achieved bet-
ter accuracy after despiking their data. Stoner and Glascock (2012) also generated multiple
measurements per sample and despiked the resulting data, ablating six lines per sample
and removing divergent measurements to derive a final averaged value. In their 2012 study,
they removed aberrant measures only for specific elements known to be elevated in temper
grains. Running multiple ablation lines or spots also facilitates assessment of actual sample
Table 23.1 Comparison of measurements on NIST679 (brick clay) by LA-ICP-MS,
MD-ICP-MS, and other bulk techniques.

LA-ICP-MS MD-ICP-MS INAA

------------------------
certified published

FM EAF Wallis and Kennett et al. NISTvalues Glascock Melloni et al. Grave et al.
Kamenov (2002[ andAnderson (1999) (2005)
(2013[ (1993)
----
mean 1-o mean 1-o mean 1-o mean 1-o mean 1-o mean 1-o mean 1-o

li 82.67 1.75 83.20 4.99 71.70 6.20 75.89 6.4

Be 4.2 0.26
B 95.51 3.31
Na [%) 0.1 0.01 0.14 001 0.15 0.097 0.13 0.00 0.123 0.003 0.06 0.0
Mg [%) 0.64 0.02 0.87 0.03 0.78 0.05 0.76 0.01 0.75 0.1
AI(%) 12.5 0.44 13.74 0.34 10.60 0.80 11.01 0.34 10.60 0.30
Si (%) 26.96 0.42 19.37 0.43 24.34 0.30
p (%) 0.86 0.005 0.08 0.01
s 293.59 32.1
K[O/o) 2.74 0.07 2.57 0.16 2.46 0.21 2.43 0.05 2.38 0.14 2.44 0.2
Ca (%) 0.19 0.02 0.14 0.01 <.20 0.16 0.00 0.16 0.0
Sc 28.45 1.68 23.7 2.32 32.80 3.14 22.70 0.40 22.53 001 23.03 1.3
Ti(%} 0.59 0.04 0.76 0.07 0.58 0.03 0.52 0.05 0.57 0.0
v 199.43 6.11 171 11.5 215.4 28.2 160.00 5.00 188.4 11.9
Cr 128.84 4.56 124 8.0 143.7 13.5 109.70 4.90 107.00 2.00 110.10 0.80 88.63 5.6
Mn 1553.69 89.52 1467 224 2025.31 175.11 1835.00 35.00 1810.85 108.8
Fe (Ofo) 8.6 0.7 11.4 2.2 9.5 0.8 9.05 0.21 9.06 0.18 9.05 0.01 9.26 0.5
Co 30.24 1.18 26.8 2.9 30.4 2.1 25.80 0.40 25.98 0.01 27.09 1.8
Ni 74.3 2.63 69.7 5.5 70.8 8.3 <75 60.70 0.40 59.09 3.7
Cu 52.12 6.34 43.9 3.5 40.1 3.3 33.3 2.3
Zn 144.37 9.58 127.3 17.3 161.1 15.3 104.00 21.00 132.50 0.90 115.82 6.8
Ga 29.8 1.8
As 7.06 3.12 8.08 0.8 10.7 3.2 9.50 0.60 9.67 0.04
Se 0.17 0.09 2.89 004
Rb 221.56 6.66 210 12.6 180.1 14.5 196.00 9.00 197.80 0.50
Sr 80.31 4.05 53.4 12.4 72.6 6.6 73.40 2.60 <80 72.87 4.1
y 33.5 3.9 34.9 7.7 35.7 3.4 37.5 2.1
Zr 165.7 16.92 199 114 138.00 23.00 139.50 0.40 150.16 8.8
Nb 21.2 0.65 26.9 3.4 12.89 0.9

(continued)
Table 23.2 Continued
LA-ICP-MS MD-ICP-MS INM

certified published

FM EAF Wallis and Kennett et aL NIST values Glascock Melloni eta!. Graveet a!.
Kame nov (2002) and Anderson (1999) (2005)
(2013) (1993)
---
mean 1-o mean 1-o mean 1-o mean 1-o mean 1-o mean 1-a mean 1-o

Cd 0.9 0.58 0.11 0.05 0.52 0.0

Sn 4.97 0.4
Sb 1.11 0.23 0.80 0.10 1.05 0.01
Cs 12.97 0.3 9.66 1.9 9.0 0.7 9.68 0.20 9.79 0.03
Ba 519.39 14.93 402 39.9 481.0 34.6 432.20 9.80 445.00 48.00 437.30 0.60 462.55 28.0
La 72.9 8.44 40.1 11.7 45.3 4.3 49.40 0.40 53.72 0.03 48.79 2.7
Ce 133.82 12.75 95.2 27.4 92.7 8.8 105.50 2.50 104.90 0.40 102.8 7.9
Pr 13.1 1.24 10.2 3.4 11.5 1.1
Nd 59.8 7.72 38.9 14.5 42.2 3.8 47.80 5.10 48.30 0.70 23.83 1.4
Sm 11.63 1.45 8.6 3.3 8.7 0.8 9.16 0.10 9.17 0.50 11.67 1.7
Eu 2.29 0.23 1.6 0.5 1.7 0.2 1.81 0.06 1.79 0.01 16.6 1.4
Gd 7.66 0.69 7.9 3.2 7.7 0.7 4.99 0.03 20.46 1.3
Tb 1.6 0.14 1.3 0.7 1.3 0.1 1.23 0.19 1.24 0.02
Dy 11.12 1.44 8.0 5.5 6.8 0.7 6.24 0.31
Ho 1.71 0.21 1.8 1.2 1.4 0.1 1.68 0.04
Er 4.96 0.54 5.0 3.4 4.6 0.5
Tm 0.69 0.06 0.8 0.5 0.8 0.1 0.62 0.01
Yb 5.66 0.64 3.7 2.5 4.3 0.5 3.82 0.13 3.84 0.04 5.15 0.3
lu 0.75 0.12 0.7 0.3 0.7 0.1 0.53 0.02 0.53 0.00 2.98 0.2
Hf 4.61 0.37 5.4 2.5 4.60 4.59 0.14 4.51 0.05 4.05 0.6
Ta 1.43 0.1 1.9 0.3 1.26 0.22 1.25 0.03
w 2.16 0.13
Tl 0.8 0.2
Pb 30.09 3.56 21.9 4.7 24.2 2.9 16.68 1.5
Bi 0.58 0.11 0.7 1.0 1.4 0.3 73.3 5.2
Th 16.07 0.65 13.5 3.2 16.1 2.8 13.70 0.20 14.56 0.04 48.86 3.0
u 3.24 0.33 2.7 0.7 4.8 0.6 2.55 0.55 2.62 0.05
P·
¥

Table 23.2 Comparison of measurements on New Ohio Red Clay (NORC)

by LA-ICP-MS, MD-ICP-MS, and other bulk techniques.
----·
LA-ICP-MS MO-ICP-MS Published

FM EAF Wallis and Kame nov (2013) Kuleffand Kjingova (1998)

_______ ________
mean
,, __ ,
1-o mean
~-
1-o mean mean 1-o

li 139.8 4.14 139

Be 3.54 0.19
8 125.4 7.51
Na (Ofo) 0.21 0.02 0.15 0.01 0.14 0.007
Mg (Ofo) 0.96 0.03 1.27 0.1 0.82 0.73
AI (Ofo) 9.35 0.35 14.8 0.7 8.69 9.45 0.38
Si (Ofo) 30.6 0.38 24.5 2.1 30.9
p (Ofo) 0.03 0 0.03 0.0
K(Ofo) 3.45 0.08 3.5 0.3 3.55 0.2
Ca (Ofo) 0.14 0.02 0.12 0.02 0.16 0.45 0.07
Sc 20.55 1.13 25.01 2.4 16.50 18.95 1.17
Ti (Ofo) 0.64 0.05 0.85 0.1 0.65 0.59 0.06
v 241.9 6.6 196 8.3 205.29 211 26
Cr 94.81 2.92 91 5.0 81.13 90.7 7.4
Mn 319.7 24.4 285 57.4 0.02 253 10
Fe (Ofo) 6.21 0.53 6.3 0.3 5.04 5.33 0.2
Co 24.76 1.08 22.8 2.9 20.41 20.2 0.6
Ni 87.04 3.7 88.1 5.5 70.60 75.9
Cu 32.15 2.54 19.4 1.7 18.05 36
Zn 140.3 11.3 101.3 9.0 82.05 101 6
Ga 26
As 8.24 7.48 23.0 "11.1 14.1 0.9
Rb 196.8 5.18 202 13.7 118.66 184 16
Sr 75.25 2.8 77.2 19.1 51.76 66 14
y 27.96 2.64 47.5 28.1 32.63
Zr 147.5 26.1 489 899.6 192.74 170
Nb 21.76 1.26 34.9 11.4 22.45
Mo 1.24 0.14 2.2
Sn 4.68 0.41
Sb 1.48 0.26 1.39 0.09
Cs 11.5 0.35 11.6 0.9 8.67 10.6 0.7
Ba 621.6 21.6 673.4 42.4 560.20 632/704 35/17
La 39.68 3.52 74.6 98.6 28.24 50.9 3.1
Ce 100.1 10.3 148.2 169.6 77.92 109.7 6.5

(continued)
-------------------

414 MARK GOLITKO AND LAURE DUSSUBIEUX

Table 23.2 Continued

LA-ICP-MS MD-ICP-MS Published

FM EAF Wallis and Kamenov (2013) Kuleff and Kjingova (1998)

mean 1-o mean 1-o mean mean 1-0

---------- -----
Pr 10.66 1.89 17.3 22.4 8.49
Nd 36.33 6.29 59.2 61.0 34.53 42.3 2.8
Sm 7 1.19 10.2 8.1 7.29 8 0.6
Eu 1.36 0.13 1.75 1.1 1.42 1.54 0.14
Gd 5.49 0.44 8.30 4.4 6.34
Tb 0.83 0.1 1.28 0.7 1.06 1.06 0.04
Dy 4.83 0.64 7.57 3.5 6.18 7.4 l4
Ho 1.03 0.13 1.54 0.6 1.21
Er 3.02 0.48 4.71 1.5 3.57
Tm 0.45 o.os 0.86 0.3 0.54
Yb 2.97 0.57 5.02 2.3 3.51 4.27 0.16
lu 0.46 0.11 0.86 0.3 0.55 0.64 0.09
Hf 4.07 0.78 16.3 26.7 5.43 7.16 0.54
Ta 1.53 0.16 2.61 0.7 1.57 1.65 0.21
w 3.01 0.31 5.7
lr 0.27
Tl 1.09 0.2
Pb 17.38 1.68 15.5 4.1 13.84
Bi 0.72 0.38 0.44 0.2
Th 13.99 1.48 18.3 4.8 12.94 15.1 0.8
u 3.3 0.51 2.85 1.1 2.70 2.96 0.34

heterogeneity, which may in some cases be higher than in mechanically homogenized clay
standards such as NIST679 or NORC.
Despite these concerns, LA-ICP-MS is, in many cases, capable of generating reliable
characterization of chemical composition for the fine fraction of ceramic pastes. For
instance, Dussubieux et aL (2007) reanalyzed a set of Middle Horizon ceramics from the
Ayacucho region of Peru previously analyzed by INAA, and were able to generate the
same three group chemical structure as was present in the INAA data, suggesting that
chemical variation within the fine fraction of those sherds was largely responsible for
compositional patterning. Larson et aL (zoos) compared results of!NAA, MD-ICP-MS,
and LA-ICP-MS analyses of the same set of Virgin Branch Anasazi ceramics. Bulk analy-
sis by INAA and MD-ICP-MS produced a three group structure in the data. Only two of
these groups were identified by LA-ICP-MS, but separate LA-ICP-MS analysis of olivine
inclusions in sherds belonging to one of the three groups suggested that the separation
of two of the chemical groups identified by bulk analysis resulted from deliberate olivine
 ICP-MS AND LA-ICP-MS 415

tempering of some ceramics and not others. Stoner and Glascock (2012) similarly reana-
lyzed both paste and temper grains in Coarse Orange Ware ceramics from the Tuxtla
Mountains, Veracruz, Mexico, that had been previously analyzed using petrography and
INAA. Like Larson et al., they were able to replicate the general INAA patterning using
LA-ICP-MS by making allowances for the contribution of volcanic ash temper grains
measured by INAA. In contrast, Wallis and Kamenov (2012) were unable to replicate fine
distinctions made by INAA in a set of ceramics from Florida, probably because composi-
tional variability resulted from variable quartz content.

CASE STUDY: THE SEPIK COAST

OF NORTHERN PAPUA NEW GUINEA

Pottery was introduced to the Sepik coast of northern Papua New Guinea about 2000 years
ago (Figure 23.4). Ethnographic observation locates potting activity centers on Tumleo
Island and at Kaiep (May and 1'uckson, 2000) from which vessels were then widely trans-
ported by middlemen elsewhere along the coast. Archaeological surveys and excavations
carried out in the 1990s revealed both a 2ooo-year sequence of ceramic wares on Tumleo
Island and the adjacent mainland area, and a wide variety of styles surface collected else-
where along the coast (Terrell, 2011; Terrell and Schechter, 2011) including recognizable
Tumleo styles as far distant as Tarawai Island (Golitko and Terrell, 2012).
The Sepik coast is currently a global center of linguistic diversity, commonly believed
to result from intercommunity isolation played out over long periods of time. Yet when
observed ethnographically, the coast was densely interconnected by social ties that readily
crossed perceived linguistic and ethnic boundaries, and a widely shared material culture.
Ceramic provenance studies were employed to determine whether or not ethnographically
observed patterns of exchange could be traced into the deep past, or whether intensive inter-
community exchange developed only during the last two centuries, as the level of observed
linguistic diversity might suggest (Golitko and Terrell, 2012).
Geologically, the Sepik coast is comprised of a variety of continental rocks and former
island arcs brought together by the collision of the Australian and Pacific tectonic plates
(Pigram and Davies, 1987). Surface geology includes outcrops of mudstones in the Serra Hills,
tuffaceous island arc limestone in the central region of the coast (including Tumleo Island),
and exposed igneous basement rocks further east near Kaiep. These outcrops are connected
by low swampy areas comprised of material eroded out of the Torricelli Mountains, which
separate the coast from the Sepik River valley to the south (Norvick and Hutchison, 1980 ).
Preliminary petrographic analysis of fifty sherds from locations across the coastal region
(Dickinson, 2011) identified seven distinct fabric groups. However, it proved difficult to
assign these fabric groups to particular production areas because most groups were differen-
tiated by the relative abundance of placer sand temper, which is widely available in local river
beds throughout the Sepik coast. Consequently, a larger study of ceramic paste composition
by LA-ICP-MS was initiated to exclude these complex and ubiquitous placer sand tempers.
287 ceramic samples and several local clays were analyzed by LA-ICP-MS (Golitko, 2011;
Golitko and Terrell, 2012).
 ~--]Ill~~
!A Excavated Sites
0 10 20 40 Km
-$- Clay sources
0 Modern villages and collection locations

Pacific Ocean {.\

N
~ Pleistocene sediments
Leitre
!ffij Mixed sedimentary and llmcstone
\tit;;} Fine grained sedimentary
E::J Coarse grained sedimenmtary
!.2:23 Mixed or undifferentiated sediment
Jm Basic igneous
Tumleo Is. !; :!: 3Mixed or undifferentiated igneous
\ I
A!i Is.
~ Basic to intermediate volcanic
~ low grade metamorphic
ri},Seleo Is.
Tarawai Is~ 1111Tuffaceous limestone I
'0~ I
Wa!is Is.

~Muschu/s.

FIGURE 23.4 Surface geology of the Sepik coast of Papua New Guinea, with ceramic and day sampling locations indicated.(© Mark Golitko.)
 ICP~MS AND LA-ICP-MS 417

FIGURE 23 .s Backscatter SEM-EDS image of a sherd cross-section from Worn (Papua New
Guinea) analyzed by LA-ICP- MS. Ablation craters are visible underneath an interpolated
contour map (kriging method) of barium content. Lighter colors correspond to higher bar-
ium content, and show increased concentration near sherd walls. A large calcareous inclu-
sion is visible at the bottom center of the sherd. (©Mark Golitko.)

Initial examination of results suggested that chemical differentiation was possible between
Aiser ware ceramics (c.woo-soo BP) excavated on Tumleo Island and surface collected at
Worn on the adjacent mainland (see Figure 23.4), both situated on similar underlying geol-
ogy. Barium, an element known to be highly mobile in ground water, was the principal
discriminator between the two assemblages leading the researchers to suspect that post-
depositional chemical leaching might account for this difference in composition. Elemental
mapping of both high- and low-Ba sherds from several locations across the Sepik coast was
conducted using LA-TOP-ICP- MS. Elemental distribution was examined by ablating grids
of 100 micron spots across sherd cross-sections (Golitko et al., 2012).
Figure 23.5 shows a contour map of barium content generated for one of the high-Ba
sherds from Worn, illustrating the clear pattern of enrichment along sherd walls consistent
with uptake from the burial environment. Elemental maps oflow-Ba sherds did not show
these consistent patterns of enrichment and were compositionally consistent with locally
available clays. Consequently, Ba was omitted from further analysis.
After excluding Ba from the analysis, eight chemical profiles were identified among the
pastes (Figure 23.6): one clearly associated with sherds and clays from the Serra Hills area;
three with the central coast region (Aitape-Barida Groups 1-3), including all sherds from
418 MARK GOLITKO AND LAURE DUSSUBIEUX

{V)"" Ramu sherds

($)"" Kaiep sherds
(®)"'Ethnographic: Tum leo ceramics Tarawai 3(x)
3 (+)""Unassigned sherds
(m) = Serra Hills days
(.&.) = Tumleo/Aitape days
+
Tarawai 2 (o) +
M 2
c
0 +
B +
c
0
Serra Hills (o) +
~
0
+ +
"cro 1
E
·~
i5 0 - +
"B
·c +
0
c
ro
u -1

Aitape-Barida 1(O)
-2
•

-1
Canonical Discriminant Function 1

FIGURE 23.6 Discriminant function plot summarizing the results ofLA-ICP-MS analy-
sis of all ceramic and clay pastes analyzed from the Sepik coast of Papua New Guinea.
(©Mark Golitko)

the production center ofTumleo Island; and four chemical signatures found only on Tarawai
(groups 1-3) and Walis Islands (Buamunding group). The first four groups could be conclu-
sively linked to production in the Serra Hills and central coastal regions based both on the
criterion of abundance and comparison with local raw materials. The later four chemical
groups likely originated from production areas elsewhere along the coast or inland in the
Torricelli foothills (Golitko, 2011). Sherds, presumed to be produced on Tumleo Island, were
transported along the coast for at least the last millennium, and it appears that linguistic
diversity on the coast has been maintained despite a long-term history of intensive inter-
community contact (Golitko and Terrell, 2012).

ICP-MS AND LA-ICP-MS IN ARCHAEOLOGICAL

CERAMIC ANALYSIS

Inductively coupled plasma-mass spectrometry is a versatile method for the chemical charac-
terization for archaeological ceramics, capable of generating highly accurate bulk characteriza-
tion of fifty or more elements at relatively low concentrations using acid dissolution, and of
 ICP-MS AND LA-ICP-MS 419

targeting specific phases in a ceramic matrix using laser ablation. ICP- MS is a viable alternative
to INAA, measuring more elements to lower detection limits, albeit at the cost of labor and
cost-intensive sample preparation. Most archaeological applications of ICP-MS for ceramic
provenance use laser ablation sampling to target specific phases in the ceramic matrix. By tar-
geting the fine fraction of a paste, individual temper grains, glazes, slips, paints, or features such
as pore boundaries or fractures, LA-ICP-MS can help untangle the multiple geological, cul-
tural, and environmental effects that may contribute to the bulk composition of an artifact.
Identification of these factors and their impact on bulk composition enables archaeologists to
make more precise and plausible provenance determinations for archaeological ceramics.

AcKNOWLEDGMENTS

Many thanks to Alice Hunt for inviting us to contribute to this volume. We also thank
Neill Wallis for sharing his measurements on standard reference materials. 1be case study
reported here was funded in part by grants and awards from the United States National
Science Foundation, Lester Armour Fund, Regenstein Fund, and Field Museum Grainger
Fund for Scientific Research.

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 CHAPTER 24

INSTRUMENTAL NEUTRON
ACTIVATION ANALYSIS
(INAA) IN THE STUDY
OF ARCHAEOLOGICAL
CERAMICS

LEAH D. MINC AND JOHANNES H. STERBA

INTRODUCTION

Neutron activation analysis involves inducing radioactivity in the elements of

interest in the sample by bombardment with neutrons and selectively measuring
the intensities of the induced radioactivities which are directly proportional to the
amounts of the elements in the sample.
(Muecke, 1980> 43)

Neutron activation analysis (NAA) is a nuclear science technique for determining the
elemental composition of ceramics, clays, and other materials at the percent, parts-per-
million (ppm), and even parts-per-billion (ppb) level. In essence, the technique works by
exposing a small amount of sample material to the neutron field within a nuclear reactor, in
order to "activate" or create radioactive isotopes of the elements present (Alfassi, 1990 ). By
monitoring the subsequent decay of these radioisotopes, it is possible to both identify and
precisely quantify the elements originally present in the sample. In the classic case of acti-
vation analysis, irradiation was followed by the chemical separation of elements in order
to measure their activities with fairly simple instrumentation. Today, however, advanced
detection instrumentation allows us to readily separate and identify elements based on
their gamma-ray emissions, so that the technique is.now generally referred to as instru-
mental neutron activation analysis (INAA).
Over the past thirty years, INAA has become the mainstay in compositional analyses
of archaeological ceramics (Perlman and Asaro, 1969; Harbottle, 1982; Neff and Glascock,
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 425
·················~·······~······································~-~

1995). Hundreds of thousands of samples have been analyzed via INAA in well-established
laboratories around the globe, generating large comparative databases of pottery and clay
artifacts for many parts of the world. These laboratories also have well-documented stan-
dards and protocols which facilitate interlaboratory calibration and data sharing, such that
comparative data are readily available and widely disseminated. INAA remains competitive
with more recent developments in multi~element analysis (including ICP-MS), and its track
record suggests that it will continue to play a major role in the bulk chemical characteriza-
tion of ancient ceramics in the coming decades.
The popularity of INAA is largely the result of its simultaneous multi-element analyti-
cal capacity, sensitivity, precision, and ease of sample preparation. Sixty-seven common
and rare earth elements become radioactive when exposed to the neutron flux in a reac-
tor; of these, at least fifty can be identified and measured quite readily using INAA (Table
24.1). By combining different irradiation and decay times, it is possible to measure many of
these elements within the same aliquot of sample material; thus, INAA labs routinely pro-
vide data on 35-40 elements for each pottery sample. Detection limits for many trace ele~
ments are excellent with minimum detectable concentrations (MDCs) in the low ppm to
ppb range, significantly lower than those offered by X-raytechniques such as XRF or EMPA,
and measurement errors are generally less that 5% for routine analyses, an important consid-
eration given the compositional complexity of most ceramics. Finally, sample preparation of
ceramics is quite straightforward, consisting of physically removing surface pigments and
contaminants by abrasion, followed by pulverization and drying of the ceramic powder; no
chemical separations or acid digestions are required.
These advantages come at a cost: per sample fees of c.$30 to> swo USD are common for
multi-element INAA. Other potential negatives include slow turn-around time (delays of up
to 4-5 weeks are required to measure some elements), and the consideration that INAA is a
bulk analysis technique; that is, JNAA provides no information on within-sample variation
or heterogeneity, such as that provided by the electron microprobe or LA-JCP-MS. Finally,
the technique is considered destructive, in that a small amount of material must be removed
from the artifact for irradiation; this material generally becomes radioactive waste and

Table 24.1 The sensitivity of lNAA in the analysis of ceramics varies by element,
from percent level to parts-per-trillion
Sensitivity Elements detected by INM

1 mg/g Si, S, Fe
10 ~g/g Ca, Cr, Se, Rb
1 ~g/g Mg, K, Sc, Ni, Zr, Nb, Sn, Ta, Os
100 ng/g Qn.~zn.~~~.Ru.~~-~k~~.~~~.~~Th
10 ng/g Na, AI, Ar, Cu, Ga, As, Br, Sr. Rh, Sb,l, Cs, Hf, W, Pt, Hg, La, Nd, Sm, Ho, Yb, U
I ng/g V, Re, lr, Au, Er, lu
1 pg/g Mn, In, Eu, Dy
Not detectable: H, He, li, Be, B, C, N, 0, F, Ne, P, Y, Tc, Tl, Bi, Pb, Po, At: Rn, fr, Ra, Pm, Ac, Pa
426 LEAH D. MINC AND JOHANNES H. STERBA

cannot be returned to the researcher following analysis, unlike samples analyzed via XRF,
for example.

FUNDAMENTAL PRINCIPLES OF INAA

Although considered a technique of elemental analysis, INAA works at the level of isotopes.
Each element in the periodic table consists of one or more naturally occurring stable iso-
topes which share the same number of protons (Z), but differ in the number of neutrons
and, thus, in atomic mass (A). A few elements are mono-isotopic; that is, having only one
natural isotope. The element aluminum is mono-isotopic: all naturally occurring aluminum
is the isotope 27Al. Most elements> however, have more than one naturally occurring isotope
(same Z, different A). Iron, for example, has four naturally occurring stable isotopes with the
following abundances: ''Fe (5.8%), ' 6Fe (91.7%), 57Fe (2.2%), and "Fe (0.3%), while elemental
copper has just two isotopes: 63Cu (69.2%) and 65 Cu (30.8%). Since the relative fractional
abundance of the isotopes is generally assumed to be constant or fixed, any individual or
single isotope can be analyzed to determine the amount of element present, although practi-
cal considerations usually identify one isotope as the preferred marker for an element.
During activation analysis, these naturally occurring isotopes undergo distinct reactions
involving the creation of radioactive isotopes (radioisotopes) and their subsequent decay.
1bis process occurs in several steps. When a sample is exposed to the flow of neutrons gen-
erated by a nuclear reactor> the bombarding neutrons collide with target nuclei present in
the ceramic material to form compound nuclei in an excited state (Figure 24-1). The excita-
tion energy of a compound nucleus is due to the absorption of an additional neutron, which
upsets the balance between attractive nuclear forces (which bind protons and neutrons

Beta Particle Delayed

~ Gamma
t Y,
Target Nucleus

The compound nucleus

almost instantaneously
de-excites through loss The still radioactive
of a prompt gamma ray. nucleus further decays
to a stable state through
foss of a beta particle
and a delayed. gamma.
Radioactive
Nucleus
An incident neutron strikes
a stable target nucleus
creating a highly unstable
compound nucleus. ''
Unstable ' '~ Prompt Stable
Compound Gamma Product
Nucleus Y, Nucleus

FIGURE 24.1 Schematic overview of neutron activation and subsequent decay.

 iNAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 427

together) and repulsive electromagnetic forces (which drive protons apart). In response to
this imbalance, the compound nucleus almost instantaneously de-excites (with a half-life
in the range of 10-· 3 to 10~ 1 3 s) to a more stable configuration, emitting one or more prompt
gamma rays (yp) or a charged particle in the process. The technique of prompt-gamma acti-
vation analysis (PGNAA), a related method of elemental analysis, monitors the decay of
these prompt gamma rays during sample irradiation. PGNAA is potentially less destructive
than sample preparation required for INAA, but with reduced sensitivity for most elements.
Following the emission of a prompt gamma ray, the resulting nucleus may be stable. More
typically, the captured neutron produces a radioisotope that decays with a half-life ranging
from seconds to many years, emitting beta radiation and delayed gamma rays (yd). These
delayed gamma rays are what make elemental determinations feasible via INAA. Both the
energy carried by the gamma ray (measured in kilo electronvolts or ke V), and the rate or
half-life of the decay are characteristic of a particular isotope. By collecting and measuring
the full spectrum of gamma rays emitted by a sample, it is possible to identify the specific
radioisotopes present and to determine the elements they represent Further, since the activ-
ities of the induced radio nuclides are directly proportional to the amounts of the elements
present, the elemental composition of the sample can be quantified precisely based on num-
ber of gamma rays detected for each isotope.
Although relatively simple in concept, the successful application of INAA requires a
detailed knowledge of three components: (1) characteristics of the neutron source (including
density and energy distribution); (2) the reactions that occur when neutrons interact with
target nuclei; and (3) the instrumentation suitable for detecting, recording, and analyzing
the resulting radioactive decays.

Neutrons and Nuclear Reactors

INAA largely relies on the neutron flux (measured in neutrons per em' per second) pro-
duced by a research nuclear reactor, whose primary function is to generate neutrons for
scientific purposes (Figure 24.2). Other neutron generators (including accelerators and iso-
tropic neutron sources) are available, but these sources generally produce too low a neutron
density to induce the radioactivities needed for sensitive elemental analysis.
Within the nuclear reactor core, neutrons are created through a controlled fission chain
reaction within the enriched-uranium fuel rods. When struck by a free neutron, the heavy
and naturally unstable nucleus of a 23SU atom will split into two smaller nuclei, releasing
considerable energy and an average of c.2.5 extra neutrons per fission. One of these neutrons
is required to induce further fissions in the fuel and perpetuate the fission chain reaction;
excess neutrons can be utilized to activate sample materials.
Because much of the energy generated by nuclear fission is released as heat (c.2oo MeV
per fission), the reactor core sits within a large pool of water which serves to cool the sys-
tem and prevent melt-down. The water provides several other critically important func-
tions as well. First, it reflects neutrons back into the core, concentrating them near the
fuel and irradiation facilities. Second, the water moderates or slows down the neutrons.
Fission neutrons are too energetic to be captured by the uranium fuel, but the loss ofldnetic
energy to water molecules increases the probability that these neutrons will be absorbed by
a :l3SU nucleus and initiate a fission event. Moderating materials such as water and graphite
428 LEAH D. MINC AND JOHANNES H. STERBA

FIGURE 24.2 The core of a research reactor provides a high~intensity source of neutrons
to activate samples. The 1-MW OSU TRIGA reactor sits within a tank of water ca. 2m in
diameter by 7 m deep. Fuel rods are loaded in a circular array and surrounded by a graphite
reflector (outer gray ring), which helps to concentrate neutrons near the core. Between the
core and the reflector is the rotating rack or "Lazy Susan'' (inner dark ring), where samples
are loaded for long irradiations. The pneumatic tube facility (largely obscured by the control
rods) delivers samples directly into the core for short irradiations.

similarly increase the probability that free neutrons will be slowed sufficiently to interact
with nuclei of the target materiaL Third, the pool water serves as an important bioshield,
blocking neutrons and gamma rays, and protecting reactor operators and researchers from
damaging radiation.
As a result of this moderation, all research reactors produce neutrons across a range of
energies, known as the neutron energy spectrum. Three main components are recog ~
nized: (1) the fast flux consisting of energetic neutrons (> - 0.5 MeV) born of the ' 35 U fis-
sion which still retain much of their original energy; (2) the intermediate flux (- 1 eV to
- 0.5 MeV) comprising neutrons which have been partially slowed down through collisions
with surrounding material down to the epithermal range; and (3) the slow or thermal flux
consisting oflow-energy neutrons (energies below- o.s eV) that have been slowed to the
point that they are in thermal equilibrium with atoms in the reactor's moderator (although it
should be noted that these "slow" neutrons still have an average velocity of 2200 m s·').
As we shall see, neutrons in these different energy ranges generate distinctive suites of
radioisotopes. Overall, the thermal neutrons are most important for INAA of ceramic mate~
rials. Most research reactors have a well-thermalized neutron spectrum, such that 90-95%
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 429

of the neutrons available are in the thermal range. Further, thermal neutrons have a much
higher probability of being absorbed by a nucleus within the sample because at low neutron
energies, the reactions of many nuclides obey the Maxwellian r/V law, which states that the
probability of neutron absorption is inversely proportional to the neutron velocity. Higher
energy neutrons can, however, play an important role in INAA. Many isotopes experience
resonance and a correspondingly high probability of neutron absorption for specific neu-
tron energies in the intermediate region. Finally, while fast neutrons are generally a thousand
times less likely to activate a target nucleus than thermal neutrons, they can be important in
the analysis of specific isotopes where activation with slower neutrons fails (routinely in the
analysis of nickel, for example, or in the determination of oxygen and nitrogen isotopes).
Research reactors differ in design, size, and power output, and, hence, in neutron density
and neutron energy spectra characteristics. Small university research reactors with 100-200
kW power can generate thermal neutron fluxes on the order of 10 12 n cm- 2 s-\ while larger
research reactors of 10-70 MW thermal power provide neutron fluxes up to 1d5 n crn-2
s- 1 . Moreover, most reactors offer multiple locations where sample materials can be loaded
for irradiation; irradiation facilities may be placed in the center of the core (in a high flux
location) or peripheral to the core fuel assembly (in a generally lower flux location). Each
irradiation location is unique: while most reactor facilities quote their peak thermal flux, it
is generally more helpful to know the neutron energy spectrum and density for specific irra-
diation locations utilized for INAA.

Nuclear Reactions
When target nuclei are bombarded with neutrons, one of several distinct types of reaction
will occur. In general terms, we can denote the processes of reaction as:

a+A-7B+b

where:

a is the projectile, i.e., a neutron of a specific energy,

A is the target nucleus in the isotope being analyzed,
B is the product nucleus of the resulting radioisotope, and
b is the resulting particle released during activation.
Nuclear reactions are usually identified by the abbreviated convention A(a,b)B or
simply (a,b).

Neutron Capture The most common type of nuclear reaction that occurs when target mate-
rial is placed within a well-thermalized beam of neutrons is "neutron capture", also known
as the (n,y) reaction in which a thermal neutron is gained and a prompt gamma is lost. 1be
absorption of a thermal neutron (nth) increases the mass of the nucleus (A) by 1 and cre-
ates an unstable compound nucleus which immediately decays through release of a prompt
gamma ray (Yp• a high-energy photon):
430 LEAH D. MINC AND jOHAN'NES H. STERBA
,, ,,,,,,,,,,

In some cases, the resulting isotope will be stable. More commonly, the nucleus remains
l
I
unstable, indicated by an asterisk('), and will undergo radioactive decay.
In the case of mono-isotopic aluminum, bombardment with thermal neutrons leads to
the following reaction: ~n + ~;Al -:? ~!Al' + yP also designated as~;Al(n, y) :!Al'.
Note that the (n,y) reaction results in a radioisotope of the same element, having increased
the mass number from A to A +1, while Z remains unchanged.
Transmutation The absorption of an epithermal or fast neutron, in contrast, creates a
highly. unstable compound nucleus which de-excites by releasing a charged particle, usually
. 1n + z"X -:? z_''X' + 1P·
a proton, d enote d t h e (n,p ) reactwn: 0 1 1 1
Note that in this case, atomic mass (A) remains the same, while the number of protons (Z)
decreases to Z-1 as the proton is lost. Other transmutations involve the (n,a), (n,2n), and
(n, t) reactions.
For aluminum, the (n, p) reaction involving the addition of a neutron and the loss of a
proton transmutes aluminum into magnesium; a similar reaction on silicon transforms it
into an isotope of aluminum:

or

It is important to note that, depending on the energy of the neutron, the same radioisotope
can be produced from two different reactions of two different stable isotopes. That is, ~:AI'
can be produced from the thermal neutron (n,y) reaction on :;At,
or a fast neutron (n, p)
reaction on~.~ Si.
Effective Cross-sections The preceding neutron interactions occur with different frequen-
cies depending on neutron energy and the nuclear properties of the target isotope. The prob-
ability of a specific reaction occurring is governed by the isotopic cross-section (cr), which can
be envisioned as the size of target that the nucleus presents to a neutron in a given energy range.
Effective cross-sections are measured in barns (1 b = 10~ 24 cm 2) and are defined for each type
of interaction. Isotopes with large effective cross-sections are said to activate readily, while it
may be difficult to build up measurable activity in isotopes with very small cross-sections. In
general, for isotope I, the number of activated nuclei (X,) generated per unit time is directly
proportional to the number of target nuclei (N;), the neutron flux (<p) in a specific energy range,
and the isotopic cross-section (aJ for the appropriate reaction: Xi oc Ni o (p1h o a,.
Half-life and Decay Constant Another important factor governing the yield of neutron
reactions is the half-life of the isotope in question, defined as the length of time required for
half of the initial activity of a radioisotope to decay. After one half-life, 50% of the original
activity remains; after two half-lives, only 25% of the original activity remains (Figure 24.3).
An isotope's half-life also governs the rate at which activity builds up in a sample being bom-
barded with neutrons, based on the probability that activated nuclei will not decay during
irradiation. Although half-life (tw) is conceptually simple, the use of the decay constant), is
mathematically much easier. Lambda can be related to half-life by the equation:

il.= ln(2)/t, 2 •

Radioactive Decay Following neutron activation, the excited nuclei will spontane-
ously undergo radioactive decay resulting in a change of the neutron:proton ratio toward
a more stable configuration. The most common decay mode involves beta decay, in which
 !NAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 431

the activated nucleus emits a ~particle, the mass equivalent of a high-speed electron. Two
distinct forms of beta decay are possible. In isotopes formed by the (n, y) reaction which
show a neutron excess, the extra neutron will be transformed into a proton by the reaction
n -7 p+ p· + v··, and an electron (WJ together with an antineutrino (v·) is emitted. In con·
trast, when a fast nu~lear reaction has generated an isotope with a proton excess, the extra
1
proton may be converted into a neutron according to the reaction p --0- n + [J • + v , and a
positron(~+) together with a neutrino (v) is emitted.
Some radioisotopes are considered "pure beta emitters:' in that they decay directly to a
stable or ground state by the emission of beta particles only. Isotopes in this category can·
not be quantified using INAA; important examples include Pl' and SJS. Fortunately, most
radioisotopes retain a small amount of excess energy which is released as gamma rays whose
energies are characteristic of the decay of a specific isotope.
These characteristic energies enable us to readily identify the parent radioisotope and,
by worldng backwards, identify the parent element, as well. For example, assuming a well·
thermalized neutron spectrum, the presence of a gamma ray at 1779 keV represents the fol·
lowing reaction and decay, and signals the presence of aluminum in the sample:

~n 111 + ~; Al ~> ~:Ar ::si + fJ + v- + Yc.r

--0- 1779 k~v with a half-life of 2.25 m.

Similarly, a gamma peak at 1369 ke V is characteristic of the following thermal neutron reac-
tion and decay, and indicates the presence of sodium in the sample:

1
n
0 1
!J+ 2311 N a--0-u24 Na ' --0- "M
12 g+pr<- 1''
+v. +y@ 1369 kevwlt. h a h a lf-11eca. 15 h r.

~~~-~~--------------------
................ 1- e-IU
/
/
_./ Build-up of activity during irradiation

///
+---11(

2 3 4 5 6
Half Lives

FIGURE 24.3 The build-up and decay of radioactivity in an isotope according to its half-life
and decay constant A.
432 LEAH D. MlNC AND JOHANNES H. STERBA

Since these decays also occur with a characteristic half-life, we have two lines of evidence to
confirm the identity of the radioisotope in question: gamma energy and half-life of the decay.
Finally, it should be noted that most radioisotopes produce more than one gamma, as they
decay to ground state through a series of intermediate steps. Each of these steps produces a
gamma ray or radiation with an energy characteristic of that particular decay. That is, the
decay of ~;AI to ground-state occurs in a single step and thus produces a single gamma. In
contrast, the decay of ~~ Na occurs with an intermediate step, generating gammas at both
2754 and 1369 keV The fraction of gamma rays that occurs at each energy is referred to as the
gamma branching ratio (y).

Gamma-Ray Detection
Gamma-ray spectra are typically complex, especially for multi-element analysis (Figure 24-4).
The decay of any one radioisotope may generate dozens of peaks of varying intensities; the
presence of up to thirty different isotopes decaying simultaneously results in many, closely-
spaced and sometimes overlapping gamma pealcs in the spectrum. Their detection and separa-
tion relies on high-resolution detectors, of which high-purity germanium (HPGe) detectors
are the current industry standard (Knoll, 2000 ).
HPGe detectors consist of a single large crystal of high-purity germanium, encased
under vacuum within an aluminum end capsule. When the assembly is cooled by liquid
nitrogen (at 77° K), the germanium crystal becomes a near-perfect semi-conductor, with
no free carriers of electrical charges but with a low threshold energy (2.98 eV), such that a
very small amount of input energy will generate an electrical pulse. Gamma-ray photons
penetrating the detector crystal create charged particles through the photoelectric effect.

12

100 B B a D D ~ B D 1a 1100 1B 1D 1G 10 1B 1~
Energy (keV)

F 1 G u RE 2 4· 4
Complex gamma- ray spectrum resulting from the irradiation of an earthen-
ware vessel from Oaxaca, Mexico. Several of the radioisotopes are represented by multiple
gamma peaks.
 1NAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 433
.. ·····- .. .. ..... - ---

As the incoming gamma~ray strikes the germanium it ejects a photoelectron, generating a

small pulse of electrical current with a voltage proportional to the energy lost by the gamma.
That is, a high-energy gamma photon will generate a larger pulse than a low-energy gamma.
A strong electrical bias across the detector crystal collects the charge associated with each
gamma (with a time resolution of 2-6 jlS), and the associated detector electronics measure
its intensity and store the information.
In modern detector systems, electrical pulses are assigned (based on pulse height) to one
of 16,ooo channels which taken together represent the entire energy spectrum. The accu-
mulation of pulses or "counts" in several adjacent channels creates a peak in the spectrum,
representing the radioactive decay of a specific isotope. The gamma energy of these peaks,
reported in ke V, and thus their isotopic identity is determined by calibrating the system using
a certified source emitting gamma rays at known energies (Gilmore and Hemingway, 1995).
Because of the sensitivity of HPGe detecters, the assembly is surrounded by lead shield-
ing to protect it from miscellaneous radioactivity, such as that produced by naturally occur-
ring radioisotopes in the environment as well as other sample material in the laboratory. Most
detectors for routine analysis are also fitted with automatic sample changers) which lower each
sample one at a time through the lead shielding in front of the detector to collect a spectrum.

NUCLIDE QUANTIFICATION: DETERMINING

ELEMENT CONCENTRATIONS

The induced radioactivities in a sample are directly proportional to the amount of each
element present. In order to quantify that relationship and convert the number of gam-
mas detected into the concentration of a given element, archaeometrists use one of three
methods.
The parametric approach (also called the standardless or absolute method) holds that
if all the parameters governing the generation and subsequent decay of radioactivity can be
specified, then the amount of an element present in an irradiated sample can be determined
directly from the area of the associated peak in the gamma spectrum. To achieve this, we
need to solve form (elemental mass) in the following equation, by supplying the remaining
constants:

Pea kA rea= Amw N A e.(a,,rp,,Irp,P')(l

' A. - e_,," )( e-''')(! ' . r· E
' - e_,,,)

where Peak Areai = total counts associated with the i representing the isotope of interest;
m= sample mass of element in grams;
ei =fractional abundance ofisotope;
NA = Avogadro's number (6.02 x 10'3 atom/mole);
AW =gram atomic weight (gm/mole) of element;
ath::::: thermal neutron reaction cross-section;
'Pth =thermal neutron flux during irradiation;
I= resonance integral (epithermal neutron reaction cross-section);
434 LEAH D. MINC AND JOHANNES H. STERBA

'Peri:::::: epithermal neutron flux during irradiation;

l
A= decay constant for the nuclide;
ta =irradiation or activation time;
td =decay time (from end of irradiation to beginning of count);
t, =count time (for collection of gamma spectrum);
y =gamma branching ratio, i.e.,% of total decays with a specific gamma energy;
E =detector efficiency at a given y energy and geometry.
This equation states that the number of target nuclei representing a given isotope is a
function of element mass (m), elemental atomic weight (AW), isotopic abundance (0;), and
Avogadro's number (NA), which holds that one gram-atomic weight of any element contains
the same number of atoms. During irradiation, a fraction of these nuclei will be activated
depending on neutron flux (<p, the density of available projectiles), the neutron capture
cross-section (o, the probability of activation by neutrons of a specific energy), irradiation
duration (t"), and half-life or decay constant (A) of the radioisotope in question. Following
irradiation, the activity of a radioactive nuclide begins to decline exponentially according
to its half-life. After some decay interval (td), the sample is placed near a gamma detector,
which detects a fraction of the total decays being emitted according to the gamma branching
ratio (y) and the detector's efficiency (E) at the given sample-detector distance and for the
specific gamma energy, over the count interval (t,).
The parametric method is not routinely employed in activation analysis, in large part,
owing to the difficulty in precisely quantifying neutron flux. A variant of the method, known
as the k-zero (k0 ) or single comparator method, uses a flux monitor (such as a small piece
ofhigh-purity gold wire) with each batch of samples in order to determine the flux for a par-
ticular irradiation. In this case, the mass of the gold wire is known, allowing researchers to
solve the above equation for flux (<p ). All other isotopes in the analyte of sample material are
then quantified using a series of ratios relative to the gold comparator.
The basic concept of the k 0 method is to collect all the elemental factors that make up the
difference in the activation, decay, and measurement between two gamma-lines of the two
different radionudides into a single factor, called the k0 factor:

where the indices c and a denote comparator and analyte, respectively (DeCorte, 1987).
As discussed above for the parametric method, these factors include differences in atomic
mass (AW), isotopic abundance (e), gamma branching ratio (y), and the cross-section for
the capture of thermal neutrons (o). While this ratio could, in principle, be calculated from
known values, it is much more convenient and the accepted approach to use widely pub-
lished, measured values (e.g., DeCorte and Simonits, 2003). To use the k 0 method at a given
facility, detectors need to be characterized in a series of measurements to determine their
efficiency (E), while the flux (<p) in a specific irradiation facility is characterized using the
gold wire.
The k0 method offers great flexibility, in that it is possible to quantify any element with
enough activity to generate a peak in the gamma spectrum. However, in most cases the mea-
surement error is about 5%. Thus, the k 0 method is mostly applied in routine measurements
where high sample throughput at low total costs is more important than highest possible
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 435

precision. To facilitate routine analyses, several suites of software have been developed that
track characterization of the facility and reduce the time needed to perform an analysis,
including the k0 freeware developed by the IAEA (Rossbach et al., 2007) and the commercial
kayzero program (DeCorte eta]., 2001).
A third approach is known as the standard comparator method or direct comparison
method. Rather than using a single comparator, multi-element standards of known compo-
sition and mass are irradiated with the samples and analyzed under identical conditions. All
the parameters determining the induced and measured activity for a given isotope (includ-
ing irradiation location and duration, flux, cross-section, counting time, sample geometry,
and detector efficiency) are held constant for both samples and standards, and thus cancel
out. Elemental concentrations in the samples are then determined on a simple weight-ratio
basis relative to the standards, element by element. That is, with correction for slightly differ-
ent decay times, the complex parametric equation above simplifies to:

Activitysmnpte mass,ampte
Activity5ti1ndurd massstmulmt~

where activity is measured in counts per second (cps) based on total peak area and mass
refers to elemental mass in mg.
The direct comparison method is held to be somewhat more precise than the parametric
approach, as well as easier to implement, but tbe analysis is limited to quantifying elements
present in the standards. Thus, it is critical to select a standard that contains all the elements
of interest, is generally similar in composition to the samples, and has been well character-
ized such that the "true" composition is known and published. In the USA, the National
Institute of Standards and Technology (NIST) analyzes and certifies a series of standard ref-
erence materials (SRMs) commonly used in the analysis of archaeological ceramics, includ-
ing NIST1633 (coal fly ash), NIST688 (basalt rock), and NIST279 (brick clay) (Gladney
et al., 1987; Korotev, 1987). An international list of other SRM providers is maintained by
the International Association of Geoanalysts (<http://www.geoanalyst.org> ). Certified
SRMs are generally more accessible, and their certified values undergo periodic review and
updating by the scientific community (published as "consensus values") (Glascock, zoo6).
However, some laboratories choose instead to create their own in-house standards spiked
with elements not well represented in the certified SRMs. In either case, it is essential to
know which standard is used as well as the specific elemental concentration values (certified,
consensus, or other) employed, since this directly affects concentration values obtained for
all the samples.
In all of the preceding approaches, it is common practice to include samples of known
composition to serve as a check on the accuracy, precision, and consistency of results across
multiple batches. 'lbese "check standards" also facilitate interlaboratory calibration, enabling
results obtained by one lNAA laboratory to be compared against those of other labs.

Irradiation and Analysis Procedures

Although analytical procedures differ by INAA laboratory, a full multi-element analysis neces-
sarily involves two irradiations: a short irradiation for isotopes with short half-lives (t~ on the
436 LEAH D. MI:t\"C AND JOH~·\NNE$ H. STERBA

order of minutes to hours), and a second, longer one to build up activity in isotopes with longer
half-lives (t" on the order of days to years).
In order to quantify elements with short to intermediate half-life isotopes (Na, Al, K, Ca,
Ti, V, Mn, Cu), reactor facilities use a pneumatic tube system to deliver each sample to an
in-core location, where it is exposed to the flux of the reactor for a brief period of time (e.g.
a few seconds up to several minutes depending on available flux). The sample is then quicldy
retrieved and placed on the detector to collect a spectrum of the rapidly decaying radioiso-
topes. Because of the short half-lives involved, decay intervals and count times are relatively
brief(e.g. a 500 s spectrum collection time).
In contrast, to quantify elements with intermediate and long half-life isotopes, including
~K~Q~~~~~~~~B~~~~b~ThTh~m~ThU
an extended irradiation is required: 4 - 40 h is not uncommon. At many reactors, samples,
along with standards or flux monitors, are bundled together and lowered into an irradiation
facility near the core, where they are rotated to obtain an even exposure to the neutron flux.
Other reactors have rotating racks of specimen holders ("Lazy Susans") into which samples
are loaded individually: the entire rack then revolves around the reactor core (Figure 24.2).
Following irradiation, two separate counts of gamma activity are required: the first after a
c.r-week decay period to collect data on isotopes with intermediate half-lives, and a second
after c.4 weeks, after the shorter half-life isotopes have decayed away, to capture data on the
longest half-life isotopes. Both of these counts may involve collection times of several hours
per sample.
Analysis of each spectrum typically requires an environmental background subtraction
based on a blank, peak identification for the isotopes of interest, resolution of possible inter-
ferences caused by closely spaced peaks, calculation of net peak areas (total gamma counts)
attributable to a specific isotope, and decay correction of all isotope activities back to end of
irradiation. The observed activity is then quantified as elemental concentration, based on
either the k0 or direct comparison method, as described above.

TRACE-ELEMENT DATA VIA INAA

1he resulting data are distributed to the researcher as a table of concentration values in per-
cent(%), parts-per-million (ppm), or parts-per-billion (ppb), depending on the element,
and associated measurement error (usually 1-sigma values reflecting uncertainty in peak
areas). Undetected elements may be represented by negative values, indicating the mini-
mum detectable concentration, or by zeros.
In INAA, measurement sensitivity, the lowest concentration of an element detectable,
varies strongly by element and sample matrix. Simply put, certain isotopes activate more
readily, and are thus easier to measure well even at very low concentrations. Assuming a
relatively clean matrix, all detectable elements can be easily quantified at levels below r ppm.
The complexity of ceramic pastes, however, provides a worst-case scenario; the detection
limits shown in Table 24.1 are a realistic indication ofMDCs attainable for ceramic materi-
als. Both measurement accuracy (the similarity of a measure to its true value) and precision
(the similarity of repeated measurements of the same quantity) also vary by element. Based
on ceramic check-standards, coefficients of variation in the range of 1-YYo are routine for the
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 437

more precise elements (including many of the transition metals and lanthanide elements),
but can exceed 8% in the more poorly characterized elements, owing to unfortunate combi-
nations oflow isotopic abundance, small cross-section, poor gamma branching ratios, and/
or spectral interferences (Bishop et al., 1990; Mommsen et al., 1991).

PREPARING SAMPLES FOR INAA

Archaeologists interested in conducting INAA should consult with laboratory personnel to

determine how samples should be submitted and in what form. Some laboratories prefer to
work with the artifact; others ask that researchers preprocess samples into a powdered analyte.
In general, archaeological ceramic materials should be cleaned of surface contamination,
crushed to a powder (the consistency of table salt), and dried. When working with ceramic
sherds, surface contamination and pigments (slips, glazes, and paints) are best removed
through abrasion with a solid tungsten-carbide rotary file or sapphire blade. A small piece
of the sherd (roughly 1.5 x 2 em) is first "cleaned" by burring all surfaces and edges and
then nipped off; it is then rinsed with deionized water to remove dust, dried overnight, and
pulverized using an agate mortar and pestle. The dried, powdered sample material can be
archived in any clean container.
For whole vessels and museum specimens, it is frequently possible to drill into the base or
other discrete location on the vessel using a tungsten-carbide or sapphire drill bit. The sur-
face around the selected location is first masked to reduce cross-contamination, and one or
more drill holes used to collect powdered ceramic material from the vessel walL In each hole,
the powder from the surface is discarded as contaminated, and sample material collected
from greater depth. The holes can later be filled with clay or putty to camouflage the damage
to the artifact.
When working with samples of raw field clay, it is advisable to first process and fire the
clay sample under conditions approximating the ceramic technology of the study area. This
allows the researcher to verify firing characteristics, burn off organic content, and remove
surface-adsorbed water: both organics and moisture contribute to sample mass and affect
apparent element concentrations. Small clay tiles roughly z x 4 x o.s em fired in an oxidizing
environment for 1 hat 800° C mimic conditions achieved by traditional potters for earthen-
ware and unglazed ceramics (Rice, 1987); higher temperatures may be appropriate to match
conditions attained for kiln-fired pots, but also may lead to the loss of volatile elements,
including Brand As (Kilikoglou et al., 1988; Cogswell et al., 1996).
In all steps of sample processing, researchers should guard against cross-sample contami-
nation by thoroughly cleaning equipment between samples, and should control for other
possible sources of contamination including chemical residue and dust within the sample
preparation area. Skin oils and salts can contaminate samples, and should be prevented by
wearing examination gloves. Similarly, equipment and metal tools that contain elements
of interest (e.g. tungsten) may be transferred to the sample, especially when grinding hard
pastes, and should be avoided (Boulanger et al., 2013). Since INAA is a bulk analysis method,
any contamination included with the sample will appear as part of the artifact's composition.
FinalencapsulationofthepowderedmaterialforirradiationistypicallydoneattheiNAAlab-
oratoryproper. A sample mass on the order ofzoo-soo mgis placed in clean vialsofhigh-purity
438 LEAH D. MINC AND JOHANNES H. STERBA

polyethylene or fused silica ("quartz"), and carefully weighed before the vials are heat-sealed.
Additional sample material may be archived for future analysis; however, the irradiated
material will not be returned to the researcher due to the presence of long-lived radioiso-
topes and will ultimately be discarded as radioactive waste.

DocuMENTING SAMPLES SuBMITTED FOR INAA

Given the large volume of samples characterized via INAA, it is increasingly important
to document what exactly is being analyzed, so that the data are useful in future studies.
Researchers play a key role in providing detailed information on artifact provenance (site,
country, latitude and longitude oflocation, excavation context), typology (ceramic ware, ves-
sel form, surface treatment, date, cultural affiliation), and collection (museum, catalog num-
ber), which should form part of the permanent record for each analysis. Ideally, researchers
or labs will additionally photograph each sherd or vessel (interior, exterior, and profile) so
that the artifact can be identified unambiguously in the future, and so that other researchers
can compare the formal and stylistic attributes of the analyzed ceramics with vessels in their
own collections. Where possible, pastes, on a fresh break, should be recorded photographi-
cally at )OX and wox using an incident-light digital microscope, as this may assist in linking
visual characteristics with distinctive chemistry. INAA labs are currently working to make
these large, space-demanding datasets available electronically as searchable databases (e.g.
Hein and Kilikoglou, 2012).

APPLICATIONS OF INAA IN CERAMIC ANALYSIS

Pew analytical approaches highlight the problems of relating human behavior to its
material residues more than the compositional analysis ofpottery.
(Arnold et al. 1991: 70)

Ceramic materials, owing to their complexity and plasticity, pose a challenge for compo-
sitional analyses. Three main sources of variation combine to affect the bulk chemistry of
pottery.
Briefly, natural factors, including the mineralogy and texture of the parent material,
along with processes of clay formation and sediment sorting (weathering, erosion, and rede-
position), combine to create the composition of the raw clay. Chemical differences among
bedrock types, for example, ultimately translate into a distinctive trace-element signature for
a specific clay source mined by potters. Cultural factors are human actions which alter the
original composition of the clay. While some clays may be used straight out of the ground,
potters frequently modify clays through sifting, refining, mixing, or the addition of temper
to create a specific "paste recipe" for a specific type of pot. Each of these actions adds or sub-
tracts a specific component, and thus changes the bulk elemental composition (Neff et al.,
1988, 1989; Arnold et al., 1991; Sterba et al., 2009). Differences in firing temperature can also
affect the concentration of volatile elements as can the completeness of firing (Kilikoglou,
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 439

1988; Cogswell et al., 1996; Sterba et al., 2009), while specific vessel uses (such as salt man-
ufacture) can strongly modify elemental signatures through the absorption of contents.
Finally, post-depositional factors may modify the composition of the pottery once it is dis-
carded, through exposure to ground~water minerals or industrial contamination (Buxeda
I Garrig6s, 1999 ).
As a bulk chemical analysis technique, INAA confounds the contributions of these dif-
ferent factors into a single compositional profile. It is therefore essential to carefully con-
sider their potential contribution and how a given factor may alter the elemental pattern
under investigation. That is, provenance studies (which focus on geographic variation in
the composition of natural clays to identify geographic origin) need to also consider the
extent to which the distinctiveness of raw clay sources has been modified by the addition
of temper or by post-depositional contamination. Conversely, when focusing on cultural
factors such as the intensity or organization of production, the degree of natural variabil-
ity within different clay sources can be critical: some clays are naturally more uniform in
composition and may give the appearance of greater processing or standardization. It is
therefore often advisable to pair INAA with visual examination of pastes through optical
microscopy/ceramic petrography, or analyze a subset of samples with an instrUmental tech-
nique such as EMPA or LA-ICP-MS to assess how constituents of the ceramic paste, such as
a specific type of mineral temper, contribute to the bulk chemical composition (Stoltman et
al., 1992; Neff et al., 2003).

Provenance Determination
The vast majority of ceramic trace-element studies conducted via INAA are concerned with
establishing vessel provenance or geographic origin (Figure 24-5). These studies are founded
on the assumption that each raw material source or clay bed has a unique geochemical sig-
nature such that artifacts made from that source can be linked to it based on their com-
positional profile (Arnold et al., 1991; Pollard and Heron, 1996). In these applications, the
sensitive, multi-element analyses provided by INAA are critical, in that multiple dimen-
sions may be needed to accurately characterize and distinguish between clays or production
sources.
Such studies typically begin with the identification of "composition groups" or "ref-
erence groups", i.e. sets of ceramic samples that are similar in composition and distinct
from other such groups in the multivariate space defined by the trace-element data
(Bishop and Neff, 1989; Glascock, 1992; Neff, 2002; Glascock and Neff, 2003). First,
preliminary groups are identified based on obvious bi- or multimodalities in element
concentrations or key element ratios, or on subgroups of samples that consistently hold
together in multivariate cluster analyses. These preliminary groups are then tested and
refined, using multivariate statistical criteria to assess internal consistency. Each case
is tested against the remainder of its group, and the jack-knifed probability of group
membership is determined using the Mahalanobis D 2 statistic, a measure of the multi-
variate distance between that case and the group centroid relative to the dispersion of
other group members around the centroid. Where sample sizes are small, within group
distances may be calculated based on principal component scores rather than element
concentrations. Cases with low probability of group membership are removed until a set
(a) 2.4 j u H;gh Cr
(b)

2.2 I
I
2.0 j

181 ... WVG-1

E '
2:. 1.6
0
;;, VWG-2
g 1.4
u .·;·.·
1.2
!:/:.... ff H;gh r;-REE Yatzec:he ~-

1.0
.......· . . '/'
Tlapacoyan _____.-;J

0.8
Atzompa
0.6

0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8

Sc: (log10 ppm)

FIGURE 24.5 Ceramic composition groups defined for the central Valley of Oaxaca, Mexico, for the Late· Terminal Formative period.
(a) Chemical separation illustrated on a bivariate plot of Cr vs Sc. (b) Provenance as determined through INAA combined witb petrographic
analysis and regional clay survey.

··~
 INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 441

of internally consistent and mutually exclusive reference groups are defined. A third and
final step then involves the assignment ofless-secure cases to their most likely composi-
tion group, typically based on discriminant function analysis. This approach calculates
a new set of axes (canonical variates) which maximize group separation: position on
these axes is used to assign an unknown case to the most similar of the predefined refer-
ence groups.
When ceramics have been obviously tempered, the effects of variable amounts of tern-
per on the bulk composition may be accounted for by using a modified Mahalanobis
distance or filter (Beier and Mommsen, 1994). In this approach, the raw concentration
data are first scaled by the measurement error; preliminary groups are then sharpened
by removing any spread introduced by the addition of temper, using a dilution factor.
Simple tempers such as quartz sand, calcite, shell, and organic materials do not signifi-
cantly alter the relative chemical fingerprint, they only add mass to the sample, effec-
tively diluting other elements present in the clay paste. By varying this dilution factor,
differences in the amount of temper added are effectively removed from the dataset.
Within-group variation is correspondingly reduced, such that even subtle differences
between similar pastes can be resolved by traditional multivariate statiStical means
(Sterba et al., 2009).
In either case, the provenance of the resulting composition groups is determined
through comparison with production debris ("wasters"), raw clays, or experimental
combinations of clay and temper, to link the compositional signature to a specific geo-
graphic location. Where no comparative materials exist, the "principle of local abun-
dance" suggests that the most abundant pottery is of local manufacture, ceteris paribus
(Rice, 1987).
Regional clay surveys, although time consuming, can play a valuable role in establishing
regional trends in clay composition, allowing any particular ceramic compositional profile
to be assigned to a likely zone of origin within the region, even though, in the vast majority
of cases, the exact locations exploited by ancient potters will not have been sampled (Neff
et al., 1992). Such clay surveys are also useful in determining the scale of geochemical vari-
ability and the areal extent of a "source" (Bishop and Blackman, 2002; Mine and Sherman,
2011; Mine et al., 2016). For example, it is critical to know whether the compositional signa-
ture of a reference group ("source") is restricted to a single clay mine, or whether it matches
clays widely distributed within the region and thus accessible to multiple potting communi-
ties. Finally, clay surveys can indicate the most probable area(s) of production for a specific
ceramic ware, and serve to focus future archaeological research efforts to locate production
facilities (Neff, 2013).

Organization of Ceramic Production and Exchange

Once provenance has been established, archaeologists can address a series of questions con-
cerning craft production and exchange. The number and location of ceramic manufacturing
loci, their spatial relationships to each other and to centers of political control, the types of
vessels produced, their percent of market share, and the distance wares travel are all char-
acteristics of regional economic systems that can be examined once the products of a given
manufacturer have been identified.
44-2 LEAH D. MINC AND JOHANNES H. STERBA
--------- --~

Trace-element data can also be employed to evaluate changes in the intensity of

l
I
ceramic production, based on the assumption that, with full-time specialization, con-
cerns for efficiency and consistency will lead to a more uniform or standardized product
(Rice, 1991). In this case, standardization of paste recipes may provide clearer evidence of
mass production than uniform vessel size and form, since these latter characteristics may
also be dictated by functional concerns. In a now classic evaluation of the standardiza-
tion hypothesis, Blackman et al. (1993) examined the composition of fused kiln wasters-
stacks of vessels from a single firing that had melted together-from the third millennium
BC site ofLeilan, Syria. They found that in this factory-like setting, within-stack variation
was less than that measured for multiple aliquots of a NIST SRM (brick clay), indicating a
high degree of homogeneity and control over paste processing. Unfortunately, it is often
difficult to compare paste standardization at different sites, since the local clays may dif-
fer in their natural degree of homogeneity (Arnold, zooo).Thus, changes in intensity are
best measured diachronically within the same clay resource area, as for example, when
the appearance of a more standardized ceramic paste is interpreted as resulting from the
transition from multiple, small-scale producers to a more centralized, workshop level of
production.

Ceramic Technology: Assessing Potters' Choices

INAA data can also clarify aspects of ceramic technology, including the selection and
modification of raw materials. Where clay surveys have identified the range of raw materi-
als, matching the ceramics to clays will indicate which of the clay resources were utilized
and which were rejected or perhaps unavailable to the potters (Fowles et al., 2007). Further,
the use of variable mixtures of different clays and/or different temper types can be mod-
eled mathematically (Schwedt and Mommsen, 2004); in some cases, we can identify potters'
innovative solutions to technological problems, such as the addition of salt to reduce lime-
popping in calcite-tempered ceramics.
A focus on the chemical fingerprint of pastes rather than the original clays can even
shed light on ceramic technology of the early industrial era. During the late 1700s,
Staffordshire, England became the predominant manufacturing center for white earthen-
wares that strove to emulate the fine paste bodies of Chinese porcelains. Millions of vessels
were produced in factory settings (Figure 24.6) and shipped throughout Europe and the
Americas, where they graced tables of all social classes, from urban centers to frontier
settlements.
Initially located near the readily available supplies of high-quality bituminous coal, the
North Staffordshire potteries were forced to import many of the raw materials needed for
ceramic production: ball clay from Devon and Dorset, Cornish stone and kaolin china
clay from Cornwall, calcined and ground (chalk) flint from the southeast of England, and
calcined ox bone from wherever available. Since all of the major manufacturers of white
earthenwares used the same basic set of ingredients and raw material suppliers, intense corn-
petition to develop a superior product led to experimentation, the development of highly
secret paste recipes, and even documented cases of industrial espionage. The resulting paste
recipes are unique, with a chemical fingerprint distinct from the pastes of competitors (Hale,
zooS). Further, technical innovations, such as the early formulation of bone china and the
·- INAA IN THE STUDY OF ARCHAEOLOGICAL CERAMICS 443

Ib)

oj

j
I
_,j
I TJ
cD . ·'8
~.3·~::~:()::0/SA . . . ~·
,

p •
<ii-101 ~~ ~=> • ,' ··..,~·.
r:~l'~¥
·2o
iJ -lS I
I!
>.·.if!·.
• •
7 • ' :• •
V :·.: 1 ,.
~ Spod<W<« A
Mioitoo B

lI Davenport 8 •
DavenportC
Enoch Woods tt Sons
~
i •
! Wm. Adams H Sons B • •.: •
-2o.L~··~---~··~--~--- " ---_J
0 10 15 20 25
Canonical Variate 1

FIGURE 24.6 (a) The industrial potteries and bottle kilns of North Staffordshire, England,
c.1900 (from an historic postcard labeled 'Fresh Air from the Potteries'). (b) Each pottery
manufacturer developed one or more paste recipes, with a distinctive trace-element compo-
sition (after Hale, zooS).

addition of cobalt to lend a whiter hue, are clearly recognizable from the trace-element
composition.

CONCLUSION

INAA has become a main-stay for bulk chemical characterization of ceramic artifacts and
clays. The sensitivity, precision, and multi-element capability of this method make it par-
ticularly well suited for characterizing these complex materials. Determination of vessel
provenance remains the most common application of INAA, and serves as a foundation
for addressing a broader range of questions concerning ceramic production and exchange.
Increasingly, however, INAA is also being employed to investigate questions of ceramic
technology and manufacturing, helping to reconstruct the choices potters made in carrying
out their craft.

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 CHAPTER 25

SYNCHROTRON RADIATION

ALAN F. GREENE

INTRODUCTION

SYNCHROTRON radiation (SR) based techniques-methods utilizing the energies produced by

the monumental particle accelerator instruments known as "synchrotrons" -have enjoyed sev-
eral decades of application in archaeological pottery analysis (Harbottle eta!., 1986; Nakai eta!.,
1991; Nakai and !ida, 1992; Kockelmann et al., zooo; Pantos eta!., 2002; Uda et al., 2005; Creagh,
2007; Creagh and Bradley, 2007). It is only in the last twenty years, however, that a coherent
body of scholars applying synchrotron methods and developing new techniques for archaeo-
logical ceramics has coalesced. This community remains a small one however, and much of
its coherence derives from participation in the biannual Synchrotron Radiation in Art and
Archaeology meeting (SRzA)' (Schreiner eta!., 2004; Eberhardt et al., 2oo8; Janssens, 2011). The
intense heterogeneity of the synchrotron community is regularly emphasized by the sheer ana-
lytical diversity of the methods and research questions employed by its members. From X-ray
diffraction (XRD) and fluorescence (XRF), to microtomography, X-ray absorption spectros-
copy (XAS), infrared (IR) microscopy, X-rayscattering (XS), and neutron diffraction (ND), the
analytical diversity of synchrotron applications results from the unique nature of the method
itself: synchrotrons present a striking level of energy "tunability" and instrumental customiza-
tion. Current approaches are therefore often merely scratching the surface of their potential
for archaeological ceramic analysis. This chapter outlines the instruments, methods, common
material foci, logistical concerns, and research contexts of synchrotron ceramic studies, includ-
ing their contributions to the broader anthropological and archaeological understanding of
global pottery making and the future of synchrotron instruments as essential research tools.

SYNCHROTRON RADIATION AS
AN ANALYTICAL RESOURCE

Synchrotron radiation is made up of highly polarized light .or electromagnetic radiation

produced in large-scale accelerator facilities and focused into a beam with a high degree of
--------·~--····

448 ALAN F. GREENE

parallelism, ranging over energies as low as infrared light to so~called "hard" X-rays (Nakai,
l
I
2005: 183-184). Equally important as the form of this radiation, however, is the process of
its generation, which is responsible for the majority of the method's utility in the analysis of
archaeological ceramics. In order to produce synchrotron radiation, electrons or protons are
sped to high velocity by a linear accelerator and sent into orbit within a storage ring or "syn-
chrotron:' Placed at various locations throughout the storage ring, magnets regularly bend
the path of the accelerated particles as they circulate, provoking the production of electro-
magnetic [synchrotron] radiation (Winick, 1994).'
Based on the polygonal ring structure of a synchrotron facility (see Figure 25.1), SR is
siphoned off at oblique angles, focused into beams, and transmitted down "beamlines" that
terminate in experimental stations, or "hutches:' Bearnlines at different points on the ring,
in relation to the position of the linear accelerator or "booster" ring structures that maintain
the movement of particles, are able to harness beam energies of different strengths and char-
acters relevant for conducting different types of analysis. Beams "tapped" from a synchro-
tron ring are four to ten orders of magnitude stronger than conventional sealed-tube X-ray
emitters and have a more consistent, continuous distribution, allowing the aforementioned
broad range of monochromatic tunability across a specific portion of the ER spectrum

generates
synchrotron
radiation

Monochromator
selects X-ray
wavelength
Incident beam
Experimental travels through
Station vacuum tube Mirror focuses
X-ray beam

FIGURE 25.1 Schematic of the Australian Synchrotron's small- and wide-angle X-ray
scattering beamline by David Cookson and jonathan de Booy. The circular structure is the
synchrotron apparatus and electron storage ring. The yellow components represent dipole
magnets that incrementally change the electron beam trajectory-keeping the particles in
a stable, closed orbit around the ring. The red and green components are quadrupole and
sextapole magnetic structures that keep the orbiting electrons in compact bunches. SR pro-
duced upon the bending of the electron beam by undulator insertion devices (also drawing
on dipole magnets) is directed down the beamline and through various X -ray optical devices
that control the bandwidth, photon flux, beam dimensions, focus, and collimation of the
rays. At the end of each beamline is an experimental station where pottery samples may be
positioned and analyzed.
 SYNCHROTRON RADIATION 449

(Pantos, 2005: 199). 1bis increased number of photons is evaluated in terms of"brilliance;'
or the number of photons produced per second multiplied by: (1) the speed at which the
beam spreads out (in square milliradians), (2) the cross-sectional area of the beam (in square
mm), and (3) the photons falling within one bandwidth (BW) of the central wavelength or
frequency (Winick, 1994):

brilliance= photons I seconds* mrad 2 * mm 2 * 0.1 %BW

The high parallelism of SR is referred to as high "collimation" and allows for the non-
destructive evaluation of archaeological pottery. Thus, SR beams are able to be generated
at energies high enough to transmit completely through a sample to study internal pottery
structures (fabric) and tuned to wavelengths appropriate for the desired instrumental tech-
nique (Pantos, 2005: 199 ). High collimation also allows an SR beam to be targeted at specific
microcrystalline structures in archaeological materials through the use of small spot sizes,
largely referred to as "small footprint" (Pantos, 2005).

INSTRUMENTATION AND LOGISTICS

Synchrotron analytical setups, the vast majority of which rely on hard X-ray beams, are
remarkably modular and adjustable, only rarely requiring sealed analytical environments
and/or restricted sample spaces like many other analytical instruments, because the SR
beam travels through air without the need of a vacuum. It is easy to generate a microbeam-
as demonstrated in several of the "Topics oflnvestigation'' subsections below-through the
insertion of slits or focusing optics. In a typical setup, illustrated in Figure 25.2, the sample
holder is located between the SR beam entrance and the detector, and incorporates software
controls and beam modifications as needed. Holders are often custom configured for each
experiment, including the use of flat stages where a potsherd or vessel receive beam energy
from above, the "standing" of potsherds along a metal rail perpendicular to the incoming
beam, or the affixing of potsherds to a flat Lexan board. However, just about any situating of
the sample between beam and detector at an appropriate distance is a viable configuration.
Translating sample stages are often employed to efficiently analyze samples in batches or to
submit them to multiple exposures through the use of incremental movements (referred to
as "local spatial averaging"). The resultant data, in quantitative, semi-quantitative, and image
formats, may be assembled and analyzed through a relevant series of statistical descriptions,
computations, or manipulations.
If the detector utilized is appropriately fast in returning data and the beam sufficiently
brilliant, samples can be rapidly processed, allowing for the quick generation of results
and high volume analysis of ceramic materials. This is an instrumentation amenable to the
analysis oflarge sample populations of excavated pottery, where N may be equal or greater
than woo. The non-destructive nature of SR also makes the method highly attractive
for the analysis of unique and/or valuable museum pieces and microsamples, exploiting
both targeted and bulk investigation. The non-destructive quality ofSR notwithstanding,
many of the techniques and studies described in the following sections rely on destruc-
tive or semi-destructive sample preparations. These include the transmission analysis and
450 ALAN F. GREENE

Slit

Si(400)
II
monochoromator
XRF

X, Z stage

Detector Controller

FIGURE 25.2 One potential schematic of an experimental setup for SR pottery analysis,
here micro-X-ray fluorescence, showing the positioning of the SR beam, sample, and solid-
state detector (Nakai 2005, Figure III-I -I).

imaging of thin sections or X-ray powder diffraction (XRPD ), which requires the removal
of abraded material from the potsherd or vessel. It should be noted, however, that SR-
based pottery analysis writ large does not require any such destructive preparations per
se. It is the choice of these specific applications of SR, these techniques, that necessitates
destructivity.
Synchrotrons are constructed at specific and differential sizes and, therefore, energy
capacities, thus delimiting the particular competencies of different facilities.' It is essential
when planning a project using synchrotron radiation to identifY the most relevant compo-
sitional or structural technique, the level of destructivity permitted, and the synchrotron
instrument where the former parameters are analytically achievable. In addition, the geo-
graphic location of synchrotrons, distributed most intensely in the USA, Western Europe,
and East Asia, can limit the ability to analyze archaeological materials, which are often
subject to legal transport restrictions. Individual synchrotron facilities are referred to by
their various acronyms. The instruments most active in SR-based pottery analysis include:
the Advanced Light Source (ALS) at Lawrence Berkeley Laboratory, USA; the Advanced
Photon Source (APS), at Argonne National Laboratory, USA; the Daresbury Synchrotron
Radiation Source (SRS), England (currently undergoing decommissioning), the European
Synchrotron Radiation Facility (ESRF), France; ISIS, at Rutherford Appleton Laboratory,
England; Source optimisee de lumiere d'energie intermediaire du LURE (SOLEIL), France;
and the Stanford Synchrotron Radiation Lightsource (SSRL), USA. These centers have
drawn more heavily upon museum materials than on recently excavated assemblages in
their analysis of archaeological pottery. In addition to the aforementioned American and
European facilities, synchrotrons are under construCtion or proposed across important
archaeological landscapes such as jordan (Synchrotron-Light for Experimental Science and
Applications in the Middle East, SESAME) and Armenia (Center for the Advancement of
Natural Discoveries using Light Emission, CANDLE). Thus, it is possible to foresee a future
 SYNCHROTRON RADIATION 451

analytical landscape in which synchrotron pottery studies are incorporated more substan-
tially into active field projects without requiring intercontinental transport.

TOPICS OF POTTERY INVESTIGATION WITH SR

Due to the exceptionally brilliant beam energies generated by synchrotrons, many of the
research questions most commonly investigated using SR focus on the delicate and nano-
scale properties of surface treatments, including paints and pigments, slips and glosses, and
(iridescent) lustre (Pradell et al., 2006, 2oo8a, 2oo8b; Sciau et al., zoo6, 2008, zan; li\ai\ez et
al., 2013). Detailed three-dimensional examination of the structures and interfaces between
surface treatments, such as slips or engobes, and the clay body are an increasingly popu-
lar area ofSR research (Meirer et al., 2013; Walton et al., 2013). Much of the existing SRlit-
erature on archaeological ceramics focuses on identifying techniques of manufacture: the
determination and reconstruction of ceramic production relying upon both the analy-
sis of archaeological samples and on experimental materials prepared in the laboratory.
Assemblage-based analysis of ceramic materials from active excavations is significantly less
common. This review treats each of the existing SR research foci in the context of their utility
to ceramic analysis more generally, as well as their broader subdisciplinary contributions. It
then addresses prospects for shifts in methodological focus and possibilities for future tech-
nique development.

SR Analysis of Paints and Pigments

Considering the abundance of small-footprint X-ray-based SR approaches for materials
analysis, it is not surprising that analysis of surface treatments, such as paints and pigments,
are predominant in SR studies of archaeological pottery. Paints and pigments are also a pop-
ular domain of research because of the comparatively low energies required to affect analy-
sis: more intense, transmission beams produced by the largest accelerators are not necessary
for this kind of research, and the vast majority of synchrotrons possess the capacity to carry
it out. Painted pottery collections of significant ancient and historical heritage have been
particularly well analyzed with SR because they can be examined in a completely nonde-
structive manner.
The most substantial body of research into paints and pigments stems from the investi-
gation of the painted pottery of the American southwest (van der Weerd et al., 2004; Geil
et al., 2013; li\afiez et al., 2013) and the blue pigments used in the manufacture of white and
blue Ming dynasty vessels in China (Wen et al., 2007). Research has also has examined the
substantial corpus of painted pottery associated with the Cucuteni-Tripolye culture of the
Eastern European Neolithic (Chapman 2002; Kohl2007). SR-based investigation of south-
western painted wares has focused on revealing and mapping pigment distributions, lever-
aging the integrated, high-volume analysis of large collections by SR ~-XRD (Pradell et
a!., 2010), XRF imaging (XRFI) (Adams eta!., 1998; Kanngie~iier et al., 2003; Vincze et al.,
2004), and vibrational microscopy with infrared SR (IR-SR) (Carr et al., 1995). The com-
bined efforts of these studies have facilitated the technological description ofPuebloan black
452 ALAN F. GREENE

pigment production and application. The analysis of American-produced majolica (Molera

et aL, 1996; Tite et al., 2008) examined differences in European and American production
(Ifiafiez et al., 2013) by identifying local technological features mixed with European pig·
ment recipes via targeted SR ~-XRD of pigment areas, supplemented by SEM investigation
(Figure 25.3).
Research into Ming blue and white pottery (Garner, 1956; Geng, 1993) using SR XRF has
shed light on both the chronological and technological aspects of raw material sources,

MSL039

cassiterite
hematite-

tassiterite (Sn0 2)
diopside - (Fe, Ca. Mg) Si 20 8
Ca-feldspar- (Na, Cal (AISi) 40 8

diopside- (Fe, Ca, Mg) Si 20 8

Ca-feldspar- (Na, Ca)(AISi) 4 08

10 20 30 40

FIGURE 25.3 From top left, counter-clockwise: photograph, reflected light micrograph,
SEM micrograph, and ~-XR diffractogram of the yellow-glazed area of a sherd from Mission
San Luis (Florida, USA) collected during the analysis of American majolica by SR (lfiafiez et
a!., 2013, Figure 4).
 SYNCHROTRON RADIATION 453
--
facilitating the reconstruction of blue pigment recipes as they changed over time and the
identification of local and imported raw materials (Wen et al., 2007). Finally, research into
the manufacturing procedures and trade routes relied on by Cucuteni people (Chapman,
2002) has focused on the Neolithic pottery produced by these ancient Europeans, relat-
ing pottery production to both local and regional scales of pigment resource procure-
ment through (SR) X-ray powder diffraction (XRPD) (Constantinescu et al., 2007; Bugoi
et al., 2008).
In this fashion, primary and dominant approaches to synchrotron-based analysis of
paints and pigments rely on XRF and XRD to record elemental and mineralogical compo-
sition, respectively (see Fan et al., 2005; Huang et al., 2005; Lei et al., 2005; Nakai, 2005).
While these studies will continue to be important for SR-based analysis of pottery paints and
pigments, several innovative approaches are already making valuable contributions. These
include methods like SR X-ray fluorescence imaging (XRFI) that apply simultaneous com-
positional and structural analysis to achieve a powerful and efficient characterization regime
(Geil et al., 2013). In the case ofXRFI, this is accomplished through the three-dimensional
mapping and classification of compositional components, allowing detailed observation of
surface and immediately subsurface features. Other innovative SR approaches to the anal-
ysis of paints and pigments include combined [l-XRD and (non-SR) SEM, which provide
complementary compositional and structural data related to pigment constituents, applica-
tion histories, and general painting technologies. IR-SR microscopy has also been used to
detect organic pigment constituents, generally with encouraging results (van der Weerd et
al., 2004).

Slips and Glosses

SR-based research has played a critical role in the investigation of slip and gloss surfaces. In
fact, slips and glosses have attracted almost as much attention in SR analysis of archaeologi-
cal ceramics as paints and pigments. The increased thickness of slips and glosses, compared
to painted decoration, has prompted analysts to use more destructive or invasive meth-
ods, such as thin-sectioning or powder diffraction (PD). However, the novel application of
microscope-coupled compositional analysis and microtomographic tools may mitigate the
invasive and/or destructive SR analysis of slips and glosses in the future (see for example
Meirer et al., 2013).
Most of the SR analyses of slips to date have focused on investigation of Mediterranean
Terra Sigillata wares. Terra Sigillata, also referred to as ''Arretine" or "Samian" ware, is a glossy
red-slipped Roman tableware dating to the mid-firstto mid-thirdcentury AD (Vernhet, 1981;
Peiia, 2007). Sciau et al. (2006, zoo8) have used SR-based techniques to both analyze the
basic technology of Terra Sigillata slips and investigate regional production variation and
unique subvarieties, such as "marbled" Terra Sigillata (Leon et al., 2010) and southern Gallic
pre-Sigillata pottery (Mirguet et al., 2009).
Initial research with SR focused on [l-XRD analysis of Terra Sigillata slips in order to bet-
ter understand the size and distribution of the constituent phases (Sciau et al., 2006), which
have been extensively studied with non-SR methods (Picon et al, 1975; Sciau and Vezian,
2002; Vendier et al., 2002). In particular, the glossy properties of the slip were confirmed to
result from a glassy aluminum and quartz matrix, within which were embedded corundum
454 ALAN F. GREENE
',,_,,

and hematite inclusions of specific sizes and frequencies. Researchers have also investi-
gated potential raw materials available to the southern Gallic La Graufesenque (Vernhet,
1981) pottery workshop using SR-based XRD during "live'' test firing, not dissimilar from
the time-resolved, live firing analysis of medievallustreware described in the "Lustrewares"
section ofthis chapter (Sciau et al., 2008). These results confirmed the use of illitic clays with
low Mg content as the essential ingredient for corundum crystallization during firing.
A subvariety of Terra Sigillata from the La Graufesenque workshop, termed "marbled"
Terra Sigillata because of swirled yellow and red slip components, has also been investigated
using SR ~-XRD and ~-XRF in order to identify the specific raw materials and production
technology involved in its rather distinct production (Leon et al., 2010). Leon et al. (2010)
identified pseudobrookite, an iron and titanium-based mineral recently recognized as a
potential modern coloring agent (Monr6s et al., 2010), as the essential component respon-
sible for the yellow marbling. Leon and colleagues argue-and their mutually reinforcing
elemental and mineralogical SR analyses, combined with several forms of microscopy, make
a rather convincing argument-that the mere presence of pseudobrookite is not responsible
for the polychrome slip. Rather, it is a combination of the raw materials, slip recipe, and fir-
ing condition that together create the marbled effect.
In southern Roman Gaul, the production of local Terra Sigillata was preceded by a ware,
termed "pre-Sigillata;' that many researchers have argued was "inspired by" or "imitated" the
Sigillata wares being produced to the east (Passelac, 1992; Genin et al., 2002; Martin, 2002).
The technological differences between the production of these pre-Sigillata imitations and
Terra Sigillata itself, therefore, constitute an important area of research for understanding
the archaeology of colonialism and technological innovation. By combining SR XRD with
electron microscopy of pre-Sigillata ware from La Graufesenque, researchers have been
able to determine that while the forms ofpre-Sigillata wares in southern Gaul may resemble
Terra Sigillata, their slips were manufactured using different raw materials and firing tech-
nology; the intentional use of a reducing atmosphere in the kiln produced a black gloss on
the vessels, a coloration not associated with Sigillata (Mirguet et al., 2009 ).
Pre-Sigillata and Terra Sigillata comparisons were also conducted by Sciau et al. (2ou),
utilizing SR ft-XRF and ~-X-ray absorption near-edge spectroscopy (XANES) analysis
on existing SEM or electron microprobe (EMP) "cross-sections" (i.e., thick sections), in
order to more clearly understand the firing technology of pre-Sigillata materials. They
have successfully identified differences in the preparation of substrate materials and fir-
ing techniques for pre-Sigillata vessels from different Gallic workshops, and from Terra
Sigillata manufactured in Gaul and Italy. The authors note that both inter- and intrawork-
shop variability can be observed and they posit that a larger scale, regional, diachronic
scale study of pre-Sigillata ware, using the same methods, would facilitate a better under-
standing of how different potters approached the sociotechnical problems associated
with this assemblage.
Another important body ofSR research focused on slips is the analysis of so-called "black
gloss" or "red figure" Attic pottery. Red figure Attic ware, produced between the sixth and
fourth centuries BC, is well-known for its elaborate firing technology, which alternated
between oxidizing, reducing, and (re)oxidizing atmospheres, to create the characteristic red
depictions on a black slip background (Noble, 1965; Boardman, 1975; Papadopoulos, 2003;
Kahn and Wissinger, 2008). Tang and colleagues (2001) usedSRhigh-resolution powder dif-
fraction (HRPD) and synchrotron-based XRF, perhaps its first application in archaeological
 SYNCHROTRON RADIATION 455

science (Tang et al., 200t:l016), to investigate whether the method would effectively char-
acterize the variability in mineralogical composition between three fifth~ and sixth-century
black gloss potsherds from a collection at the Manchester Museum. Although the pri-
mary goal of the study was to demonstrate the utility of the method, initial findings dem-
onstrated that the compositional differences previously observed in analyses of red figure
pottery are related to differences in manufacture technology and not, as previously sup-
posed, to the differential capabilities and detection limits of the instruments employed. In
particular, Tang et al. established that the slip recipe, its ferrous content, and vitrification
extent are determined by sociocultural and technological choices. Soil conditions are also
pointed to as having had a potential impact on the ferrous phases observed in these materi-
als. Their research demonstrates the contribution of SR to diachronic technological studies
of archaeological pottery.
Most recently, a study combining SR XANES with scanning transmission electron
microscopy (STEM) and LA-ICP-MS has challenged the hypothesis that Attic red fig-
ure wares were produced through a single, multi-atmosphere firing (Walton et al., 2013).
Analysis of three structurally distinct components of the black gloss ornamentation on a
single potsherd revealed significant mineralogical differences, but rather minor elemen-
tal ones, between two of the three ornamentation subparts, the so-called "relief line;'
"contour line;' and "background gloss" (Figure 25-4). Thus, the authors conclude that at
least two firings were necessary to achieve this microstructural result, suggesting that the
black gloss decorations were applied over the course of, or rather between, multiple firing
events.
Another study, undertaken by Gliozzo et al. (2004), used SRX-ray absorption spectros-
copy (XAS), together with SR HRPD and electron microscopy, to evaluate the oxidation
state and define the material properties responsible for differences in the appearance of sur-
face treatments of black gloss pottery from across Etruria. The gloss on black gloss pottery
ranges from a brilliant shining appearance, to silver black, to matte, and Gliozzo et al:s study
was able to establish that, while slip thickness and porosity have some influence, the firing
protocols and slip recipe used in its production are primarily responsible for its appearance.
SR XAS was used to demonstrate the link between the Fe oxidation state in the gloss and its
appearance.
Finally, a study of Roman black gloss pottery by Meirer et al. (2013) demonstrates the
remarkable "multimodality" -that is, the ability to analyze objects from multiple scalar
perspectives and multiple instrumental platforms (see Greene and Hartley, forthcoming)-
of SR instrumentation. Analysis of one Campanian B sherd and one pre-Sigillata sherd
from the La Graufesenque workshop using SR XANES suggests rapid technological shifts
in the production of these wares during the first century AD (Meirer et al., 2013). Meirer and
colleagues, using synchrotrons in France (European Synchrotron Radiation Facility, ESRF)
and the USA (Stanford Synchrotron Radiation Lightsource, SSRL) (along with standard
(non-SR) XRD and Raman spectroscopy), exploit the ability ofSR instrumentation to com-
bine high-resolution compositional and structural analysis, specifically XANES-enabled
full field hard X-ray transmission microscopes (TXM). By performing compositional
mapping and determinations of sample porosity (derived from tomography) in concert,
the researchers were able to: (1) establish that sophisticated firing technology allowed pro-
ducers to (re)oxidize both samples without (re)oxidizing their slips, and (2) determine
that significant differences in firing technology between the per-Sigillata and Campanian
456 ALAN F. GREENE

(a) l

(b)

(c)

FIGURE 25.4 The three micro regions of interest on a "black gloss" or "red figure'' potsherd,
as investigated by Walton and colleagues with a diverse set of SR methods (Walton et al.,
2013, Figure>).

B potsherds likely involved both lower temperatures and shorter duration firing for the
Campanian sample. Unfortunately, the small sample population means the authors' asser-
tions regarding short-term technological change require further evidence. However, the
elegant and comprehensive nature of the approach, combined with its integrated and
-------------~~~---"-~-""

SYNCHROTRON RADIATION 457

simultaneous compositional and structural analyses, set a new standard for multimodal
analysis of surface treatments.

Lustrewares
If paints and pigments represent the most external, protruding surface treatment available
for archaeometric investigation and slips thicker and more significant surface structures,
lustre glazes~ rich metallic layers with iridescent optical properties~are a surface treat-
ment situated somewhere in between (Pantos, 2005; Caiger-Smith et at, zoo6; Pradell et aL,
zoo6, zoo Sa, zoo8b; Reillon and Berthier, 2006). Pottery decorated with lustre glazes or "lus-
trewares" are formed through a special firing process. After the ceramic body has been fired
and the glaze vitrified, which can result from single or multiple firing events, a paint or paste
containing a Cu or Ag oxide suspension is applied to the ceramic body. The vessel is then
fired at low temperature in a reduction kiln (Pradell et aL, 2006, zoo8a). During this firing
event, interaction between the metal oxide suspension and the glaze results in ion exchange
and "melt" activities that promote the reduction of the CuiAg and help distribute them
across the glaze surface, resulting in a lustrous appearance. Pradell and colleagues (zoo6,
2oo8a, 2008b) have used SR to investigate lustreware manufacturing techniques across the
Middle East due to the method's non- or minimally destructive nature and its multimodal
ability to be tuned and applied in multiple beam configurations and analytical modes. Initial
research, using SR-XRD, focused on characterizing the lustre layers observed in experimen-
tal samples produced using recipes from the Islamic Period to determine the effect of various
metal and flux mixtures, ceramic body compositions, and firing atmospheres on resultant
lustre. Oxidizing or inert atmospheres were shown to be essential firing components, prior
to the reduction-driven formation of metallic states in the glaze (Pradell et al., 2oo6: 203).
Subsequent SR studies of lustreware have utilized time-resolved temperature experi-
ments, the firing of lustre materials or layers in front of a ('live" SR beam, in order to docu-
ment the stages and atmospheric conditions under which specific ionic exchanges take place
(Pradell et al., zoo8a). Figure 25.5 provides an example of the high-temperature XRD pattern
from one of these time-resolved analyses. The rather dramatic experiments utilized high-
temperature SR XRD, XRPD, and L-edge Cu XANES oflustreware reproductions at both the
European Synchrotron Radiation Facility (ESRF) and the Daresbury Synchrotron Radiation
Source (SRS).
Pradell et al. (zoo8b) have also engaged in diachronic and regional analyses of variation in
lustreware production across the Middle East between the tenth and thirteenth centuries AD.
They examined the structure and composition of the lustre glaze using SR ~-XRD, XANES,
and extended X-ray absorption fine structure (EXAFS) analysis to evaluate changes in tech-
nology at different production centers and their relationships to concurrent sociopolitical
shifts in the Early Islamic world. The findings (Smith et al., zoo6; Pradell et al., zooS) suggest
that the rise and fall of Fatimid dynasty rule appears to have coincided with important tran-
sitions from low-lead to high-lead lustre/glaze recipes.
Research by Reillon and Berthier (zoo6) at the Louvre's accelerator facility Accelerateur
Grand Louvre d'analyse elementaire (AGLAE) has focused on the optical properties and
structural arrangements of the metallic nanoparticles in lustrewares. These nanoparticles
are essential to the iridescent properties of lustre glazes. At AGLAE, Reillon and Berthier
I
I

J
458 ALAN f. GREENE

illite
quartz alpha
magnetite
cuprile
C"'
l

quartz beta

10 60 cinnabar
angle (29) hematite
met.3Cinn<lbar
I •.. ll.j.,

FIGURE 25.5 An example of a high-temperature XRD pattern collected during "live" time-
resolved temperature experimentation by Pradell and colleagues (zoo Sa, Figure 4). Prepared
lustre paint was applied over a glaze surface prior to the temperature-controlled experiment.
Colors denote distinct crystalline phases as identified by SR XRD, while the triangle symbols
indicate their respective emergence and disappearance over time.

used accelerator-based particle induced X-ray emission (PIXE) and Rutherford backscat-
tering spectroscopy (RBS) to determine the elemental distribution and patterning (micro-
structure) of phases in lustre glazes, and explain the physical basis for lustre, demonstrating
in the process that composition alone cannot explain its optical properties. In this way, com-
positional observations receive essential context from structural SR-based data pertaining to
particle size collected in parallel.

Mineralogical and Elemental Characterization by SR

It has yet to be demonstrated that there are significant advantages to bulk compositional
analysis of archaeological ceramics by SR. However, it has indeed been used to perform XRD
and XRF studies of mineralogical and elemental composition. The greatest potential advan-
tage ofSR-based instruments for compositional characterization is the method's modular or
multimodal capacity (c.f. Greene and Hartley, forthcoming).
Broekmans and colleagues, studying north Mesopotamian pottery from Tell Beydar,
Syria (2004, 2006, zooS), used SR XRPD to evaluate the compositional diversity of these
materials. Initial SR analyses (Broekmans et al., 2004), in concert with semi-destructive
 SYNCHROTRON RADIATION 459

ceramic petrography and SEM analysis, examined limestone-tempered Early Bronze Age
cooking wares from the site to understand how their mineralogical content and maxi~
mum firing temperatures promoted their technological suitability for food preparation.
In another project, researchers identified three fabric groups within the "metallic ware"
assemblage recovered from Tell Beydar (Broekmans et al., 2006). Metallic ware is a fine
ware manufactured from very dense clay, free of aplastic inclusions, and resembles con-
temporary metal vessels in form. By comparing the metallic ware assemblage to other
potting traditions at the site and evaluating the intra-assemblage variety of the analyzed
material, Broekmans et al. (2006) were able to use SR XRPD data to differentiate local
from non-local metallic ware and to identify calcareous "imitations" of the dominant
non-calcareous metallic ware assemblage (Broekmans et al., 2006: 226). Using the same
method, Broekmans et al. (zooS) also compared the paste preparation and firing of the
cooking ware, tableware, and metallic ware assemblages and demonstrated that each sub-
assemblage required a rather distinct set of production techniques. Thus, for Broekmans
and colleagues, this work produced useful information about specific local and regional
production trends, but it is less clear exactly how the research has contributed to the
broader understanding of Early Bronze Age life in Mesopotamia differently than had it
been performed with non-SR methods.
Other characterization studies have focused on the pottery from Early Bronze Age
through Islamic Period Kaman-Kalehiiyiik, Turkey (Matsunaga and Nakai, 2004), utiliz-
ing SR XRF and XANES to examine iron spectra and firing differences; and on Attic white-
ground lekythoi ceramics (Walton et al., 2010), using XANES and EXAFS to understand
more precisely the role of these materials in the pyrotechnics of cremation burials. Both
studies were designed to confirm existing archaeological interpretations of the assemblage,
rather than to examine new aspects of these materials.
Ceramic compositional studies conducted with synchrotron-based neutron beams, such
as the one available at the Rutherford Appleton Laboratory in Oxfordshire, England, can be
done non-invasively and non-destructively (Barone et al., 2011: 1060). Research by Barone
and colleagues (zon) has demonstrated that time-of-flight neutron diffraction (TOF-
ND) can be used to identify the mineralogical composition of archaeological ceramics as
accurately as standard (non-SR) XRPD. '!he authors note, however, that fine-grained and
homogeneous texture are necessary for accurate TOF-ND, which poses a difficulty for its
application to the analysis of numerous archaeological potting traditions.

FUTURE PROSPECTS FOR SR IN POTTERY

ANALYSIS: THE LIGHT FANTASTIC

The different approaches and research strategies discussed in the preceding sections out~
line a broad analytical terrain for the SR-based investigation of archaeological ceramics,
focused most intensely on their surface treatments. There iS no reason, of course, that pow-
erful SR energies cannot be more usefully applied to the analysis of ceramic bodies (e.g.,
through more penetrating "transmission" forms of X-ray scattering and tomography), or
460 ALAN F. GREENE

to larger~scale phenomena relevant to the paste preparation, formation, firing, and use of
archaeological pottery. As experienced SR researchers build more extensive relationships
with the archaeological community, such opportunities will undoubtedly present them-
selves. In fact, combining the strengths of multimodal SR analyses with morphometric and
typological ones provides context and spatiotemporal resolution for the mineralogical and
chemical data collected by many SR methods.
SR-based studies have, thus far, used a wide variety of experimental approaches, most
intensively X-ray absorption spectroscopy, diffraction, fluorescence, and scattering
most intensively. However, as SR moves from an emergent subfield to a more widely
recognized approach to archaeological ceramic analysis, standards and procedures will
undoubtedly come into finer focus and more active debate. For example, should not
the archaeometric standards for sample population size followed by users of non-SR
instruments apply to SR research as well? Can SR continue to be lauded for its non-
destructivity if samples are often powdered and thin-sectioned? These questions are as
much logistical as methodological and ethical: synchrotron researchers have not built
relationships with archaeologists from whom they would acquire large assemblages for
analysis; synchrotrons are located in limited geographic locales and are decidedly non-
portable; and canonical techniques require specific, and sometime destructive sample
preparations, no matter the source of radiation used in their execution. Nevertheless,
these issues are imminently surmountable through innovative efforts in the develop-
ment of more formal analytical protocols, increased professional interaction, additional
synchrotron development and construction, and development of techniques that are
less destructive and invasive.
An example of SR analytical research and technique development occurring side-by-
side is the Making of Ancient (MAE) Eurasia (MAE), a collaboration between scholars at
the Advanced Photon Source (APS) synchrotron, the Australian Synchrotron, and at vari-
ous American universities, including Stanford University and the Stanford Synchrotron
Radiation Lightsource (SSRL). By collating archaeological ceramic assemblages from multi-
ple domains across the Eurasian landmass, these efforts are advancing the SR analysis oflarge
sample populations·( n <: woo) in order to take advantage of the powerful, diverse, and flexible
properties of the resource. The APS is a particularly powerful instrument (7 GeV) and MAE
is attempting to leverage this power to perform penetrating, non-destructive analyses of the
composition and microstructure of the internal body (non-surface) portions of potsherd and
whole vessel samples.
'!be wide variety of available SR methods for the investigation of archaeological ceramics,
combined with the rather decentralized nature ofits publication and alack of strictly-delim-
ited, "standard" analytical practices, are characteristic ofboth the subfield's emergent nature,
but also ofSR itself as an analytical tool. Its flexible, tunable, and modular properties enable a
remarkable host of differential approaches to similar analytical goals or research objectives.
On the one hand, an analyst may fmd the lack of clearly defined methodology frustrating,
but on the other hand, it allows a degree of technique development to occur in the context
of each analytical project. This ability to both analyze and methodologically innovate makes
synchrotron radiation a particularly dynamic and exciting approach to the study of archaeo-
logical ceramics.
 SYNCHROTRON RADIATION 461

NOTES
-~----------~--~---~-

1. See <http:/ /www.bnl.gov/sr2a/ and http:/ /www.icom~cc.org/51/news/?id=263#.

VC)NUytdUa8> for details on the 2012 and 2014 meetings of this research group,
respectively.
2. While circular particle accelerators like synchrotrons cannot produce protons, it is pos~
sible to produce neutron beams as a byProduct of the acceleration of other particle types
(Winick, 1994). See the section "Pottery Characterization with SR'' in this chapter for an
example of neutron beam application in archaeological pottery analysis.
3. The website lightsources.org maintains a useful list of existing synchrotrons, facilities
under construction, and those simply proposed.

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 PART V

INVESTIGATING
CERAMIC
MANUFACTURE
 CHAPTER 26

ETHNOGRAPHY

KENT D. FOWLER

INTRODUCTION

CERAMIC ethnography is a research method used for documenting the manufacture, dis-
tribution, use, and discard of ceramic objects in modern societies. Being particular to a
time and place, ethnographic researchers have the benefit of focusing on the complexity
of relationships between ceramics and society. As a method, ceramic ethnography gener-
ates data that forms a "system of reference" for problem-oriented research strategies aimed
at either improving the analogical repertoire of archaeology (David and Kramer, 2001), or
"a better understanding of the diverse ways material culture operates in living societies"
(Cunningham, 2003: 393). 'Wallowing in the particular" and engaging in "thick descrip-
tion" allows an exploration of the relationships amongst people and things; a major focus
of anthropological and archaeological inquiry. Beyond this, ethnographic data provides
breadth and depth for archaeologists interested in defining regularities in human behavior
and generating cross-cultural correlates that "allow the archaeologist to climb the pyramid
of inferences and interpret archaeological facts in terms that are specific to an historical situ-
ation for which there is not necessarily any analogue" (Roux, 2007: 173).
1be aim of this contribution is to consider how ethnographic research contributes to the
understanding of present and past ceramic manufacture. In doing so, it is necessary to set
certain limits on a rich and varied literature. I emphasize research approaches over theo-
retical ones, and the breadth of geographical and linguistic coverage is limited to poignant
or illustrative examples of attempts to service more nuanced, complex, and realistic under-
standings of pottery production systems. Winnowing the contributions of ceramic ethno-
graphic research in this way allows us to explore particular concepts, problems, approaches
and apparent truisms affecting how we move from the study of things to the "intangible
qualities of social existence" (Costin, 2007: 145).
Explaining variation in pottery and potting practices is the main issue of interest for both
ethnographers and archaeologists, despite working within different domains of inquiry
(Figure 26.1). The ethnographic present and the archaeological record are incommensu-
rable, but compatible, domains (David, 1992; Schiffer, 2013). In this case, both share potter's
work as a medium through which we can understand societies. Archaeological analyses
of ceramics proceeds by reconstructing manufacturing processes using physicochemical
470 KENT D. FOWLER

DOMAIN OF ETHNOGRAPHIC INQUIRY

DOMAIN OF ARCHAEOLOGICAL INQUIRY

Modern cultural context

of ceramic production Ceramic products,
in situ debris and
features

1 1
Observation of
technical variation in Reconstruction of
manufacturing processes manufacturing processes

1
Socia! interpretations
of technical variation
l
Soda! interpretations
of technical variation

l
Past cultural context
of ceramic production

FIGURE 26.1 The domains of ethnographic and archaeological inquiry into pottery manu-
facturing practices and the two principle areas of contribution ethnographic observations
and explanations may lead to the understanding of past ceramic production systems.

and experimental data to characterize technical variation across space and through time
(Costin, 1991; Tite, 1999). However, the results of experiments and material science data
have "no inherent social meaning" (Arnold, 2006: 3). To provide social interpretations of
technical practices, archaeologists must work with ethnographic models that explain why
practices and products vary. There are two entry points for ethnographic observations into
the archaeological domain. First, qualitative and quantitative observations of manufactur~
ing provide a baseline and reference points for reconstructing manufacturing methods
through experiment and comparison. Second, the ethnographer is uniquely situated to
infer the variety of technical and social factors influencing variation in manufacturing pro-
cesses, and thereby may bolster interpretations of how the context of production influences
artifact variation.
Two main approaches have provided empirical observations of manufacturing prac-
tices: ethnoarchaeology and material culture studies. Ethnoarchaeology is "research that
includes an ethnographic component and is carried out with the analogical needs of the
archaeologistin mind" (David and Kramer, 2001: n). Ethnographic data comprise the source
side of analogical arguments as long as the questions asked are archaeologically relevant ones
(Costin, 2000; Hegmon, 2000; Stark, 2003). In contrast, material culture studies "explicitly
 ETHNOGRAPHY 471

focus on human materiality in the present" (Wobst, 2013: 246), but are also concerned with
the past, the present, and the mediation between the two. Such studies are grounded in the
premise that there is multivocality to the material constitution of social relations that is not
sufficiently captured by any one conventional discipline.
Theoretically, the study of ceramic manufacture falls along a rather messy continuum
(David and Kramer, 2001; Stark, 2003: zoo; Raux, 2013). Positivist (or scientist) frameworks
sit at one end and humanist and symbolic (or hermeneutic) frameworks at the other (David,
1992). Typically, positivist approaches aim at discerning formal relationships between the
material record and the organization of production through "the use of rigorous methodol-
ogy, controlled experimental approaches;' and the use of ethnographic contexts as "actu-
alistic laboratories for refining and enhancing analytical techniques" (Stark, 2003: 201).
Positivist research questions are concerned primarily with elucidating the technical fac-
tors (ecological and economic factors, and the physicochemical and mechanical proper-
ties of ceramic objects) that distinguish variation in objects and manufacturing practices.
A humanist/symbolic framework emphasizes the range of cultural factors (historical, social,
cosmological) that impact variation in objects, manufacturing practices, and the operation
of production systems. A close reading of non-Anglophone social theory, particularly from
France, encouraged this focus on cultural factors. The Techniques et Culture school argued
that manufacturing is as much a technical process carried out with the functional require-
ments of the user in mind as it is a socialization process embedded with meaning and manip-
ulated to serve the social and philosophical/religious needs of the artisans (Petrequin and
Petrequin, 1993; Lemonnier, 1992; Cresswell, 2010; Raux, 2013). The basic difference between
these two approaches to ceramic analysis is how the research question is framed: the posi-
tivist approach in ethnoarchaeology asks how objects capture manufacturing practices that
characterize production systems (Costin, 1991), whereas humanist/symbolic frameworks
start by asking how society influences the making of things.
Regardless of approach or theoretical framework, ethnographic observations may serve
the aims of those whose questions are archaeological, ethnoarchaeological, or address
human materiality. One outcome that ties together ethnographic contributions using either
approach and under various theoretical frameworks, are the physical and sociocultural con-
straints on the pottery manufacturing process.

CONSTRAINTS ON CERAMIC MANUFACTURE

Six main categories of constraint influence the manufacture of ceramics and contribute to
variation in a ceramic assemblage. Each group is sufficiently coherent to stand on its own,
but alone they do not provide a complete explanation of pottery manufacturing practices.
The first constraint is tradition. 1be concept of tradition has been a source of much con-
fusion in anthropological research because it is often defined negatively, in opposition to
modernity (Graburn, 2001). However, Horner (1990) reminds us that tradition is the pro-
cess of handing down knowledge, practices, and things from one generation to the next,
and functions as a "reservoir" of knowledge and behavior, and a source of identity. For pot-
tery-making, Gosselain and Livingstone Smith (2005) emphasize tradition as "specific and
general knowledge, pertaining to the way individuals situate themselves in time and space:'
472 l<FNT D. FOWLER

Tradition, in this specif1c sense, explains potter's assertions that they have not modified
tools, techniques, or recipes since learning them. "This is the way we learned it;' or "This is
how my mother did it;' are statements that link individuals and practices in the present day
to the past by acknowledging shared behaviors between themselves, their elders, and ances-
tors. Such explanations for doing things bracket what is perceived as the range of possibili-
ties open to potters. In doing so, potters emphasize continuity, define "new," and marginalize
situational reasons for altering behavior, such as the short-term vagaries of economics and
kinship dynamics. The specific and general knowledge that embodies tradition is well suited
to synchronic research and an archaeology of the longue duree.
The second category includes technofunctional constraints. Tradition and techno-func-
tional constraints are closely connected: tradition drives and shapes perceptions or con-
ceptions of technical necessity. Potters work within a set of technofunctional compromises:
strength, mechanical stress, thermal stress, permeability, porosity, and density are all prag-
matically considered in design and manufacturing choices. Tradition is manifest in these
perceived technical requirements by how potters explain technofunctional choices made
during manufacturing. For instance, removing rocks with certain physical properties from
clays may be done because "these cause the pots to break during firing:' When making such
statements, potters describe how the decisions they make during one stage of production
are not entirely independent of operations performed in other stages. Mitigating risk then
seems to be linked to the notion that vessels must be made in a particular way. By follow-
ing a specific set of behaviors at each stage in manufacturing potters attempt avoid failure
during later stages or when objects are used. However, there are numerous physicochemi-
cal solutions to technofunctional problems faced during manufacture. For example, clays
may be hand sorted, crushed, ground, sieved, or levigated to remove rocks with undesirable
properties. In reality, any one (or combination) of these techniques can be used to remove
non-plastic materials, and a method can be changed without jeopardizing operations in later
stages or perceived technofunctional requirements.
Researchers ascribing to the positivist mode have made tremendous strides in our under-
standing of these technofunctional constraints and their impact on the relationship between
pottery and people. Treating pottery as tools (Braun, 1983) has provided insightful reasons
for potting practices, such as the use of mineral tempering to improve heat conduction in
the development of direct cooking technology (Skibo and Schiffer, 1989). Yet, ethnographic
research reminds us many potters use only a single paste recipe for a complete functional
repertoire, including cooking vessels (Gosselain and Livingstone Smith, zoos; Gossselain,
2011). The perception of what is required and acceptable both during manufacture and in
finished products is also not restricted to potters. Those who use pottery also play a signifi-
cant role in influencing manufacture.
Demand refers to the producer-consumer relationship; an exchange relationship that sees
parties swap something of value (Bagozzi, 1975). The process of ceramic manufacture is more
complex than a potter creating and supplying useful things to a community; there has to be
a perceived need or desire for these things. Following a useful distinction made by Marx,
Humphreys and Grayson (2009) note that valuation can be of two kinds: "exchange value;' a
product's worth relative to other things and services available; and "use value:' which satis~
fies the wants and/or needs of the consumer by being used. These values are independent of
each other, however the type of value placed on products by the consumer governs demand.
Indeed, Arnold (zoos: 127-167) has aptly demonstrated how exchange and use value sway
r
'
ETHNOGRAPHY 473

what kinds and how much pottery is made with consequent effects on the organization of
production, the manufacturing practices of potters, and distribution mechanisms. For
instance, LaViolette (2ooo: 62) has shown that consumers eschew effective thin-walled
cooking vessels made by potters in the inland Niger delta because they are fragile; in this
instance use value governs demand. Demand, therefore, is not merely an economic transac-
tion in which potters react to the kinds and quantities of pottery required. Rather, the pro-
ducer-consumer relationship runs deeper. This is most evident in the symbolic dimensions
of manufacture. After all, values are symbolic constructions (Robb, 1998: 334).
The symbolic meaning or significance associated with pottery has long fallen under object-
centered analyses of style. However, ethnography offers an opportunity to explore with pot-
ters the symbolic significance of particular materials and behavior. Beliefs about natural
resources and how people should act in the world tie ceramic manufacture to broader sys-
tems of thought; for it is from these ideologies that perceptions of materials and people are
drawn. Ideological constraints can be deep and pervasive, such as the widespread associa-
tion between pottery making, pottery, and people in Africa (David et al., 1988; Barley, 1994;
Gosselain, 2002: 205-208). Without reference to a rich constellation of metaphor, meton~
ymy, and allegory it is difficult to understand (or even discuss with potters) the physical attri-
butes of pottery (e.g. naming of vessels parts) and similarities in the physical treatment of
pottery and people. Materials also can be ascribed particular status, such as the "divine" raw
clays used in Yaane medicine in Ghana (van Dongen et al., 2011). Never used for making
pottery, medicine clays are exclusively used fOr constructing shrines. Tims, behavior is con-
strained by perceptions and concepts of the materials. The manufacturing process itself can
also be a source of ascribing meaning to people and events in other ways. Following from
the earlier example, removing rocks with certain physical properties from clays may be done
because "these cause the pots to break during firing;' but failure during a firing may be taken
as a portent of bad luck within a community, such as a death, and not as a result of negligent
processing (Fowler, 2014). This is not a means of deflecting responsibility by a potter. Firing
faults affecting a whole batch are so rare that its occurrence must signal something dras-
tic has happened. Symbolic significance, therefore, is not restricted to the study of objects
or their aesthetic qualities. The very practice of making pottery is imbued with meaning
(Dobres, 1999), although not all operations are equally symbolically loaded.
The archaeological study of symbols and symboling involves the study of representations;
the relations between the material and immateriaL The meanings we invest in the material
world, including ourselves, define symbolic life, which is neither superficial nor always a
realm of contestation (Robb, 1998: 336, 339). Ceramic ethnography provides a means for
realizing what are the right questions to ask when it comes to thinking about those "intan-
gible qualities of social existence:'
One symbolic construction, identity, is a major organizing principle influencing manu-
facture. As such, the identity of potters is a constraining factor contributing to variation in
ceramic manufacture because the skills and knowledge involved in potting, as in other tech-
nological processes, are "associated with particular identities and values" (Robb, 1998: 336).
Identity has received a tremendous amount of attention because how potters are situated
in society directly impacts their access to material and social resources, including clientele
(Gosselain, 2oo8; Lyons and Freeman, 2009 ), and may explain why people do not always
express identity through the appearance of their wares (MacEachern, 1998). What appears
very significant archaeologically is how the various communal identities held by potters
474 KENT D. FOWLER

(e.g. age and gender, social status and class divisions, ethnicity in cultura1ly pluralistic set-
tings) and the interaction networks experienced by them, influence and contribute to the
range of available technical options. Gosselain (2ooo) first proposed that the social net-
works potters belong to differently impact the choices they make during manufacturing. As
choices become more technical and inflexible, smaller networks of people influence them.
For instance, more people influence what pots will look like, but fewer people influence the
specialized gestures used to shape vessels. Importantly, the skills and knowledge potters rely
upon are not all specialized and unique to pottery manufacture. Potters, like the rest us, find
inspiration in and are influenced by the entirety of their social life, including activities unre-
lated to potting.
PThe final category of constraints affecting ceramic manufacture moves us outside potting
to other realms of activity, which include the other interconnected sets of activities potters
are responsible for or participate in. This involves more than considering scheduling and
task symbiosis (Arnold, 1985). Rather, explaining technical variation in this way examines
relationships amongst techniques, motor patterns, and equipment used in multiple domains
of behavior, such as food processing, graphic arts, or other crafts. This is little explored terri-
tory in ceramic ethnography and ethnoarchaeology, but there has been some solid concep-
tual work on how to think about interrelatedness of activities in ways that cross the divide
between present and past (e.g. Ingold, 1992).
One of the most important conclusions resulting from empirical studies of relation-
ships within and between pottery-making communities is that technical and social factors
do not equally constrain and influence different steps and stages in the manufacturing
process. Careful appraisal of manufacturing operations has revealed contradictions in
links previously made between manufacture and production (e.g. how potters are socially
situated versus consumers; Lyons and Freeman, 2009), manufacture and consumption
(e.g. better performing cooking vessels are not valued by consumers; LaViolette, 2000)
and little explored factors that motivate and influence potter's behavior (e.g. competition
from immigrant potters; Gosselain, 2oo8). These observations hold value for archaeo-
logical interpretations of manufacturing practices and the social contexts in which these
occurred because potters do not weigh constraints equally during production. Simply
stated, there is plurality in what influences potters during every step and stage of the man-
ufacturing process.

PLURALITY OF CONSTRAINTS

Resource Procurement
Five groups of natural resources are potentially involved in making ceramics: clay, water,
temper, pigments, and fuel. Only clay, water, and fuel are obligatory. Tempering material
may or may not be added to a raw or processed clay paste to achieve the technical and/
or physical properties desired by potters, such as color, texture, porosity, and workability.
Likewise, the use of pigments and other material for making washes, slips, paints, or glazes
are typically used only to modify the visual attributes of ceramics, and their use varies con-
siderably cross-culturally.
 ETHNOGRAPHY 475

nm

86%----il-(-)~--9"'
Cumulative pereent
of day distances
Cumulative pt~r~ent
of temper diStances

FIGURE 26.2 'The distances travelled to ceramic resources (clay and temper) by potters
from 117 communities (data from Arnold 1981, 1985, 2005, zoo6).

One of the most enduring ethnographic contributions to archaeological interpretations

of resource procurement is Arnold's (1985, 2006) "distance threshold model" or "ceramic
resource area model" (Figure 26.2). This predictive model of procurement strategies pro-
poses maximum distance thresholds that correlate with how far sedentary people will travel
to clays and tempering materials. The principle ofleast-effort ostensibly explains a potter's
labor to obtain clay, temper, and water, and defines the spatial limits of energy expended
to obtain these resources. However, Arnold (2ooo, 2005, 2006) fully acknowledges that a
range of factors, not considered in the model, govern a potter's practices. Gosselain and
Livingstone Smith (2005: 34) summarize how procurement strategies in Africa may be
affected by the local geology, individual perceptions of raw materials, settlement and land
tenure patterns, competition amongst potters, local and regional social interactions, and
techniques used in other steps of manufacturing.
An improved understanding of the technical and social reasons that impact resource
procurement has altered ceramic provenance research designs, particularly sampling strat-
egies of potential raw materials for comparative purposes. Clay deposits used by present
day potters as well as those potentially used in the past are regularly sampled to improve
how "local" versus "non-local" are defmed in both geological and social terms (e.g. Stark
et al., 2ooo; Kennett et al., zooz; Stahl et al., zooS; Marques et al., 2010). It is incumbent
upon those conducting characterization analyses of archaeological ceramics to establish
at least a local baseline for assessing the geological origins of resources used in ceramic
manufacture. However, it is rare to find detailed analyses of samples from clay deposits
used by modern potters, in addition to their processed clays (especially mixed clay bodies),
and finished vessels that would form a complete ethnographic comparative sample (e.g.
Middleton, 2012).
476 KENT D. FOWLER

Archaeologists have challenged the idea that the distance to resources and clay and temper
quality are universally important considerations of potters, arguing that the co-occurrence
of resources on landscapes (e.g. water, clay, fuel, temper) is a better explanation for why cer-
tain clays and temper are used for pottery manufacture (Kelly et aL, 2011). This relationship
between the acquisition of resources and the other activities undertaken by potters, such as
collecting water and domestic fuel, was predicted for some time by ethnographic research in
Africa (Gosselain, 1994; Gosselain and Livingstone Smith, 2005). Considering such social
factors provides "a nuanced, more complex, understanding" of why potters would choose
to use resources nearby or farther away, and moves us away from "a static perception of pot-
ters' behavior towards a more dynamic and realistic one" (Gosselain and Livingstone Smith,
2005: 34).

Processing
Processing involves the transformation of clay from a raw material to a workable paste and
ceramic body. While it is possible to use clay in its natural state (Silva, 2008), this appears
to be uncommon (Rice, 1987: 118-124). Rather, most potters modify clays in some way
using one or more techniques. The potential diversity of clay "recipes" may well appear
limitless and largely influenced by technical requirements, However, ethnographic work
has shown that the making of suitable clay bodies through processing is governed by
both technical and non-technical considerations. Suitability is, of course, highly subjec-
tive. Yet, it has been suggested that "tradition;' technical constraints, relationships with
other realms of activity, and symbolic concepts are key elements that influence variation
in processing techniques and the resulting "recipes" (Gosselain and Livingstone Smith,
2005: 40-41).

Shaping
The shaping stage, also called "primary forming" (Rye, 1981: 62) or "roughing out" (Courty
and Raux, 1995), is distinctive in the manufacturing process. Generally, shaping techniques
leave no apparent traces on the finished product. It is an activity usually done by individ-
ual potters, and can also be distinguished from other manufacturing stages by the use of
specialized gestures, as opposed to tools or knowledge of clays and skills acquired during
other activities, such as grinding grain (processing), collecting fuels and firing, or learn-
ing to draw. Gestures are more commonly referred to as "motor habits" that are mastered
through repeated practice during early learning and subsequently internalized. As such, it
has been widely argued that they prove to be especially resistant to change (see Gosselain,
2000 ). Change may be of little interest to a potter because even when knowing about other
shaping techniques they seldom adopt them (see Gosselain, 1995: 176-180; Hosler, 1996;
Petrequin and Petrequin, 1999 ). When new techniques are adopted, such as in southwestern
Niger (Gosselain, 2008), they are used only to make the wares introduced into an area. New
techniques are not transferred to the manufacture of an existing repertoire despite the fact
that similar-looking vessels can be shaped using many different techniques. Thus, shaping is
likely to remain stable throughout a potter's lifetime, and it often reflects those most rooted
 ETHNOGRAPHY 477

and enduring aspects of social identity, such as kinship, language, gender, and class subdivi~
sions (see Gosselain, 2000).

Decoration
The decoration afforded pottery has undoubtedly received the greatest attention by archae-
ologists. It is the basis for generating classifications and typologies of pottery styles used to
infer chronology and group identity. The study of pottery decoration has been approached in
two ways: design and techniques (Rice, 1987: 248-249). Design is the execution of elements
(the smallest unit of decoration, such as line or an impression) into increasingly larger com-
ponents (motifs, or fixed element combinations) on a space available (e.g. a vessel surface).
Both elements and motifs can be combined in specific ways (a configuration) to form basic
units that are arranged in particular layouts or structures in a design space. Together, tools
(equipment) and techniques (e.g. stamping, grooving, burnishing, etc.) generate elements.
Thus, for a potter, the tools and techniques they use to alter the visual and tactile aspects of
pottery are as important as design concepts because they are fundamental to the execution
of design elements. Tools and techniques are then basic analytical units and an archaeologi-
cal understanding of them is required to properly understand how design is materialized.
Research based on tools and techniques as the basic units of analysis has made several
important observations about the relationships between design and techniques and their
influences on each other. Amongst these, is the realization that pottery decoration is part of
a broader decorative system that occurs on other material culture, spanning from architec~
ture, to woodwork, basketry, and clothing (Evers, 1988), and can even extend to body modi-
fication in the form of ornamentation, tattooing, and scarification (David et al., 1988; Barley,
1994). Given the potential functional and symbolic linkages that can be envisioned through
the use of a shared repertoire (Sterner, 1992; MacEachern, 1994), it is perhaps surprising that
potters themselves may be quite reserved in ascribing any deep symbolic significance to dec-
oration. They may instead describe the practical merits of changing the texture of vessels
(e.g. to prevent slipping during use) or emphasize that the aesthetic qualities are appreciated
and admired by clientele, but carry no obvious meaning or messages. As "insiders;' it may
not immediately apparent to potters, or even their intent, to signal distinctiveness or belong-
ing through a decorative repertoire as part of a general style system.
As a result of the potential ambiguity involved in the most visual features of ceramics
and the ease with which decoration can be learned, it has been suggested that decoration is
susceptible to borrowing. The pace of adopting new techniques is not agreed upon. Gelbert
(2003), for instance, has shown how potters moving into a new area and experiencing a shift
in clientele will not adopt new techniques for some time. Likewise, Gosselain (2010, 2on)
has reviewed how change through borrowing and innovation appears to affect the compo-
nents of decoration, rather than design structure or grammar. This observation mirrors that
made by Rice (1987: 249) when she argued that basic units are "the most immediately rec-
ognizable components of a design, and so may be easily borrowed or imitated from artist to
artist:' Gosselain (2010) notes how it is at the level of basic units where the symbolic function
of decoration may lay and where collective identities are expressed. Indeed, this is confirmed
by Bowser's (2ooo) work in the Amazon, where she demonstrated that political identity of
Quichua and Achar potters was signaled by differences in design symmetry (a basic unit),
478 KENT D. FOWLER

the framing of design fields, the use of color, and specific motifs. Thus, at the level of basic
l
I
units and below (elements, motifs, configurations) is where identity may be expressed within
groups. Wallaert-Petre's (2001) work indicates that such identities may even be detectable
in the different gestures and postures of potters during shaping and decoration; that is, the
actions involved in executing design elements. Differences in structure and grammar may
then be used as indicators of larger-scale group identities. There is no clear consensus as
to the size or social referents for these groups. However, earlier ethnoarchaeological stud-
ies indicate that design grammars can at least distinguish different communities (Friedrich,
1970; Arnold, 1983; Hole, 1984; Graves, 1985), whilst material culture studies suggest that dif-
ferences in design grammars can effectively distinguish language groups in some regions
(Huffman, 1980; Evers, 1988).

Drying and Firing

Drying is the stage of manufacture during which residual moisture is drawn from the object
through evaporation. Firing is the ultimate stage of manufacture; transforming a clay object
into a ceramic. It is both transformative in the physicochemical sense and in the cultural
sense, because it is only after firing that objects are ready to be used in society at large.
Working mainly from the physical characteristics of pottery and, more rarely, the remains
of structures, such as kilns and installations such as firing pits, archaeologists have relied
on estimations of firing temperatures as a proxy of ancient firing procedures (Tite, 2008),
including the kind of structure used and regime differences in terms of maximum tempera-
tures reached, heating rates, exposure to temperatures (soaking time), and duration of the
firing. The contribution of ethnography to the understanding of ceramic firing has been
twofold.
First, firing procedures, despite their variety, fall within one of two broad cat-
egories: "open" firing (bonfires and pits) and kiln firing (Rice, 1987: 152-163; Gosselain,
1992: 152-163). Associated with each category is a firing regime that consists minimally
of different heating rates (fast versus slow) and heat input (low versus high). Second,
the study of present-day firing technologies has highlighted both technological and
social issues with estimating past firing technologies from thermal profiles derived from
the mineralogy and/or microstructure of sherds (Tite, 1995, 1999). Livingstone Smith
(zoor: 999), for example, has demonstrated that different firing procedures "may result in
similar thermal profiles" mal<ing it "impossible to relate a particular set of thermal char-
acteristics (duration, maximum temperature, heating rate and soaking time) to a specific
firing procedure:' What appears to be most important in firing is achieving particular
soaking times (Figure 26.3).
Another astute observation is that potters, by and large, are either unaware (Livingstone
Smith, 2001: woo) or uninterested in the advantages and disadvantages of their procedures,
apart from those aspects of firings they deem to be under their direct control. Many potters
simply follow an established procedure to fire pots; others are thoughtful about the conse-
quences of altering fuels and adjusting the scheduling and location of firings, or the quantity
and positioning of vessels within firing structures/installations.
Unless potters must strictly adhere to a schedule in order to meet demands (such as
weekly markets), they tend to vary fuel, scheduling, firing locations, and batch size as a
 ETHNOGRAPHY 479

Temperature Range Temper~turt R~ngc for

>80% of Soaking Time

Bonfire

Bonfire with
Insulation

Pit

Kiln

0 200 400 600 800 1000 1200

Temperature (°C)

FIGURE 26.3 Range of :firing temperatures and soaking times for firings in West Africa.
The majority of soaking times fall within the same temperature range (>700 to <90o"C)
regardless of firing structure or fuel used. Data from Livingstone-Smith (2001).

result of social demands, not just economic or technical ones. Altering fuel combinations,
scheduling, and output, for instance, are reliant upon the other activities undertaken by
potters. Moreover, firing is usually a collaborative undertaking, during which multiple pot-
ters, sometimes from different workshops, manage fuel collection and firing surveillance.
The public and collaborative or communal nature of firing lends itself to the exercise of pre-
scriptions and prohibitions governing where firing takes place and who is able to participate
(e.g. Armstrong et al., 2oo8; Fredriksen, 2012), but these symbolic factors do not appear to
affect the technical behavior of potters in terms of structures, fuels, and consequent thermal
profiles.

Post-Firing
Post-firing treatments are properly defined as any modifications to ceramic objects tbat
occur after firing. By far, they are the least understood archaeologically. There are two
main reasons for this. First, potters may ascribe both aesthetic and functional qualities
to post-firing treatments. Incising motifs, polishing, adding pigments and organic coat-
ings, and smoking vessels to give them a black appearance, are all operations that can
occur after firing. The use of some of these techniques can· be explained as an extension
of the decorative process meant to "finish" vessels properly. It is significant, though, that
these treatments occur after firing, and not before. Distinguishing when these treat-
ments occur during manufacture provides insight into variation in chaines opiratoires
480 KENT D. FOWLER

that are socially and, perhaps, temporally significant. For instance, amongst Zulus in
South Africa, the blackening of serving and drinking vessels has symbolic significance.
The sorghum beer served and drunk from blackened vessels during celebrations of
various kinds is linked with avoidance and respect behaviors that are unique to Nguni
societies (Armstrong et al., 2008: 516-520). Blackened vessels invite the ancestors to cer-
emonies, and to use other kinds of containers would offend them and cast a pall on the
event. Such vessels have been characteristic of the regional Nguni pottery repertoire
for over a millennium. These vessels form diagnostic break from earlier potting tra-
ditions, marking the movement of Nguni people into southeastern Africa (Huffman,
2004). Conflating vessel blackening or any of the post-firing treatments with "decora-
tion" misses the opportunity to explore why these behaviors occur at this stage in the
manufacturing process. For example, post-firing vessels may be afforded organic coat-
ings, resin applications, water treatments (e.g., soaking, sprinkling), or be cooked with
porridges (e.g. Lawton, 1967; Gosselain, 2002: 191-192). These treatments are bound
up in functional explanations, but are considered culturally or socially necessary to
strengthen and waterproof vessels.
The second reason post-firing treatments are not well understood archaeologically is
due to the nature of the materials used in post-firing treatments. It is extremely difficult
to distinguish the chemistry of the organic materials used in post-firing treatments from
what may have been foodstuffs. As such, lipids and other biomarkers of organic material
preserved in vessels ·may be interpreted erroneously as former food contents (Diablo et
aL, 1995). Nevertheless, materials and concoctions used in these treatments are extremely
interesting because many of the ingredients are also used as foods, medicines, in making
other objects (dyes, textiles, baskets) and building; some are even symbolically associated
with illness, people, and the human body (Gosselain, 2002: 197-198, 210-211), ancestors,
and in some instances, more broadly with social norms and concepts of danger and pollu-
tion (Armstrong et al., 2008). Ceramic ethnography draws us into using pottery to think
about materials and behaviors that have little or nothing to do directly with the objects
themselves.

SYNTHESIS

Using ethnographic data, there have been several attempts to correlate which constraints
most heavily influence the different stages of ceramic production. Gosselain's (2ooo) synthe-
sis of African data considered how sociocultural and technological constraints impact the
visibility of techniques on finished products, how easily techniques are changed or replaced
by others, and how knowledge is transmitted during and after learning the craft both within
and between generations. The influences fall into three general categories or basic groups
(Figure 26-4):

(1) Techniques that are the most highly visible on finished vessels are the most techni-
cally flexible and are more easily transmitted after learning the craft. They fluctuate
through time and vary locally to reflect more superficial, situational, and temporary
identities, such as age, economic situation, and the demands of clientele.
 ETHNOGRAPHY 481

VISUAL Et TACTILE
Processing (additives)
Decoration
Shaping (preforming)
Firing (post-sintering)
Post-firing

CLAY PREPARATION Et FIRING

Selection
Extraction
Processing (pretreatments, removal
of plastics, homogenization)
Firing (structures)

SHAPING
(roughing out)

LOW FEW

Social Network Influence on Technical Knowledge

FIGURE 26.4 Models of the technical and social influences on ceramic manufacturing
based upon African case studies (see Gosselain 2000, 2002).

(2) A second group of techniques, such as clay preparation and firing practices, are not
easily visible on finished products and are less likely to be modified after learning
because they are only known or visible by potters and their assistants. These more
restricted interactions reflect the access potters have to local or regional social
networks.
(3) The last group is composed of shaping behaviors. Potters are reluctant to change shap·
ing techniques, therefore they reflect the most enduring and slowest changing aspects
of potter's interaction networks and identities, such as kinship, language, gendered
technical practices, and class divisions.

These three suppositions form a basis for examining relationships among techniques and
constraints because each has a corresponding technical correlate and expectations of spa-
tial and temporal distribution. It would be imprudent to believe that these relationships are
universal. Yet, this model stands as a basis for exploring the intersection of ethnographically
identified constraints on pottery making.

CoNCLUSIONS

Over the past six decades, documenting the ways pottery can be made and what charac-
terizes different traditions around the world has focused on non-industrialized production
482 KENT D. FOWLER

systems (Stark, 2003).1be two ethnographic approaches used to document modern ceramic
manufacture ask different questions of those who make pottery: ethnoarchaeology is struc-
tured around archaeological questions while material culture research aims to understand
the social contexts in which pottery is made and used. Theoretical frameworks emphasize
explanations of variation in products and practices as the consequence of technical or social
constraints on pottery production. A maturing realization that these explanations are not
mutually exclusive has lessened tensions along this theoretical continuum (Stark, 2003).
Ceramic ethnography has great potential for developing theory and method of ceramic
manufacture by forging ever-closer relationships between ethnographic and experimental
observation (Rou:x, 2007). Ceramic ethnographers are also uniquely positioned to identify
attitudes towards materiality through participation and social action, and how "the prop-
erties of material, technological processes and functional performance" can act "as crucial
pathways towards" the archaeological goal of inferring social meaning form the study of
artifacts in their contexts (Hurcombe, 2007: 538). Ethnographic study of ceramic manufac-
ture remains indispensable to archaeological ceramic analysis, providing context for the way
in which material and immaterial concerns of people may, or may not, find expression in
ceramics, and how these are associated with other kinds of material culture and practices in
human societies.

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 CHAPTER 27

EXPERIMENTAL FIRING
AND RE-FIRING

MALGORZATA DASZKIEWICZ AND LARA MARITAN

INTRODUCTION

FIRING represents an important stage in the pottery production sequence, since this thermal
process transforms raw incoherent clayey material into ceramics and determines its miner~
alogical and physical properties. A variety of firing technologies were used to manufacture
archaeological ceramics. Differences in firing technology range from the use of pyrotech-
nological installations to the type of fuel used. On the basis of ethnographic studies (for an
overview of the topic, see Rye, 1981; Rice, 1987) there are two basic types of firing technology:
open firing and kiln firing, characterized by the following features:

(i) open firing (non-kiln firing, bonfire): firing done in a small, concentrated area,
sometimes in a pit or depression partially excavated in the ground, without any per-
manent kiln structure; characterized by a short firing cycle, rapid heating rate and
irregular temperature, non-uniform firing (Le. local changes in redox conditions
and temperature, which can vary by 100°C from place to place), maximum temper-
ature reached is typically lower than 900°C, direct contact among the vessels, fire
and fumes released by fuel combustion, irregular draft, and firing rate dependent
on the types of fuel (wood, grass, straw, twigs, seaweeds, animal dung) (Rye, 1981;
Gosselain, 1992 and references therein); when the firing is set in a depression it is
defined as pit firing; temporary covering made for instance of broken ceramic, which
isolate the vessels and avoid the decrease of heating, can be employed.
(ii) kiln firing: firing using pyrotechnological installations characterized by a com-
bustion chamber (firebox), where the fuel burns, and a firing chamber; not always
characterized by high firing temperatures, up to 1000-1300°C, homogeneous dis-
tribution of the heating, controlled draft and atmosphere (redox conditions), and
ability to maintain the maximum temperature; classification of kilns is based on the
shape of the firebox and/or on the type of structure dividing the firebox from the fir-
ing chamber (Rice, 1987).
48R MAtGORZATA DASZKIEWICZ AND LARA MARITAN

Firing process is very complex with myriad variables each contributing to the mineralogi-
cal and performance characteristics of the vessel; duration of the firing cycle, heating and
cooling rate, maximum temperature, soaking time (time of maintenance of the maximum
temperature), draft, and atmosphere (oxidizing or reducing) control the thermodynamic
reactions in mineral phases contained in the ceramic fabric and degree of vitrification, as
well as physical properties of the vessel such as porosity, strength, toughness, and thermal
conductivity. When working on the reconstruction of the technological process used by
ancient potters, comprehensive knowledge of the thermal behavior of the ceramic body dur-
ing such a process is required. What is needed is a method which, through the analysis of the
finished product, determines the technological process as close as possible to the ancient
one. This is an equation with many unknowns. We should also be careful that our solu-
tions are not erroneous resulting from the transfer of our contemporary thinking to ancient
technology.
The following chapters describe the conclusions resulting from experimental firing as well
as a method of re-firing fragments of ancient pottery to be used in the reconstruction of the
ancient firing process. We can only determine the equivalent firing temperature, which is the
same as the original firing temperature, when identical firing conditions are used. The esti~
mation of EFT is possible by comparing the composition and properties of ancient sherds
with the results of experimental firings of samples made from a similar body (static meth·
ods) or by re-firing fragments of the original sherds and observing changes in composition
and properties (dynamic methods). Furthermore, re-firing small samples of the original
sherds at temperatures well above the original firing temperature allows ancient pottery to
be classified according to its thermal behavior, which is dictated solely by the material com·
position of the samples if they are re-fired in identical conditions.

Experimental Firing
Experimental firings attempt to reproduce ancient firing technologies, in order to evaluate
the influence that each parameter involved in the firing process has on the compositional,
physical-mechanical and chemical properties of the fired products. Ceramics from archaeo·
logical sites contain a variety of information about the production process, which can be
understood and interpreted through comparison with experimentally produced pottery for
which all the conditions or variables are known. Experimental firings can either replicate
ancient firing technologies by using analogous firing techniques in the field or in kilns mod-
elled after archaeological exemplars, or take place under more controlled laboratory condi·
tions in electric furnaces.
Firing experiments are typically designed to solve technological issues about specific
ceramic productions and are used most often to estimate the maximum firing temperature.
In order to constrain the firing temperature of the pottery, the mineralogical composition
and/or the microstructural features of the ceramic bodies of archaeological ceramics need
to be compared with those of ceramic replicas obtained through firing experiments carried
out on base clay materials analogous, in terms of chemical, mineralogical, and textural com-
position, with those used in the archaeological ceramics of interest. The specific conditions
of the experimental firing must be based on the macroscopic, microscopic, and microstruc-
tural analysis of the archaeological pottery under investigation, which often can provide
 EXPERIMENTAL FIRING AND RE-FIRING 489

Table 27.1 Basic atmospheric conditions during firing

in antiquity (after Maggetti, 1991 ).
Numerous variants are also possible
Type of firing Heating-rna intenance Cooling

more ancient A reducing oxidizing

t B reducing reducing
more recent c oxidizing oxidizing

information about the firing atmosphere and ranges of maximum temperatures reached. In
addition, the firing technology used, open firing vs. kiln firing, can often be deduced from
the amount of pottery, homogeneity in terms of body color, standardization of the ceramic
production, and/or by the archaeological remains of pyrotechnological installations.
Ethnographic observation and archaeological evidence indicate that firing atmosphere
are deliberately controlled and manipulated by the potter through changes in draft and
fuel. The three basic atmospheric situations are presented in Table 27.1, although numer-
ous variants and more complex procedures were often used. For example, Greek black and
red figure vases were produced according to a complicated three-phases firing process,
which produced the red color of the vase and black of the applied slipped figures or black
color of the slipped vase and red color of the left open unslipped figures if the conditions
are reversed. Black-figure vessels were kiln-fired in oxidizing conditions until about 8oo 0 C.
Next, a reducing environment was created by closing the kiln's vents burning green wood to
subtract oxygen from the firebox and the firing chamber and the vessels are fired to about
950'C (Schreiber, 1999 ), which causes the reduction of the iron and the melting of the slip to
producing a black vitrified gloss. In the final stage of firing, the vents were opened to allow
the air to flow creating an oxidizing atmosphere during cooling facilitating the oxidation of
iron to produce the red coloration of the vase body while the sintered gloss remained black.
Experimental firings can be classified as experimental archaeology or laboratory con-
trolled, depending upon whether the firing is carried out "in the field" or in a laboratory.

Experimental Archaeology Firings

Experimental archaeology firings are important activities addressed to the reproduction of
possible firing procedures, based on archaeological evidence, used in the past to obtain cer-
tain types of pottery. These experiments therefore mainly aim to test if specific firing struc-
tures and firing methods were adopted (Ther and Gregor, 2011), or to replicate a range of
pottery types experimentally (Harrison, 2008).
In experimental archaeology, both in the case of bonfire or pit firing technology, or
using kilns modelled on archaeological remains, complete "green" vessels (or green bodies,
defined as the intermediate products of the ceramic process, composed of a clayey material
and eventually of added temper; they correspond to a shaped body before being fired) can be
placed on and among the bonfire's fuel or inside the pit, or in the kiln chamber, respectively,
490 MALGORZATA DASZKIEWICZ AND LARA MARITAN

for firing. The advantage of conducing these types of firing experiments is represented by
the possibility of directly testing the influences that different parameters/factors have in the
firing itself as well as in the final products. The possibility, in fact, of monitoring the ther-
mal regime, in some cases also the atmosphere during the experiment, and the macroscopic,
mineralogical and textural features of the final products, represents an important instru-
ment for understanding the ancient production procedures, supposed to be adopted for the
production of specific pottery types (see for instance: Maggetti et aL, 2011; Ther and Gregor,
2011). It is worth knowing that a certain type of firing structure can be used according to dif-
ferent procedures, producing different types of fired materials, in terms ofboth aesthetic and
technological features (Ther, 2004). The possibility of regulating the thermal regime (heat-
ing and cooling rate, soaking time), the draft (removing the object from the bonfire, open-
ing or closing the chimney in kilns, or removing the covering from clamp kilns), as well
as burning different types of fuel, allows the experimenters to test different possible firing
procedures, which therefore can produce different products. Temperature distribution and
variation during the firing can be measured placing thermocouples in different positions in
the bonfire or in the kiln.
In the case of bonfire, variation in temperature during firing and heterogeneity in the
temperature distribution within a single firing are very dependent on the density of stack-
ing the object up, and on the type, quantity, and distribution of the fuel (Gosselain, 1992;
Livingstone-Smith, 2001), as well from the procedure of firings. The removal of any pos-
sible covering material, or of pots from the fire, determines immediate cooling down of the
objects in a few minutes and contact with the oxidizing atmosphere, which can change the
color of the object if fired until that moment in reducing conditions. On the contrary, natu-
ral cooling in the ashes promotes a reducing atmosphere as well as making the cooling rate
some ten minutes longer (Ther and Gregor, 2011). Despite bonfires mostly lasting for less
than a couple of hours, in some cases, such as in the firing of big piles of bricks (Figure 2p),
it can go on for many days.
Intermediate types of structure between bonfires and kilns are represented by clamp kilns,
characterized by temporary insulation (Ther, 2004), which can be removed during firing to
allow the oxygen to go into the kiln and to cool the pottery down very quickly, or after the
firing is finished.
In the case of firing in traditional kilns, such as those used for ceramic production as
adopted in many artisanal ceramic workshops (Figure 27-1), temperature distribution can
be monitored in the same way, with thermocouples placed in different positions of the kiln
firing chamber, in order to verify the variability on the maximum reached temperatures as
function of the kiln structure, type of fuel, and draft. The regulation and cl1ange of the firing
atmosphere can be done by lowering or increasing the draft, closing or opening the chimney,
or covering the holes of the firing chamber vault. Changes in the draft can also significantly
change the thermal regime in tl1e kiln. Therefore, regulation of draft can deeply influence
both the quality and aesthetic features of the fired products (Lipovac Vrklian eta!., 2012).
Experimental archaeology on !din firings is normally based on the finding of remains of
ancient kiln structures. Due to the help of engines and in many cases of modern potters,
kilns with planimetry and building structure reproducing those deduced from the ancient
remains, can be erected and used for experimental archaeology (Ther, 2004; Lipovac Vrk!ian
et aL, 2012).
 EXPERIMENTAL FIRING AND RE-FIRING 491

FIGURE 27.1 (a) Examples of open firing of bricks at Soba (Blue Nile, south of Khartoum,
Sudan) (kindly provided by Gian Luca Zacchiroli) in which the fuel, composed mainly of
dung, was placed at the base, between the bricks and all over the pile to burn; and (b) of a
traditional updraft kiln at Tell Mishrifeh (central-eastern Syria); (c-d) perforated vault and
floor of the firing chamber, which favor the draft during firing.
492 MAtGORZATA OASZKIEWICZ AND LARA MARITAN

1he more information available about the archaeological ceramic firing technology being
simulated, the more reliable the results and the interpretation of data obtained from experi-
mental firing studies.

LABORATORY -CONTROLLED FIRING

Experimental archaeological data are very useful when open firing techniques (Gosselain,
1992 and references therein) and kiln firing (Rye, 1981; Rice, 1987) are reproduced in labo-
ratory furnaces. These types of experiments are carried out when it is necessary to have a
precise control over the firing process in order to isolate and evaluate the influence of differ-
ent conditions on the mineralogical and physical-mechanical features of the fired products.
Laboratory furnaces equipped with a digital microprocessor are best suited for experimental
firing because the firing diagram can be precisely set and controlled, with a high precision
both on temperature (few degrees) and time. The firing diagram can be defined as the graph·
ical display of the temperature variation with the time, being a representation of the firing
cycle; here, three main segments can be defined as heating, maintenance of the maximum
temperature (soaking time), and cooling (Figure 27.2).
The inconvenience that laboratory furnaces often present is that the firing chamber is
small, restricting the size of the unfired objects (called also green bodies) which can be fired.
Therefore, for laboratory studies, green bodies are typically prepared as briquettes of some
cubic centimeters, molding the mixture of the clay, water, and eventually temper, by uniaxial
pressing. The application of adequate pressure (normally some MPa) guarantees the expul-
sion of the water excess (Garcia-Tenet al., 2010) and the consequent reduction of the green
shrinkage. Moreover, except in rare cases where furnaces are equipped with a heat reduction
system, the cooling stage occurs according to the furnace drift, analogously to what happens
in traditional archaeological kilns. This can be about 40-so'C per hour, and has a non-linear
behavior, illustrated in Figure 27.2.

Maximum temperature
• Residence

"
~
E
~
v
800
700
600
~ 500 C'o 0l
E
400 '"g
"'300
200
Soaking time :
100'

0 6 12 18 24 30
Time (hours)

FIGURE 27.2 Sketch of a typical firing diagram used when programming an experimental
firing in a laboratory with a furnace.
 EXPERIMENTAL FIRING AND RE-FIRING 493

Laboratory-based firing experiments, however, suffer from important limitations related

to the significant differences between the conditions that can be reproduced in a laboratory
and those that occurred archaeologically, particularly in open firings. Open firing is charac-
terized by high heterogeneity of heating and oxygen distribution; for example, different parts
of the same vessel can experience firing temperatures differing by hundreds of degrees, lead-
ing to different mineralogical transformations in a single pot (Maggetti et al., 2011). Therefore,
reproduction of open firing in laboratory furnaces, where the heating is generally uniformly
distributed for irradiation from electric resistances, reduces the heterogeneity observed in
archaeological ceramics or experimental ceramics obtained through ethnographic-like firing.
Moreover, laboratory furnaces normally operate in an oxidizing atmosphere, with an oxygen
fugacity of 0.2 bar. Only in rare cases, such as adhoc furnaces, can the atmosphere be fluxed
with inert gases (such as nitrogen) to reduce the oxygen fugacity and reproduce very low oxi-
dizing or non-oxidizing atmospheres (Maritan et al., 2006). However, due the risk and diffi-
culties of handling dangerous gases, such as CO, and CO which are primarily produced from
the combustion of natural fuels (such as wood and other vegetal remains, charcoal and dung),
laboratory firing experiments involving these gases are nor reported in literature. A possible
solution to the dangers of working with CO and CO, gas is to saturate the firing atmosphere
by firing briquettes alongside pieces of charcoal, both placed within partially isolated cups
(Tenconi, 2013; Ten coni et al., 2016), in which the limited flowing of air is just sufficient to oxi-
dize the carbon, creating a partially reducing atmosphere around the briquette. In addition,
the heating rate of laboratory furnaces is typically significantly slower than that recorded in
open firings, which can reach 8oo°C in 10 minutes. Tube furnaces provide the fastest heating
rate, 20-30°C per minute, and can approximate open firings better than traditional chamber
furnaces which heat at a rate of some oc per minute.
For all these reasons, laboratory firing experiments are better adapted to the reproduc-
tion of kiln firings, for which the heating and cooling rates of the furnace can be considered
analogous to those of archaeological kilns.
Firing experiments are often used in archaeometric studies of pottery to produce com-
plete sequences of briquettes, formed from the potential raw materials used to manufac-
ture the ceramics of interest, in a wide range of temperatures. The experimental ceramic
briquettes are characterized by different physical properties related to f1ring conditions and
temperature, such as color, mineralogical composition, porosity, and amount of the amor-
phous phase. During firing, the clay material undergoes important transformations, which
depend upon the mineralogical composition of the clay body, the grain size of the non-plas-
tic inclusions (minerals and rock fragments), the maximum firing temperature, the heating
and cooling rate, the kinetic of reactions, the oxidizing/reducing conditions during firings,
and the size and thickness of ceramic body.
Transformation reactions (such as breakdown of mineral phases occurring in the green
body, crystallization of new minerals, formation of an amorphous phase) generally occur at
the sub-solidus state and are thermodynamically and kinetically dependent (Riccardi et al.,
1999; Maritan et al., zoo6; Maggetti et al., 2011). This means they can occur at different tem-
peratures in relation both to the heating gradient and the firing atmosphere. Therefore, the
mineral associations that are produced during firing, and which can be detected for instance
by X-ray powder diffraction of the fired briquettes, can change in dependence on the length
of the firing process and the type of firing atmosphere. Figure 27.3 illustrates, as an example,
how the mineralogical composition of a chloritic-illitic clay very rich in carbonate (by other
(a) !Kiln firing! (b)
RT 300 35l> 400 450 500 ~5{1 ~UO 6b~ 700 150 ~00 ~00 Y[)() ~~0 1\)00 JO~U l JW
) Kiln firing I
o.l I I I II II I I I I I I II I I "'
" Oz''

"
111{110)
Chi (002)
Chl{OOJ)

"",,, ,,,
'"'
'"
Port '"
Port
0
'"
'"" uuj_J_J_LLLJ__L_[__j__~
Heml L

(c) !open firing)

Oxidising Firing tem~cratme I"C) Roducing
{d) jopen firing I O"idi>ing f-iring temperature ['C) Redu~ing

" "'
"' "',,,,
lii(OO 11!{00 ,,
,,
",,
!11{11 11\{11
Chf(oo;

,,",,
Chi(Oi): •)
Chi {oo (h1{00

,, ,,,,
,,
"'"
Po;
lo
"

l '"
Gh
"
,,
Ma 0
I
Ho

M~' 0"
l
- CJaYl Cneml(:of compositiOn {XRFj- ~ --· - -- ----- --r;:;;;;:alog<<:al co,;;;;osoMr.< (XRD)" - - - - - - - - ---r;;:tterbe~ts --
~so, Al?03 fc7 0, 0~~~- ! Ot~-W,
a h9.93 051
1•0
1
14.84 4.83 OJ)l !SO 30.25 067
Na 20 K20
319
P,O, Tot
010 9S29 2518
lOI
115
Oz PI
lO
Kfs
4
Ill
12
Chi
10
Kin Dol
6
Ca,
34 5 I 54
Wr
29
PI
25
_1>~~~9 07~~~~8_______~0~2~~~~~~~-~-'-"-~ 5 _ 1 4_ _ , __ - - ' - - - ' - -'---~___1__1_~--· ~ .. -'-·
FIGURE 27.3 Bar charts showing the changes in the mineral composition as a function of the firing temperature of briquettes fired
according to kiln firing and open firing in reducing and oxidizing atmosphere of two clays. Kiln firing: heating rate of zoo°C/h, soak-
ing time 6 h, cooling rate of about 50 °C/h; oxidizing atmosphere was provided firing the briquettes in air [f(O,) ~ o.z bars].

d)
 EXPERIMENTAL FIRING AND RE-FIRING 495

authors also defined as calcareous clays) (Maritan, 2003) changes when it is fired in a kiln or
in an open firing and in both oxidizing and reducing conditions. The decomposition of some
mineral phases, such as dolomite and calcite, and the crystallization of magnesium oxide
(periclase MgO) and calcium silicates (gehlenite Ca,Al(A!Si)0 7 and diopside CaMgSi,0 6 as
a result of the reaction between the carbonates (calcite and/or dolomite), decomposed clay
minerals and quartz) occurs in the kiln-fired ceramics at sooc lower than in open firing, as a
consequence of the kinetic factors, and of the grain size of non-plastic inclusions. Similarly,
in the kiln-fired briquettes, portlandite (Ca(OH),), formed as the CaO produced during the
decomposition of calcite, at temperature above 8oo°C, but larnite (Ca,Si04 ) forms in bri-
quettes made from the same raw materials in open firings above 90o 0 C. Firing atmosphere
also affects the thermal products present in ceramic vessels. Hematite (Fe 20 3), for example,
crystallizes in oxidizing conditions regardless of the soak time or maximum temperature
(Nodari eta!., 2007), but magnetite (Fe30 4 ) forms in reducing atmospheric conditions when
fired above 750°C (Nodari eta!., 2004). The mineralogical associations defined from each
set of firing experiment on a specific set of raw materials can be used to constrain the firing
temperature of ancient pottery produced using analogous base-day materials, in terms of
chemical and mineralogical composition and texture, and according to a type of firing (kiln
or open) hypothesized on the basis of the archaeological evidence.
In the same way, fired briquettes can be studied microscopically (Quinn, 2013) in order to
evaluate the physical transformations and microstructural changes which occurs during fir-
ing (Riccardi eta!., 1999; Maritan, 2003; Maritan eta!., 2007 ). For example, as the firing tem-
perature increases the internal structure of non-plastic inclusions are destroyed resulting
in the loss of certain optical properties, such as the disappearance of interference colors in
crossed polarized light of mollusk shells (Plate 5a-b) and micritic limestone fragments (Plate
5e-f). Changes in porosity, such as shape, besides depending on the material, preparation of
the body and forming technique, are also related to firing temperature; transforming from
small and irregular voids (vughs), characteristic of low firing temperature, to larger regu-
lar vesicles at higher temperatures (Plate 5c-d). Other important changes related to firing
temperature and conditions take place in the microstructure of the groundmass as it under-
goes gradual vitrification, such as the loss of birefringence, which determine an optically
active micromass to become inactive with firing increasing temperature, and the formation
of bridging structures, caused by the partial melting of the mineral phases for local reactions,
that can be observed between grains (Plate 5g-h).
Numerous other microstructures and mineralogical transformations can be observed
in clay-based ceramic materials that are related to and dependent on firing temperature
and conditions. Therefore, the comparison of microstructural and mineralogical features

FIGURE 27.3 Continued

Open firing: heating rate: 25°C/min, soaking time: 10 minute) cooling rate of about 100 oc;
h; reducing atmosphere was obtained by fluxing N, at a pressure of 0.5 bars, after filtering
with H,S0 4 , CaCl, and Mg(Cl0 4 ), to avoid air contamination; oxidizing atmosphere was
provided firing the briquettes in air [f(O,) S'! 0.2 bars]. Abbreviations: Qz: quartz; PI: pla-
gioclase; Kfs: K-feldspar; Ill (om) and (no): (om) and (no) reflections in illite; Chi (om)
and Chi (oo2): (oo1) and (002) reflections in chlorite; Kin: kaolinite; Dol: dolomite, Cal: cal-
cite; Per: periclase; Port: portlandite; Lar: larnite; Gh: gehlenite; Di: diopside; Hem: hematite;
Mag: magnetite;*: mineralogical composition was semi~quantitatively estimated using the
software FASES (Krajewski eta!., 1985); W L' liquid limit; W p: plastic limit; PI: plasticity index.
-
496 MALGORZATA DASZKIEWICZ AND LARA MARITAN

of ancient ceramics and of fired briquettes, obtained from firing under analogous condi-
tions of clay materials with very similar mineralogical, chemical, and textural composition
to that used in the specific ancient production, can constrain the firing temperature of the
potsherds.

RE-FIRING

The term "re-firing" refers to laboratory firing in controlled conditions of previously fired
products at a defined temperature. This term is used in reference to laboratory firing at
temperatures both below and above the original firing temperature, despite the fact that
laboratory firing at a temperature higher than the original firing temperature represents a
continuation and not a repetition of the firing process and, thus, is in reality the original
firing. The term "original firing temperature" (To) is reserved for the temperature at which
a ceramic product was fired by the potter who made it. In contrast, the term "re-firing tem-
perature" (Tr) refers to the temperature at which a previously fired product was fired in the
laboratory.
Analysis based on macroscopic observations of the thermal behavior of samples after re-
firing is a technique classed as one of the thermal methods of ceramic analysis. Ihe name
MGR-analysis was suggested by Daszkiewicz in 2001 at the European Meeting on Ancient
Ceramics (EMAC'o1 in Fribourg); it is an abbreviation of matrix groups by re-firing
(Daszkiewicz et al., 2001).' This technique consists of firing ceramic fragments in controlled,
standardized conditions and subsequently defining their thermal behavior. Depending on
the number of temperatures at which the re-firing process is carried out, this technique is
referred to either as full MGR-analysis (re-firing at 400, 6oo, 700, 8oo, 900, woo, 1150 and
12oo'C) or abridged MGR-analysis (re-firing at 1100,1150 and 12oo'C)
As with other types of scientific analysis, accuracy, precision, repeatability, and reproduc-
ibility of results are vital in MGR. Accuracy, the proximity of the analytical results to the true
value-in this case the original firing temperature-is verified through the analysis of test
materials and/or ceramic vessels from ethnographic studies. The accuracy of the measure-
ment depends upon the parameters of the re-firing process; namely the heating rate, soaking
time at the peak temperature, and atmosphere. Analysis of model briquettes revealed that
in a fully oxidizing atmosphere the same result is achieved with a heating rate of 2oo'C/h as
with one of 30o'C/h, and after a soaking time of 1h, 2h, or 3h. Thus only the temperature is
significant for the results. 2
The precision of re-firing analysis of model briquettes depends entirely upon the opera-
tional precision of the laboratory kiln. However, analytical precision for archaeological sam-
ples is potentially affected by the heterogeneity of the ceramic body (precision of sampling).
Moreover, archaeological ceramic materials could have undergone changes linked to altera-
tion processes. The range of changes is dependent on the quality and variety of the ceramic
fabric and on post-depositional conditions (see Chapter 11 in this volume). '!he effect of the
alteration process on the state of preservation of archaeological ceramics should be taken
into consideration when preparing samples and interpreting the results of re-firing.
The reproducibility of analysis of the same piece of potsherd after an interval of several
months or, as is often the case, several years or, for example, after the kiln has been replaced
 EXPERIMENTAL FIRING AND RE-FIRING 497

or repaired, is imperative. Therefore, the consistency of results obtained from multiple mea-
surements is monitored by re-firing a prepared model briquette together with each series of
archaeological pottery samples.

Reconstructing the Original Firing Process by Re-Firing

If re-firing is carried out using the same conditions as the original firing, then during the
course of re-firing at a temperature below the original firing temperature (To) no physi-
cochemical changes should take place in the re-fired ceramic material; phases "frozen" in
the ceramic fabric at the To will not change until the firing process, interrupted at the To, is
resumed. Exceeding the original firing temperature (Tr> To) during the course of re-firing
results in the resumption of those processes which were taking place in the ceramic material
and interrupted at the moment when the original firing at the To was completed. This effect
is used to estimate the temperature at which archaeological ceramics were originally fired.
These methods using various temperature-dependent changes are summarized as dynamic
methods. 3
Because the temperature at which changes occur also depends on firing atmosphere and
time, the result of this analysis should be referred to as the equivalent original firing tem-
perature Teq (Tite, 1969). Teq corresponds to To when the original firing and cooling took
place under the same conditions as the laboratory firing and cooling. In general, all those
parameters which undergo change when a ceramic body is fired could be taken into consid-
eration: color, linear changes (shrinkage, expansion), vitrification, physical ceramic proper-
ties (open porosity, water absorption, apparent density, bulk density), phase composition
(with limitations arising from alteration processes), texture, structure, velocity of propaga-
tion of acoustic longitudinal waves in ultrasonic range, changes in mechanical properties
(flexural strength, compression strength, tensile strength). This list could easily be enlarged
to include other parameters, discussed in Heimann (1982).
Taking into account the gradient of temperatures in a pottery kiln or in an open fire, anal-
yses that allow the original firing temperature to be determined with an accuracy of± 50°C
are regarded as sufficient. Therefore, re-firing is typically carried out at intervals of 50°C or
100°C, depending on the parameters being investigated 4 The range within which the equiv-
alent original firing temperature falls is one where the bottom of the range is defined by the
highest re-firing temperature at which changes in the analyzed parameter are not observed,
and the top of the range is defined by the lowest re-firing temperature at which changes are
first observed (Tr max:;:; Teq ;::Trmin)·
Laboratory re-firing is typically conducted in air (oxidizing conditions). For ceramics
which were originally fired under different conditions, such as a reducing or partial oxi-
dizing atmosphere, the Teq value determined will also be affected by this change in atmo-
sphere between the original firing and re-firing. Scanning electron microscope observation
of changes in vitrification levels in briquettes re-fired in an argon~saturated atmosphere
and dilatometric analysis in argon flow, carried out on fragments of gray pottery originally
fired in a reducing atmosphere, revealed that the Teq values for these samples were a max-
imum of 70°C lower than those fired in air (Daszkiewicz and Raabe, 1989a, 1989b, 1995).
This difference is smaller than the temperature gradient in a pottery kiln and can be con-
sidered insignificant when To is used as an indicator of technological advancement and/or
498 MALGORZATA DASZKIEWICZ AND LARA MARITAN

skill. Nevertheless, To is often a significant (or even the only) technological parameter corre-
lated with cultural change in a given territory, and is also frequently a distinguishing feature
between products made at different workshops or between imported and locally produced
ceramics.
The fastest aud easiest way of determining Teq is to analyze changes in sherd color before
and after re-firing.S For this analysis, nine small slices (one for each re-firing temperature)
are cut from every sherd along a plane perpendicular to the vessel's axis. The size of the slices
therefore depends in one direction on the wall thickness of the vessel and should be 1 to 2 em
in length and at least 1 to 2 mm in thickness. These slices are then re-fired in an electric labo-
ratory furnace, using the standard procedure, at 400, 6oo, 700, 8oo, 900, 1000, noo, 1150
and uoo°C in air, static (this means without air flow), with a heating rate of 200°C/h and
a soaking time of 1 hour at the peak temperature, and cooled with the kiln for 1 hour, after
which they are removed from the kiln and left to continue cooling until they reach room
temperature. An additional slice is removed from each ceramic sample and retained as a
reference for the original appearance of the sherd, i.e. its appearance before re-firing. This
process is referred to as full MGR-analysis 6
Several examples of MGR-analysis are shown in Plate 6. Sample 1 represents the MGR-
analysis of a briquette cut from a model ceramic sample fired at To= 9oo"C (with the same
conditions as used for the re-firing)-' The color of the re-fired briquette does not change
after re-firing at up to 900°C (TrmaJ; the first changes are observed after re-firing at woo°C
(Trmin). The same illustration also shows re-fired briquettes cut from archaeological pottery
(samples 2 to 6). Sample 2 was originally fired in an oxidizing atmosphere. The temperature
at which the first changes in the re-fired fragments become apparent is Trmio = 90o"C. The
same is true for sample 3, but the color of its gray core had already changed after re-firing at
6oo"C due to the burning out of organic substances.
This change in color is linked to the difference in conditions between the original firing
and the re-firing and may result from the reduction of iron oxide, the presence of organic
material, or both. The temperature at which these sherds change color depends therefore on
the nature of the gray/black color. In Plate 6 examples 3 and 6, the dark core fades after re-
firing at 6oo'C, and the entire cross-section gradually becomes the same color as the outer
edges of the cross-section (i.e. the inner and outer walls of the vessel). This "original" color
changes markedly after re-firing at 9oo"C in the case of sample 3 and at 70o'C for sample 6,
indicating that the Teq falls within 8oo-9oo'C and 6oo-7oo"C respectively. In these sam-
ples, only the latter stages of the original firing took place in an oxidizing atmosphere (creat-
ing the rind oflighter colored matrix along the edges of the vessel profile), but not sufficiently
long enough for the core of the vessel walls to completely oxidize. The black color of sample
5 derives from organic matter which was not burned out during firing in a partial oxidizing
atmosphere. As with sample 6, its Teq, determined by MGR-analysis, was between 6oo and
7oo"C, which explains why the calcite temper observed in both samples is not thermally
decomposed. Sometimes minimal changes in color are observed in archaeological sherds
already after re-firing at 40o"C. These changes are linked to the burning out of organic impu-
rities from use and/or deposition. As mentioned earlier, further changes in color indicate To
as described.
Ceramics which were fired without any change in atmospheric conditions during the
original firing process often possess indicators about the stability of the temperature in the
kiln or open fire. Sample 4 in Plate 6 illustrates re-fired briquettes cut from a sherd originally
 EXPERIMENTAL FIRING AND RE-FIRING 499

fired in an oxidizng atmosphere but displaying two colors in cross-section. A change in the
color of the core is observed after re-firing at 900°C, whilst the edges of the sherd do not
change color until it is re-fired at woo 0 C. TI1is indicates that the original firing was carried
out at Teq < 900°C and that during the course of the original firing process the temperature
range slightly exceeding 900°C was reached only briefly.
In the case of ceramics that were originally fired without complete combustion of organic
matter, it is essential to determine the re-firing temperature at which the black/black-
ish-brown color of the sherd fades because this temperature is correlated with the type of
organic material added to the ceramic body, which is often the only means of distinguish-
ing between ceramic workshops (Daszkiewicz et aL, 2002; Daszkiewicz and Kolosowska,
2004). Meanwhile, the temperature at which the black surface of the pottery vessel (and/or
sheen) fades during the course of re-ftring is strictly correlated with the technology used by
ancient potters to create the black surface and sheen (Daszkiewicz and Baranowski, 2010).
A polished surface blackened by carbon (fumigation) changes in color from black to red-
dish/beige/brown after re-firing at 6oo°C. If the coating layer is a black iron-rich slip, the
black color of the slip begins to fade around 700°C as a result of the reoxidation of the black
iron phases. The color of the slip changes to brown-gray or grayish-brown until it reverts to
a red/brown (depending on the composition of the slip) after reoxidation is completed at
900-10oo 0 C. This contrasts with the black-gloss variety of coating-layer, 8 where the black
color does not change when re-fired at up to woo 0 C. MGR-analysis is also a good tool for
analysing glazed ceramics in order to ascertain the technological process which produced
them. When a glazed ceramic was bisque fired prior to the application of the glaze, the To of
the ceramic body is higher than the flowing temperature of the glaze.
Structural MGR-analysis is a variant of full MGR-analysis that involves examining the
appearance of a ceramic fragment (surface texture) under a reflected light microscope both
before and after re-firing. Re-firing is carried out as outlined above, in steps on wo°C, but
each re-firing is carried out on the same briquette (Plate 7a). After each re-firing step a high-
resolution photomicrograph is taken, always of the same area. At temperatures exceeding the
To, thermal alterations of the ceramic become visible, such as changes in color, pore shape,
or cracks. This technique is particularly useful for estimating the temperature to which over-
fired ceramics, such as over-fired kiln wasters or fire-damaged ceramics (e.g. in a merchant's
depot), were subjected. No changes in pore shape are detectable in the over-fired sample in
Plate 7b up to noo°C (Trm"). Changes in vitrification and pore shape start after re-firing at
1150°C (Trm;,), indicating that the sample was over-fired (Teq) between noo-1150°C.
Re-firing of the same briquette also allows the Teq to be estimated by analysing changes
in physical ceramic properties, depending on Tr (K-H analysis9). 10 achieve this, open
porosity, water absorption, and apparent density were determined after each re-firing using
hydrostatic weighing.w Figure 27.4 illustrates the physical ceramic property values versus
re-firing temperature of a briquette cut from the model ceramic sample shown in Plate 6,
originally fired at To = 900°C. An increase in apparent density accompanied by a drop in
water absorption and open porosity is detectable after re-firing at woo°C (Trmin)> indicating
that this temperature is higher than the original firing temperature. The example presented
here, according to K-H analysis, was originally fired at Teq:::::: 900-I000°C, consistent with
the known To. Maximum apparent density for this material occurs at uoo 0 C. Additionally,
the apparent density values of a sherd after re-firing at 120o°C can point to differences in
ceramic body preparation in those instances where analyzed sherds are made of the same
500 MALGORZATA DASZKIEWICZ AND LARA MARITAN
,,,,_,,,-.,,,,,,,,,,

FIGURE 27.4 Determination of the original firing temperature using the K-.H method (Teq
900-1000°C).

raw material (Daszkiewicz, and Bobryk, 2001), because where the same raw material is con-
cerned any differences noted in its open porosity are linked to differences in the de-.airing of
the ceramic body. 11

RAW MATERIAL CLASSIFICATION

USING MGR-ANALY§IS

MGR-.analysis can be used for the classification of ceramic sherds according to the compo-.
sition of their matrix material because the thermal behavior of plastic components during
firing is governed by their chemical and phase composition (Daszkiewicz and Schneider,
2001). Before it became a routine use it was preceded by a control series of comparing chemi-
cal analyses using the WD-.XRF technique on several thousand samples, and thin-section
studies of several hundred samples. Numerous experiments have shown that the opti-
mal temperature for re-firing in order to identify matrix type is 1200°C. Plate 8 shows five
samples of archaeological pottery re-fired at 8oo°C, 900°C, and 12oo°C: note that it is not
until the samples were re-fired at 1200°C that differences associated with the sherds' chemi-
cal composition became clearly visible (the two samples which fire yellow have the same
chemical composition, which differs from that of the three identical reddish-brown firing
samples).
Classification of ceramic sherds according to the mineralogical and chemical composi-
tion of the matrix (MGR-groups) requires only abridged MGR-analysis, i.e. re-firing at three
temperatures. Firing conditions are the same as those described in the section on determin-
ing Teq. The thermal behavior and appearance (color, shade of color, and texture) of samples
 EXPERIMENTAL FIRING AND RE-FIRING 501

Cr Ni Zn Rb Sr Zr Ba

A 50.2 0.88 15.0 7.54 5.48 17.9 0.50 2.08 0.26 123 238 149 102 80 218 168 297
B 48.2 1.45 13.9 9.10 8.07 16.5 0.49 1.74 0.43 157 288 182 89 54 419 189 244

FIGURE 27.5 Two samples made of the same marly clay re-fired at noo"C. A ; sample
without intentional temper. B; sample tempered with crushed basalt (temper is meleted at
this re-firing temperature). Photographs were taken with a macro lens by M. Baranowski.

re-fired at three different temperatures (noo°C, nsooc and 1200°C) are taken into account
when defining individual MGR-groups;" however, definitive classification is based on ther-
mal behavior at 1200°C.
Different colors and shades of the re-fired matrix are indicative of different matrix min-
eralogy and chemistry. Therefore, samples displaying the same color and shade after re-
firing at 120o°C are manufactured from plastic raw material of the same composition and
are considered a single MGR-group. Ceramics from a single MGR-group which also have
the same non-plastic inclusions (same non-plastic material group) were manufactured
from the same body and have a similar chemical composition. They show the same fabric.
However, ceramics from the same MGR-group belonging to different non-plastic mate-
rial groups, because they were intentionally tempered with different non-plastic compo-
nents or different quantities of the same components, show different ceramic fabrics and
have different chemical compositions. This means that two sherds made from the same
clay can belong to two different fabrics and/or chemical groups, but to the same MGR-
group because chemical and fabric groups consider the bulk composition of the sherd,
matrix material and temper, whereas MGR-groups consider only the matrix material
(Figure 27.5). Therefore, in provenance studies, both MGR and chemical analyses should
be conducted.
Macroscopic analysis of non-plastic inclusions in ceramic fabrics after re-firing is benefi-
cial because many mineral phases are more clearly visible in samples after re-firing (Plate 6,
sample 6). MGR-analysis can be used to classify ceramic sherds according to the composi-
tion of their non-plastic components (clastic material groups; CM-groups) and to make an
assessment of the recipe, i.e. the ratio of the non-plastic inclusions to the matrix. The results
of this classification are more reliable than the macroscopic descriptions of temper seen in
fresh fracture widely used by archaeologists.

MGR-ANALYSIS DATA REPORTING

The growing use of MGR-analysis in the study of ancient pottery, both as an auxiliary
method to bulk chemical and petrographic analysis, as well as for the rapid and inexpensive
502 J\'lALGORZATA DASZKIEWI(;Z AND LARA MARITAN 1
raw material classification of large quantities of ceramic sherds, has made it necessary to
establish a standard formula for writing up results. The principles of classifying re-fired sam-
I
ples in raw material classification are outlined below.
Based on the color of samples after re-firing at 12oo'C three fundamental categories of
matrix minerals can be identified: non-calcareous, calcareous and mixed matrices. The fol-
lowing criteria are used in matrix classification:

(i) Samples are considered to have a non-calcareous matrix if no calcium silicate or

calcium aluminum silicate phases form during laboratory re-firing in air at a tem-
perature of 1200'C, which is indicated by the fact that the samples do not take on a
greenish tint after re-firing.
(ii) Samples are said to have a calcareous matrix if calcium silicate or calcium aluminum
silicate phases form during laboratory re-firing in air at a temperature 1200'C, indi-
cated by the fact that these samples do become greenish in color (or have a greenish
or greenish-yellowish tint, or grayish-green tint).
(iii) Samples are considered to have a mixed matrix if various irregularly distributed
patches of greenish color are noted in the fabric after re-firing.

Matrix texture is identified based on the appearance of samples when re-fired at uoo 0 C.
Principal matrix textures are as follows (examples are shown in Plate 9 ):

sintered (SN): the sherd is well-compacted; it may or may not become smaller in size in
comparison to the original sample, whilst its edges remain sharp
over-fired (ovF): the sample changes in shape; bloating, however, does not occur nor
does the surface of the sample become over-melted
slightly over-melted (sovM): over-melting of the sample surface is observed, but there is
no change in shape, and edges remain sharp
over-melted (ovM): the surface of the sample becomes over-melted and its edges become
rounded
semi-melted (sMLT): over-melting of the surface occurs, changes in sample shape are
observed (not just rounded edges), but no bloating is noted
melted (MLT): the sample becomes spherical or almost spherical in shape
bloated over-fi~ed (BlovF): the sample expands in volume, but the surface does not
become over-melted
bloated over-melted (BlovM): the sample expands in volume and its surface is
over-melted
flowed (Fl): the sample flows into a thin layer

The non-plastic phases of the matrix can alter the appearance of samples after re-firing,
especially where grains of carbonates are present, as these decompose when fired at
temperatures exceeding 6oo-7oo'C (e.g. Plate 6 sample 6). The destruction products
expand by taking up water and by subsequent re-carbonatization. The following behav-
iors can be distinguished: the re-fired fragments crack; the re-fired fragments crumble
to a powder.
 EXPERIMENTAL FIRING AND RE-FIRING 503

CoNCLUSION§

Experimental firings are a very powerful method to understand the dynamics of the firing
process, all the possible modification that could have been used in the past and presently
testified by ethnographic stndies. The analysis of the compositional and structural changes
with the temperature, in combination with the firing cycle duration and redHox conditions
on fired briquettes obtained by laboratory firings, in which the firing process can be planned
ad hoc, can provide precise information of the ancient firing technology of specific types of
pottery.
It should be strongly emphasized that the results of experimental firing cannot be directly
transferred to the results of re-firing. It is necessary always to keep in mind that each ceramic
body has its own very specific features and, especially for ancient ceramics, there is no such
thing as a typical clay/body or a typical thermal behavior of typical clay/body (how it is
unfortunately found in publications).
There are only very few instances where the raw material used by ancient potters is cur-
rently available for experimental firing (as is the case, for example, with clay used in the
manufacture of Terra Sigillata in Rheinzabern) and the ancient technological process is
known. This situation may represent a limit when ancient pottery is compared with modern
experimental firings, which can cause an over- or underestimation of the ancient firing tem-
perature. Therefore, the advantage of re-firing fragments of ancient sherds instead of firing
model briquettes is that the interpretation of the re-firing results is securely based on the
same material composition. Re-firing can be used to obtain information about the original
firing process: about the temperature of the original firing (also within the range where origi-
nal phases were already thermally decomposed and new ones did not build), about the firing
atmosphere, about the firing cycle duration and the soaking time at maximum temperature,
about the number of times glazed pottery was fired in those cases where the hemisphere
point of the glaze is known, and about the technological process which led to the creation of
a black surface (for a simplified classification of archaeological pottery with a black surface).
Re-firing at temperatures higher than the original firing temperature can also be used to
classify the raw material used for the manufacture of ceramics, hence to carry out a classifica-
tion based on the variety of the plastic part of the body and an assessment of the non-plastic
part of the body (MGR-analysis). It is a powerful tool for revealing inhomogeneities in sherds
and for determining the composition of the matrix independent of any possibly added non-
plastic material. Therefore, re-firing is a useful auxiliary method to chemical analysis.

NOTES

Although parts of this chapter have been co-authored, Lara Maritan is solely responsible
for the sections "Experimental Firing;' "Experimental Archaeology Firings;' "Laboratory-
Controlled Firing;' and Malgorzata Daszkiewicz is responsible for the sections "Re-firing;'
"Reconstructing tbe Original Firing Process by Re-firing;' "Raw Material Classification Using
MCR-Analysis;' and "MGR-Analyis Data Reporting:'
504 MALGORZATA DASZKIEW!CZ AND LARA MARITAN

1. The principles of MGR~analysis were formulated in 1987-1990 by Daszkiewicz whilst

working on her PhD thesis on the technology of fourteenth-sixteenth-century pottery
from Plock (Daszkiewicz, 1992). MGR-analysis was not intended as a means of evaluating
phase composition in qualitative and quantitative terms (other than to provide a general
identification of the clay type used by ancient potters), but as a means of quickly classify-
ing samples in terms of their matrix. Since 1987 the author has carried out MGR-analysis
on almost 12,000 fragments of ancient ceramics ranging in date from the Mesolithic to the
medieval period from Europe, the Near East, Egypt, Sudan, and the New World. Model
analyses have also been conducted. MGR-analysis results have always been, and con-
tinue to be, correlated with the results of chemical analysis (WD-XRF) and thin-section
studies. Experiments have also been carried out on originally black/gray colored ancient
ceramics fragments. These samples, after re-firing in air (standard MGR-analysis), were
re-fired once again in various conditions that led to their becoming black/gray once
more. Moessbauer spectroscopy was used on these samples to gauge what it was that
was responsible for their coloration (part of this study is published for gray ware from
Plock: Daszkiewicz and Raabe, 1995).
2. Results of model analyses carried out by the author during 1987-1990 on clay from the
Plock region, and jointly with Bobryk in 2014 on jockgrim clay (used in the manufacture
ofRheinzabern sigillata).
3. The opposite of dynamic methods are static methods, in which specific characteristics of
a given sample are analyzed and the results are used to draw conclusions about the origi-
nal firing temperature (To). Static methods can be used to define these characteristics, for
example, the degree of vitrification, or to make an estimate of firing temperature based
on the presence/or absence of clay minerals, calcite, gehlenite, and diopside. The occur-
rence of specific phases and the degree of vitrification are dependent not only on the
original temperature but also on the chemical, as well as mineralogical and petrographic,
composition of the ceramic body, grain sizes and on the firing process (atmosphere, heat~
ingrate, soaking time at the peak temperature and time during other stages of firing). But
during the firing process the clay-temper mixture is not within a thermodynamic phase
equilibrium and the temperatures at which particular phases occur depend on kinetic
and many other factors. In addition, changes in phase composition also sometimes occur
during the course of the sherd's deposition in its archaeological context, e.g., second~
ary deposition of carbonates or rehydroxylation of clay minerals and decomposition of
calcium silicates (e.g. gehlenite). The use of dynamic methods is decidedly preferable (in
this author's view) because of the ambiguous interpretation of results associated with
static methods.
4· Analysis of Neolithic to Christian period pottery recovered from the Fourth Nile Cataract
region (Sudan), has shown that determining the original firing temperature with this
accuracy is sufficient as an indication of the technological level of the given period/cul-
ture, or of a production center/workshop (Daszkiewicz et al., 2003).
s. The use of color in order to assess original firing temperatures was first proposed by
Matson (1971), who fired raw materials which may have been used for making archaeo-
logical ceramics and subsequently compared the color of the fired briquettes to the color
of the original archaeological ceramics.
6. A similar method, the Thermal Color Test (TCT) was devised at the Laboratory for
Ceramic Research (Department of Geology, Lund University, Sweden) for the purpose
of determining original firing temperatures (Hulthen, 1976; Lindahl, 1986; Stilborg, 1997).
In this test always the same ceramic fragment is re-fired at I00°C increments up to a
 EXPERIMENTAL FIRING ANDRE- FIRING 505

temperature ofwoo°C and the Munsell Soil-Color Chart is used to classify the colors. The
color codes are then transferred to diagrams and the temperature at which change occurs
is identified.
J. 1bis is only one example from an extensive model study of firing and re-firing ceramic
samples at various temperatures (Daszkiewicz and Bobryk, unpublished).
s. Gloss is a slip which due to repeated very fine levigation is enriched in potassium and
iron and thus vitrifies earlier than a normal slip (but it is not a glaze composed like glass).
Because of the vitrification a re-oxidation is limited. It makes a glossy surface and is typi-
cal for Attic black and red figured vases and Roman Samian Ware. Another possibility for
black glossy surfaces used already in Neolithic periods is fumigation of polished vessels.
9· At an archaeometry conference held in Cologne in 2001 this name was suggested by
M. Daszkiewicz in memory of Dr. H. Kilb and Prof. H. W. Hennike, who introduced the
measurement of changes in values of apparent density versus re~firing temperature (Kilb
and Hennicke, 1980 ).
10. Prior to this assessment, samples must be boiled in distilled water for two hours in order to
fully saturate all open pores with water. The samples are then cooled to room temperature
(the term "room temperature" refers to a temperature of 20°C) and weighed twice, mak-
ing note of the mass of the sample immersed in water (mww), and the mass of the moist
sample weighed in air (mw)· Next, the samples are weighed for a third time in air, having
first been dried to a constant mass in a dryer at 105°C and cooled to room temperature in
a desiccator. This is the method used fOr determining the mass of a dry sample (ms)· Open
porosity, i.e. the percentage of the amount of water absorbed by a given volume of sample,
c m -m
was determined using the 10rmula p "' ' x 100 and expressed as a percentage.
" mw -m ww
Water absorption, i.e. the percentage mass gain of the sample soaked in water in relation
to the mass of the dry sample, was determined using the formula N mw - m,, x 100 and
m,
expressed as a percentage. Apparent density, i.e. the mass of the sample in relation to its

volume, was determined using the formula d~ = X pH 0 and expressed in g/cm 3

mw -mww 1

PH 20 =bulk density of water at temperature of measurement; in this analysis, the tempera~

ture of measurement is room temperature and Ptho = 1g/cm3).
u. According to the hypothesis propounded by M. Daszkiewicz, this analysis allows ceramic
workshops to be identified based on assessment of the degree to which the ceramic body
was de-aired. This was tested on Terra Sigillata featuring makers' stamps, made at four
workshops in the Roman production center ofRheinzabern (Daszkiewicz et al., 2001).
12. These observations are similar to those described in the sintering test devised at Lund
University (Hulthen, 1976; Lindahl, 1986; Stilborg, 1997). In this test the same fragment is
re-fired in 50°C intervals starting from woo°C and continuing until it reaches melting point
(which could be up to 14oo'C); after every stage of re-firing the sample's behavior is noted.

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506 MALGORZATA DASZKJEWICZ AND LARA MARITAN

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between the Protohistory Communities from the Northern Italy, Particularly Focusing on
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~-------------- ..................
CHAPTER 28

FOURIER TRANSFORM
INFRARED SPECTROSCOPY
(FT-IR) IN
ARCHAEOLOGICAL
CERAMIC ANALYSIS

SHLOMO SHOVAL

INTRODUCTION

Infrared Spectroscopy Studies of Ancient Pottery

FT-IR spectroscopy has recently become widely utilized for investigation of ancient ceramic
and archaeological artifacts (Roberts et a!., 2008; Kurap et a!., 2010; Nel et a!., 2010; Weiner
2010; Ravisankar et al., 2011, 2014; Shoval et al., zona; Rutherford et al., 2012; Izzo et al., 2013;
Shoval and Paz, 2015). This method provides a mineralogical fingerprint of the ceramic and
is preferred to other mineralogical techniques to identify the mineral composition of ancient
ceramics (De Benedetto eta!., 2002, 2005). The major advantage of FT-IR spectroscopy is its
ability to identify the composition of both crystalline minerals (Barilaro et a!., 2005, 2008;
Akyuz eta!., 2007, 2008) as well as the pseudo-amorphous phases of the fired-clay ceramic
(Shoval et a!., 2oua). Although the XRD (X-ray diffraction) method is the technique tra-
ditionally used for mineralogical analysis (Heimann and Maggetti, 1981; Maggetti, 1981), it
unsuccessfully observes the pseudo-amorphous phases of the fired-clay ceramic, because they
lack distinct XRD peaks. Moreover, analysis by FT-IR spectroscopy is almost non-destructive
for the artifacts (Calia et al., 2011), since it requires only a small amount of ceramic material
(approximately 1 mg), whereas the XRD method requires a significantly larger sample. FT-IR
spectroscopy is a simple, fast, and reliable analytical tool and is relatively inexpensive. In addi-
tion, short analysis time means that researchers obtain results almost immediately, and with
by portable apparatus the FT-IR analysis can be done in the field.
510 SHLOMO SHOVAL

Infrared spectroscopy is based on the manner in which radiation in the infrared range of
the spectrum interacts with a material (Weiner, 2010). Infrared radiation is absorbed differ-
entially by functional groups of the material according to the structure and vibration of their
bonds and crystal lattice, The functional groups absorb infrared radiation frequencies which
are resonant with their crystal structure (i.e. have the same energy as the transition energy
of their bonds); therefore the frequencies absorbed by a material are characteristic of the
structural-chemical composition of that materiaL In the infrared spectrometer, the sample
material is irradiated with full spectrum infrared light and the output or unabsorbed radia-
tion is measured by the detector. The absorption of specific wavenumbers (spatial frequency
of a wave) by the material means that some frequencies of radiation do not reach the detector
of the spectrometer. As a result, the intervals of absorption are recorded as series of bands
(peaks) on the infrared spectra, The FT-IR spectra are usually depicted as absorption unites
versus wavenumber units (in em·') at the range 4000-400 cm· 1• Each mineral has character-
istic bands in the spectra which enable its identification (Farmer, 1974), These characteristic
bands are used to identify the mineralogical composition of a materiaL

The Mineral Composition of Fired-Clay Ceramics

FT-IRis a powerful technique for assessing the mineralogical composition of archaeological
ceramics. These ceramics were produced by firing of clay raw materials. During firing, the
primary clay of the raw material is transformed by a series of reactions to fired-clay ceramic
(Maggetti, zoo9; Maggetti et aL, zon), Two main types of ceramics were produced in ancient
times: calcareous (calcite-rich) ceramics and non-calcareous ceramics (Fabbri et al., 2014).
Their mineral assemblages depend on the type of the raw material and the temperature of
the firing (Shoval et aL, zona),

Mineral Assemblage ofNon-Calcareous Ceramic

In the firing of non-calcareous raw material at temperatures no higher than 950°C the ini-
tial clay is transformed to fired-day, which is defined as meta-day (Shoval et aL, zona), This
transformation occurs through a thermal process called dehydroxylation. Kaolinite clay trans-
forms to meta-kaolinite, and smectitic (montmorillonitic) clay transforms to meta-smectite
(Shoval et aL, 2011a; Shoval and Paz, 2015), In this process, the kaolinite clay dehydroxylates at
approximately 450-soo'C (Frost and Vassallo, 1996; Dion et aL, 1998), forming meta-kaolinite,
which is characterized by a pseudo-amorphous short-range ordered structure (Freund, 1974),
Smectite (montmorillonite) clay dehydroxylates at approximately 6oo'C, forming meta-smec-
tite with a pseudo-amorphous structure (Heller-Kallai and Rozenson, 1980 ), At fhe same time,
illite clay dehydroxylates at approximately 550-9oo'C (Gualtieri and Ferrari, 2006), forming
meta-illite. The consolidation of the ceramic body by sintering of the fired-day usually occurs
in firing around 90o'C (Grimshaw, 1971; Rice, 1987), In this process, the meta-day grains stick
to each other. In heating of kaolinite above 95o'C the meta-day progressively transforms to a
defect spinel-type phase and at higher temperature to poorly crystallized cubic mullite (Shoval
et aL, zonb ), The formation of well-crystallized phases of mullite is observed at approximately
12oo'C The major phases formed by the progressive heating of smectite have been identified
as spinel, mullite, cordierite, and cristobalite (Seyama and Soma, 1986),
 FT-IR IN ARCHAEOLOGICAL CERAMJC ANALYSIS 511

Mineral Assemblage of Calcareous Ceramic

In firing of calcareous raw material, the presence of calcite affects the thermal reactions.
The calcite decomposes through a thermal process called decarbonation. During decar·
bonation, carbon dioxide (CO,) is released, and free-lime (CaO) is formed (Fabbri et
al., 2014). Under prolonged ceramic firing the decarbonation takes place at temperatures
between 6oo and 8oo°C, depending on the form of the calcite, the impact of the clay, and
the firing conditions (Shoval et al., 1993; Maggetti et al., 2011). In parallel to decarbon·
ation, a process of dehydroxylation of the clay to form the pseudo-amorphous phase of
meta-day takes place (Shoval, 1988). In ceramic firing above 8oo°C, the free-lime from
the decarbonated calcite generates newly formed firing silicates by reaction with the
fired-clay. These firing silicates include minerals such as gehlenite, anorthite, larnite and
diopside-wollastonite (Maggetti, 1982; Shoval, 1988; Dondi et al., 1999; Cultrone et al.,
2001; Trindade et al., 2009 ). After firing, recarbonation of the excess free-lime takes place
by the reaction with water vapour and carbon dioxide from the air, forming crystalliza·
tion of fine reformed (recarbonated) calcite within the ceramic material (Shoval et al.,
zona; Fabbri et al., 2014).

SAMPLE PREPARATION FOR FT-IR SPECTROSCOPY

The spectra presented in this work were obtained using a )asco FT-IR spectrom·
eter (Series 4000) with Spectra Manager software. Part of the spectra was recorded using
ThermoScientific Nicolet (Series DXC) with Omnicsoftware. KBr (potassium bromide) disk
was used as carrier transparent material for the analysis of the sample in the apparatus. A
small sample of the ceramic is first powdered, dispersed in KBr, and then pressed into a disk.
For that, 1mg of the powdered sample was mixed with 150 mg ofKBr by grinding in an agate
mortar. Before analyzing, the disk can be also dried in an oven at no°C and then repressed
to improve the resolution of the spectra. Analysis of the bulk ceramic gives the composition
of the ceramic matrix mixed with the temper particles (the latter known also as non-plastic
component and inclusions). Particular pottery attributes, such as separated pastes, temper
particles, binders, glazes, slips, paints, and pigments can also be analyzed after picking under
a zoom stereomicroscope.

FT-IR SPECTRA AND SPECTRAL

ANALYSIS OF CERAMIC

Representative FT-IR Spectra of Archaeological Ceramic

Figures 28.1 and 28.2 show original spectra and spectral analysis by curve-fitting and
by second-derivative. The figures display the IR spectra in the range !800-400 em-•
of representative Iron Age pottery from Levantine sites and Bronze Age pottery from
Canaanite sites. The figures illustrate the different minerals composing the ceramic
512 SHLOMO SHOVAL

according to their indicative bands. Diagnostic bands are: 1030-1090 cm- 1 of fired-
clay (meta-clay), 1420-1450 em-' of calcite, 778 and 798 (band-doublet) of quartz; 912-
915 cm- 1 of silicates.

Spectral Analysis by Curve-Fitting and Second-Derivative

In order to improve the identification of different minerals and minor phases of the ceramic>
the original spectra were analyzed by curve-fitting and by second-derivative (Figures 28.1
and 28.2). The spectral analyses presented in this work were obtained using the GRAMS/
AI 32 software package of the 1bermoScientific Corporation. The curve fitting of the spectra
were carried out with the "peak fitting function" of the software. Lorentzian band shape and
in several spectra Gaussian band shape were chosen for the fitting. Second-derivatives of the
spectra were obtained with a derivative "gap" function of the "Grams» software.
The FT-IR spectra of the pottery may exhibit composite bands often representative of
mixtures of minerals. These composite bands may overlap partially, appearing as asymmet-
ric bands or as band-shoulders. For example, in the spectra of the ceramic the main SiO
band arises from contribution of meta-smectite, meta-kaolinite, and quartz, which bands
are partly overlapped (Figures 28.1 and 28.2). The spectral analysis enables the separation of
these partial overlay band> and improves identification of individual compositional phases
in the ceramic fabric (De Benedetto et aL, 2002; Shoval eta!., zona). The curve-fitting tech-
nique has the ability to convert the composite bands into its components, which are eas-
ily quantified. In this manner, the broad bands, asymmetric bands, and band-shoulders are
separate into their components. The second-derivative technique enables us to identify the
exact frequencies (wavenumbers) of the composite band components. For example, spectral
analysis enables the separation of the main SiO band to components of meta-smectite, meta-
kaolinite, and quartz (Figure 28.2).

Quantification by FT-IR Spectroscopy

The FT-IR method adds a quantitative dimension to mineralogical analysis of archaeologi-
cal ceramics. The relative intensities or the relative integrated areas of the absorption bands
and their components of individual minerals in the curve-fitted FT-IR spectra (Figure 28.1)
are proportional to their concentrations and thus enable quantification of the detected min-
erals. Calibration curves, prepared for the ceramic with known concentrations of a mineral,
are used as references for the calculations.

Relative Amount of Calcite

The relative amount of calcite in the ceramic can be detected by the intensities or the inte-
grated areas of the main C03 band of calcite at 1420-1450 em-' relative to that of the main
SiO band of the fired-clay (meta-day) at 1030-1090 em-' (Shoval, 2003). For example, the
higher intensity of the C0 3 band in the spectra of Figure 28.1a compared with its intensity in
Figure 28.1b indicate a larger concentration of calcite in the fabric of the former. The overall
percentage of calcite in the ceramic is calculated from the relative intensities or the relative
 ,,
•tt····
. ·..

I
[a) ': COJ (b)
Calcareous
kaldte-rich)
(\'' Calcite 1 Non-calcareous kalcite-poor)
ceramic matrix
C03
Calcite / / ~ \\ SiO

"j
.eg );~~\
';;: :;<
- -
$\0 Meta-day
~; _ .e
~ ~ ~ ~~ ,;,~;to
~ 5I0 ii
:'.':
~ Meta-day ;g
H20 C03
Cak1tc
j H20

1600 1400 >200 1000 800 600 •oo 1600 1400 1200 1000 800 600 •oo
Wavenumber km- 1) Wavenumber (l:m··lj

loT SiD
Ouart~eta-day
[d) SiO
Meta-clay
Ceramic matrix rich in quartz Ceramic matrix rith in silicate SiO
minerals (without quartz} Silicates
SiO
SiD
C03
Meta-day,
Quartz,
Silicates

~"r
g
Jl tr\~
SiO C03
Quartz
~ Calcite
doublet
C03 1 !i
H20 Calcite H20
Water

1600 1<00 1200 1000 800 600 400 1600 <<GO >200 1000 800 600 400
Wavenumber (cm- 1) Wavenumber (cm- 1)

FIGURE 28.1 Curve-fitted FT-IR spectra of the ceramic material of representative Iron Age pottery from Levantine sites: (a) calcareous (cal-
cite-rich) ceramic (storage jar; TH-3); (b) non-calcareous (calcite-poor) ceramic (cooldng pot; TH-106); (c) ceramic material rich in quartz
(white painted jug; CYI-27698); (d) ceramic material rich in silicate minerals, without quartz (white painted amphora; CYI-16).
 I

(,) (b)
Ceramic material composes Ceramic material composes
of Metakao!inite of meta-smectite
., w~ v r~
~
~
N
~ w ~ N m m ~
~

-
~

- w
M ~ ~ ~
m
[;l
-
00

~ H20
"'c c
w ~

H
~
c
1l
w

c
MS c H

] Q
.§ H20

"' "'
.,
~
~
~

~
~ M
$ M M

-
M ~
w w
-
w ~
00 moo
m~
~~
;!:
MS
MK,Q MK MS
1600 1400 1200 1000 800 600 1600 1400 1200 1000 800 600

Wavenumber {cm- 1) Wavenumber (cm- 1)

(c) (d)
Ceramic material composes of mixture Ca-Al-silkate (gehlenite)
of metakaolinite and mate-smectite in ceramic material
~
M
00 M
N
(f;
w, "'
1\W

~ j
\j
~
~

~
H20
-e -e $ om
c
.§
~
N~
i<.O..n

"' I M

;$; '!
w

------
~-

1600 1400 1200 1000 800 600

MC
1600 1400 1200 1000 800 600

Wavenumber {cm- 1) Wavenumber (cm- 1)

FIGURE 28.2 FT-IR spectra and second-derivatives of the spectra of the ceramic material of representative Bronze Age pottery from
Canaanite sites: (a) ceramic material composed of meta-kaolinite ("metallic" type platter; LEV-24); (b) ceramic material composed of
meta-smectite (cooking pot; LEV-26); (c) ceramic material composed of a mixture of meta-kaolinite and meta-smectite (platter; LEV-
13): (d) firing silicate (gehlenite) in ceramic material composed of a mixture of meta-kaolinite and meta-smectite (platter; ZEV-12). MK =
metakaolinite, MS =meta-smectite, G =firing silicate (gehlenite ), H =hematite, Q =quartz, C =calcite.

'!!i.Wi-/blF.¥/jJ'J:I"::_\1:']::~·-p,·" "
l
 FT-IR IN ARCHAEOLOGICAL CERAMIC ANALYSIS 515
-------~--

integrated areas of the C03 and SiO bands measured from the curve fitting_ Calibration
curves with known concentrations of calcite are used as references for the calculation.

Relative Amount of Quartz

The main SiO band of quartz at 1084 em-' is commonly distorted by that of the fired-day
(meta-kaolinite)_ Thus, the relative amount of quartz in the ceramic is determined by the
intensity or integrated area of the band-doublet at approximately 778 and 798 em-' relative
to the main SiO band of the fired-day at 1030-1090 em_,_ For example, the higher intensity
of the quartz band-doublet in the spectra of Figure z8.1c compared with its intensity in
Figure z8.1b indicated that a larger concentration of quartz is present in the fabric of the
former.

Identification of Amorphous and Disordered Phases

FT·IR spectroscopy has the ability to identify the pseudo-amorphous phases of the meta-
clays in the composition of the ceramics (Shoval et al., zona). The wideness and shape of the
characteristic bands and their shift in frequencies convey information about the structural
organization and crystallinity of the material. Broad bands usually reflect poor crystallinity
and structural disorder, whereas sharp bands reflect well crystallized minerals. For example,
the broadness of the main SiO band of the meta-day at 1030-1090 em-' (Figures z8.1 and
z8.z) reflects the structural disorder of the meta-day phases due to their pseudo-amorphous
structure. In addition, the broadness and shift of the main C03 band of the reformed calcite
at 1430-1450 em-' (Figure z8.1a) reflects its poorly crystalline microcrystal structure.

FT-IR SPECTRA OF REFERENCE STANDARDS

TheIR spectra of pottery usually consist of multiple absorption bands from several different
minerals and phases within the ceramic fabric. Attribution of the bands in theFT- IR spectra
of the ceramic and their assignment to different minerals is accomplished with the support
of both the literature (Farmer, 1974; De Benedetto eta!., zooz; Shoval et al., zona) and refer-
ence standards of minerals presented here. Figures 28.3, 28-4, and z8.5 show the FT-IR spec-
tra and second-derivatives of individual reference standards of minerals typically found in
ancient ceramic fabrics. Figure 28.3 brings the FT-!Rspectra and second-derivatives of refer-
ence standards of firing silicates} Figure 28.4 demonstrates reference standards of carbonate
and silica minerals, and Figure z8.5 shows reference standards of minerals typically found
in initial raw materials. The characteristic absorption bands of these reference minerals are
used as fingerprints for the identification of the mineral composition of the ceramic.
 l
i

(a),----------------, (b),----------------,
Meta kaolinite Meta-smectite

/\ ~5(/
~
:;; ~
-e ~w
-e ~
~ ~ ~ <C
0 ~

"
1600 1400 1200
~
1000 800 600
$
•
1600 1400 1200 1000 800 600
Wavenumber (cm- 1) Wavenumber km- 1)
(d),----------------,
~ ~-
Mullite Gehlenite

~
~
j :;;
-e
~
~
::;<

1600 1400 1200 1000 800 600 1600 1400 1200 1000 800 600
Wavenumber (t.:m- 1) Wavenumber (cm- 1)

vr ',~
{e) 1 (f) ]

l Diopside
g(\ {\ ~"
*
l[~y-,Jfl/g
~ ;e
\ 0
~~C>
...... «> N
16
R
~
~
-e
~
<:
<"> \ - M )!.:~ <.!> N~ ~
~ v 2 f\~/\<P"' (\
"'
1600 1400 1200" 1000
Wavenumber (cm- 1)
800 600 1600 1400 1200 1000
Wavenumber (cm- 1)
800 600

FIGURE 28.3 FT-IR spectra and second-derivatives of reference standards of firing silicates: (a) meta-kaolinite,
(b) meta-smectite, (c) mullite, (d) gehlenite, (e) anorthite, and (f) diopside.
 i!,

1•1 (b) , - - - - - - - - - - - - - - - - - - - - ,
' "",
..•

~ ~~--~
I
I

"uc u
u
ill
c
-ll -ll
~
~ .§
"'
~v·
" ~ ~v~
§ ,
-o

1600 1400 1200 1000 800 600 1600 1400 1200 1000 800 600
Wavenumber (cm- 1) Wavenumber (cm- 1)

[c) (d),--------------------,
Quartz

~ ~
~
~~
"~ ~ .§
"" ~ "'
~v 2g
~~
1600 1400 1200 1000 800 600 1600 1400 1200 1000 800 600
Wavenumber (cm- 1) Wavenumber {cm- 1)

[e) , - - - - - - - - - - - - - - - - - - - - , (f) , - - - - - - - - - - - - - - - - - - - - ,
Opal Crystobalite

~
1i $ c
-ll ~
~

""
I
$ ;;
~
1600 i400 1200
" 1000 800 600 1600 1400 1200 1000 800 600
Wavenumber (cm- 1) Wavenumber (cm- 1)

FIGURE 28.4 FT-IR spectra and second-derivatives of reference standards of carbonate and silica minerals: (a)
calcite, (b) aragonite, (c) vaterite, (d) quartz, (e) opal, and (f) crystobalite.
(a) (b)
Kaolinite i'n§, fl~ ~ ~ Smectite (mootmO'illooite)

11"\{\ ll~i

Jl '~
0
§ ~ G
;j! ~

0 ;;)
:e
Sf --
1600 1400 1200 1000 800 600 1600 14DO 1200 1000 800 600
Wavenumber {cm- 1) Wavenumber km- 1)

kl (d)

I
K-feldspar

~
1i
-e• R ~
.§ ~

w .:s
« «
m
g
~
1600 1400
:::
1200 1000 800 600
I 1600 1400 1200
o•
§
1000 BOO 600
Wavenumber [cm- 1) Wavenumber {em - 1)

-1}- . . . ~b
(e) (~

7~- I
Hematite

"c

~
~~ 1' . ~
v
g
-2
< ~ I! !l ~
~j ~

1600 1400 1200 1000 800 600 1600 1400 1200 1000 800 600
Wavenumber {cm- 1) Wavenumber (cm- 1)

FIGURE 28.5 FT-IR spectra and second-derivatives of reference standards of minerals typically found in initial raw
materials: (a) kaolinite, (b) smectite (montmorillonite), (c) illite, (d) K-feldspar, (e) gypsum, and (f) hematite.

W4..4
 FT-IR IN ARCHAEOLOGICAL CERAMIC ANALYSIS 519

MOST COMMON ABSORPTION BANDS

IN THE INFRARED SPECTRA OF CERAMICS

The most common absorption bands observed in the spectra of archaeological ceramics are
SiO bands of frred-clay and silicates, C03 bands of carbonates (in calcareous ceramic), H,O
bands of absorbed water, and OH bands of reformed clay.

SiO Bands of Fired-Clay

The main SiO band of the fired-clay appears strong and broad at approximately 1030-1090
em-' (Figures 28.1-28.2). This SiO-stretching mode is accompanied by a combined SiO,
AlO bending mode at 465-470 em·• (Figures z8.1-28.2). Tbe second-derivative of the spec-
tra enables us to differentiate between different types of meta-clays of fired clay ceramics
(Shoval et al., zona; Shoval and Paz, 2015). The most common types of meta-clays in com-
positions of ceramics are meta-kaolinite and meta-smectite. They are distinguished by the
location of the main SiO component in the second-derivative of the spectra. The appearance
of the component of the main SiO band 1070-1090 cm- 1 is relate.d to a composition of meta-
kaolinite (Figure 28.2a), whereas the location at 1030-1060 cm- 1 is related to a composition
of meta-smectite (Figure 28.2b). These frequencies are in accordance with reference spectra
of meta-kaolinite and meta-smectite (a-bin Figure 28.3). The existence of some quartz with
the meta -kaolinite may contribute an overlapped component around 1084 cm- 1 (din Figure
28.4). The reconstruction of some reformed (rehydroxylated) clay from the meta-smectite
may contribute an overlapped component at 1030-1040 cm- 1•

SiO Bands of Quartz

SiO bands of quartz are commonly observed in the FT-IR spectra of ancient ceramic.
However, quartz is identified by the band-doublet at approximately 778 and 798 em_, (Figure
28.rc), because its main SiO band at 1084 em·• (din Figure 28-4) is commonly distorted by
that of the meta-kaolinite. In the second-derivative of the spectra the main band of the quartz
is overlapped with that of the meta-kaolinite. The SiO-bending mode of quartz appears at
465-470 em·• (din Figure 28.4), but it overlapped the combined SiO, AlO bending mode
of meta-clay and silicates in the spectra of the ceramic (Figure 28.rc). Quartz appears in the
ceramic as a stable primary mineral, which was inherited from the raw material. It is found
both as coarse grains (quartz temper) or as fine particles (silt quartz) within the ceramic
material.

SiO Bands of Firing Silicates

SiO bands of firing silicates (gehlenite, anorthite, !amite and diopside-wollastonite) may
also be observed in archaeological ceramics. In the second-derivative, the diagnostic band of
520 SHLOMO SHOVAL 1
the firing silicates (mainly gehlenite) are located around 912 em-' (Figure 28.2d). Indicative
bands of reference standards of the firing silicates are demonstrated in Figure 28.3. The fir-
I
0

ing silicates are formed during elevated firing through thermally induced reactions of the
meta-day with CaO derived from the decomposition of the calcite. Gehlenite and plagio-
clase-anorthite are formed in progressive firing of calcareous kaolinite clay, whereas diop~
side-wollastonite and larnite are crystallized in progressive firing of calcareous smectite. It
should be noted that some thermal phases which seem to be formed by the firing can be
inherited from the raw material. For example, in using basaltic soil for raw material, the min-
erals plagioclase and pyroxene may be inherited from the basalt residue, not from elevated
firing temperature.

C0 3 Bands of Calcite
C0 3 bands of calcite are commonly observed in the FT-IR spectra of ancient ceramic (Figure
28.10). The indicative bands of reference standard of calcite are demonstrated (a in Figure
28-4). The main co, band of the calcite in the pottery is located in the range 1420-1450 em->.
This band appears strong in the spectra of calcareous ceramics (Figure 28.1a), which contain
fine particles or crystals of calcite dispersed in the fired ceramic paste (Fabbri et al., 2014).
Reformed (recarbonated) calcite, which is crystallized after the firing by recarbonation of
the free-lime, is commonly found in ceramics. However, in low-fired pottery the calcite in
the ceramic can be primary (initial, natural, original); namely, inherited from the raw mate-
rial and preserved without change. The distinction between reformed and primary calcite
by IR spectroscopy is made possible by the fact that the main C0 3 band of the reformed
calcite appears at higher frequency (1430-1450 em-' (Figure 28.6a) than that of the primary
calcite (1420-1430 em->; Figure 28.6c). Moreover, in the second-derivative of the spectra of
the ceramic the main C0 3 band of the reformed calcite splits into two strong components
around 1426 em··> and 1476 em-> (Figure 28.6a), whereas the later component appears weak
and shifted in the second-derivative of primary calcite (Figure z8.6c). Mono-crystal calcite
temper in cooking pots behaves as primary calcite (Figure z8.6b)

H 2 0 Bands of Absorbed Water

Some water is absorbed into archaeological ceramics (Shoval et al., 1991). In FT-IR spectra of
ceramics, the H,O-stretching band is observed very broad around 3430 em-' (Figure 28.6d)
and the H,O bending mode at 1630-1640 em-' (Figure 28.1). The water is strongly absorbed
by the pseudo-amorphous meta-clay phase, which has a very large active specific area.
Indeed, these water bands persist even after drying the KBr disks at 25o"C (Figure z8.6d). In
addition, some interlayer water may locate within the reformed (rehydroxylated) clay min-
erals in the ceramic material. Although after ceramic firing the fired-clay ceramic was dehy-
drated, over time, a slow process of rehydration took place by adsorption of water from the
environment (Heller eta!., 1962; Shoval et al., 1991; Muller et al., zooo; Shoval and Paz, 2013).
(a)

~
-1!
Reformed calcite ln pottery
,-.n.., {b}

~
iii
{'
0
§
rm
,
l
~
~
'I
§
ill

1700 1600 1500

Wavenumber (cm"" 1)
1400 1300 1200 1700 1600 1500 " 1400
Wavenumber (cm- 1)
1300 1200

(d) J ,.,_.., __ --•*--•

lf\:"'' "'' "

(c) A.> -•-•• ,_

CH
ii ~
iii
.:l {'
j ~
« 'I
l ___.--/ I
~
1700 1600 1500 1400 1300 1200 3800 3600 3400 3200 3000 2800
Wavenumber (cm- 1) Wavenumber (cm- 1)

;~"""-J~l"'-----OH--------~
(,)

il ~ l~!v ~
\ .
ill •
N ill
Q ~ ~
~ 1

~ 'I o\. .J:gQ

0--.__
*
N-

~
~
3800 3600 3400 3200 3000 2800 3800 3600 3400 3200 3000 2800
Wavenumber (cm- 1) Wavenumber (cm- 1)

FIGURE 28.6 FT~IR spectra and second~derivatives of reformed minerals in pottery. Right: the OH starching
region demonstrating (a) reformed (recarbonated) calcite in calcareous ceramic (storage jar; TH-32) and (b) coarse
(temper) particles of mono-crystal calcite in non-calcareous ceramic (cooking pot; TH-8), in comparison with (c)
unheated calcite. Left: (d) reformed clay in ceramic (storage jar; TH ~30; the KBr disks dried at 250'C), in comparison
with (e) unheated smectite and (f) unheated kaolinite. CH = CH groups of organic matter.
522 SHLOMO SHOVAL

OH Bands of Reformed (Rehydroxylated) Clay

In addition to the water band, a weak OR-stretching band of reformed (rehydroxylated)
clay is often observed in ceramic material as a weak shoulder around 3630-3660 cm- 1• This
band is partly distorted by the band of the absorbed water and is best observed after drying
the KBr disk at 250°C (Figure 28.6d). It can be also detected by the second-derivative of the
spectra of the ceramic. TI1e location and shape of the OR-stretching band of the reformed
clay (Figure 28.6d) resemble that of unheated smectite (Figure 28.6e), not that of kaolinite
(Figure 28.6f). The source of the OR-stretching band is the reconstruction of some reformed
(rehydroxylated) clay from the meta-day (Heller eta!., 1962; Muller eta!., 2000; Shoval et
a!., 2ona). Although after the ceramic firing the fired-clay ceramic was dehydroxylated, over
time, a slow process of rehydroxylation and recovery of structural hydroxyl groups took
place within the fired-clay (Shoval eta!., 1991). The slowness and predictability of the rehy-
droxylation process has led some to suggest rehydroxylation as a method for dating ancient
pottery (Wilson eta!., 2009; Shoval and Paz, 2013; Chapter 37, this volume).

THE APPLICATIONS TO ARCHAEOLOGY

Analysing the Composition of the Ceramic

FT-IR spectroscopy provides information about the mineral composition of archaeological
ceramic. As such, it can be used to address questions about the technology of ceramic pro-
duction, firing temperature, sourcing the pottery, and raw material provenance (Maggetti,
1982; Heimann and Maggetti, 2014). This method can also be used to characterize the com-
position of different of classes of functional pottery, such as tableware, storage, and cooking
vessels (Shoval, 2003; Shoval and Beck, 2005).

Calcareous and Non-Calcareous Ceramics

The FT-IR spectroscopy facilitates differentiation between calcareous (Figure 28.1a) and
non-calcareous ceramics (Figure 28.1b ), and thus supplies information on the technology of
the production of the vessel (Fabbri eta!., 2014). This method can be used for quantity esti-
mation of the calcite relative to the clay, from the relative intensities of the main C0 3 and the
SiO bands in the spectra. Such a study reveals that different classes functional pottery were
manufacture by using calcareous and non-calcareous technologies (Shoval eta!., 2006). For
example, Iron Age storage and tableware in Galilee has calcareous composition (Shoval,
2003), while cooking pots from the same area have non-calcareous composition (Shoval and
Beck, 2005). Calcareous technology is advantageous to obtain sintering at lower firing tem-
peratures. Lime is considered a flux, and vessels prepared from this lime-rich or calcareous
clay sinter at lower temperatures (Maggetti eta!., 1984). On the other hand, non-calcareous
technology was used for the manufacture of cooking pots in order to produce ceramic which
was stable for cooking directly over a fire and was able to withstand repeated heating and
cooling. Ceramic is a poor heat conductor, thus the walls of the vessel should be resistant to
thermal shock, without damage.

J
 FT-IR IN ARCHAEOLOGICAL CERAMIC ANALYSIS 523

Meta-Kaolinite and Meta-Smectite ofFired-Clay Ceramic

Two main types of meta-clay are defined by the second-derivative of the spectra: meta-
kaolinite (Figure 28.2a) and meta-smectite (Figure z8.2b). The identification of meta-kaolin-
ite in pottery is an indication that kaolinitic raw material was used for their production
(Figure 28.2a), whereas the detection of meta-smctite is an indication that smectitic (mont-
morillonitic) raw material was used for their manufacture (Figure 28.2b). In some spectra
both components appear, indicating that the ceramic raw material consisted mixture of
smectite and kaolinite (Figure z8.2c). Each of these raw materials has its advantages (Shoval
and Paz, 2015). Kaolinitic raw material is most suitable for ceramic production. Kaolinite
clay does not swell or shrink upon wetting and drying, and can be fired to high temperatures
to form high-quality impermeable, thin-walled, durable vessels. The unique qualities of this
raw material facilitated large-scale production of a variety of forms to be produced from
the same clay. Smectitic raw material is usually less suitable for ceramic production since it
swells or shrinks upon wetting and drying. Tempering of clay raw materials was probably
applied in order to reduce these difficulties. The use of smectitic raw material enables the
potter to reduce the firing temperature and, potentially, the investment of production. The
smectitic clay that comes from soil, in particular, is relatively poorly crystallized and rich
in natural iron oxide, both of which induce earlier sintering. In addition, Canaanite cook-
ing vessels were manufactured from smectitic raw material in order to receive appropriate
mechanical properties of flexibility which are required for cooking direct over a fire (Shoval
and Paz, 2015).

Analysis of Particular Pottery Attributes

FT-IR can also be used to identify the composition of particular pottery attributes, such as
pastes, temper particles, binders, glazes, slips, paints and pigments, after their separation
from the bulk ceramic.

Analysis of Temper Particles

Although petrography is the technique traditionally used for identification of the temper
particles in ceramic, FT-IR spectroscopy can be also use for this purpose, after picking the
particles from the ceramic. The later method can be used for identification of carbonate par-
ticles (mono-crystal calcite, limestone, and chalk), basalt fragments, quartz grains, and sev-
eral other minerals (Figure 28-4). Their identification provides information about tbe raw
material and the provenance of ceramic production.

Analysis ofPaints and Pigments

FT-IR spectroscopy is also utilized for investigation of paints and pigments on the deco-
ration of ancient ceramics (De Benedetto et al., 1998; Sabbatini et al., 2000; Casadio and
Teniola, 2001; Mazzocchin et al., 2003; Weerd et al., 2004; Akyuz et al., 2007; Mangone et al.,
2009; Centeno et al., 2012; Buzgar et al., 2013). Analysis of paints from decoration of pottery
is available due to the small sample required for FT-IR spectroscopy. Figure 28.7a-b shows
(a) (b)
Black paint
on pottery BM BM
Red paint
on pottery RH ~c
BM, FC ,.
~

/?'
N
0
~
v 0 v
,.;;
/
u N u
c ~ c
ro ro
-f' -f'
_§ ~
~
< <

700 650 600 550 500 450 700 650 600 550 500 450
Wavenumber {cm- 1) Wavenumber (cm- 1)

(c) ~ ~ (d) MC
Black Mn02
pigment 7\fri 0
j
Bulk ceramic

~
~
v

! \~
u
u u
c c
I /~
ro ro
-f' -f'
0
£< 1l
<

700 650 600 550 500 450 700 650 600 550 500 450
Wavenumber (cm- 1) Wavenumber (cm- 1]

FIGURE 28.7 FT-IR spectra of paints and pigments: (a, b) black and red paints picked from the decoration of representative Iron
Age Cypriot-type bichrome pottery from Tel Dor (CYI-25 and 14), (c) reference of black Mn02 pigment, (d) bulk ceramic of the
background. (For the spectrum of hematite see fin Figure 28.5). BM = black manganese pigment, RH = red hematite pigment,
MC =meta-day.
 FT-IR IN ARCHAEOLOGICAL CERAMIC ANALYSIS 525

the FT-IR spectra of black and red paints picked from the decoration of!ron Age Cypriot-
type Bichrome pottery from Tel Dor. The spectrum of the black paint (Figure z8.7a) is simi-
lar to that of the black MnO, pigment (Figure z8.7c) indicating the use of black manganese
pigment for the black decoration. As the same, the spectrum of the red paint (Figure z8.7b) is
similar to that of the red hematite (Fe,0 3) pigment (fin Figure 28.5) indicating the use of red
iron pigment for the red decoration. However, the later observation is more complicated due
to some overlapping of the hematite bands with bands related to the bulk ceramic material
(Figure z8.7d).

Estimation of the Firing Temperature

FT-IR spectroscopy is often used for estimating the firing temperature of archaeological
ceramics (Shoval, 1993, 1994, 2003; Paz eta!., 2009; Barone eta!., zoos, zona, zonb; Velraj et
a!., 2009a, 2009b, 2012). This estimation provides information on the technology of the fir-
ing and the quality of the ware (Rice, 1987: Orton eta!., 1993; Velde and Druc, 1999; Maggetti
et al., zon). Although several methods are available for evaluation of firing technology
(Grimshaw, 1971; Rice, 1987), the estimation of the firing temperature by FT-IR spectroscopy
is advantageous for low-fired ceramics. The later ceramics are fired below the thermal crys-
tallization of firing silicates, and their meta-clay composition is amorphous for detection by
XRDmethod.
The estimation of the firing temperature by FT-IR spectroscopy is based on the following
principles:

The shift of the main SiO band. The main SiO band of the meta-smectite in the FT-
IR spectra of the pottery is progressively shifted to higher frequencies as the firing
temperature increases (Shoval et al., 20lla). For this determination, the location
of the main SiO band of the meta-smectite is detected from the second-derivative
of the spectra. For example, the shift of the main SiO band from 1035 cm' 1 (Figure
28.2b) to 1065 cm' 1 (Figure 28.2c) indicates that the latter pottery was fired at higher
temperature.
The presence of primary or reformed calcite. Progressive firing of calcareous clay above
700-800°C leads to decomposition of the primary calcite of the raw material and after
firing to the crystallization of reformed calcite within the ceramic (Fabbri eta!., 20 14).
Thus, a composition of reformed calcite within the ceramic (Figure 28.6a) is indicative
for high-fired ceramics, whereas a composition of primary calcite (Figure 28.6b) char-
acterizes low-fired ceramics. 1be location of the main C0 3 band at 1430-1450 em·'
is an indication of reformed calcite (Figure 28.6a), whereas the location at 1420-1430
cm· 1 is an indication of primary calcite (Figure 28.6b). In the second-derivative of the
spectra the splitting of the main C0 3 band and the observation of a strong component
around 1476 em·' is characteristic of reformed calcite (Figure 28.6a).
The presence of firing silicates. Progressive firing of calcareous clay above 800°C leads
to the formation of firing silicates within the ceramic (Fabbri eta!., 2014). In this pot-
tery, the identification of thermal phases of firing silicates within the ceramic (Figure
28.2d) is indicative of high-fired ceramics, whereas the absence of these thermal phases
526 SHLOMO SHOVAL

(Figure 28.2c) is indicative oflow-fired ceramics. The presence of firing silicates (mainly
gehlenite) within the ceramic is best observed by a band at 912 cm· 1 in the second-deriv·
alive of the spectra (Figure 28.2d).

Provenance Social Context of Pottery Production

FT-IR spectroscopy analysis may be used to assess the provenance of pottery production.
In parallel to petrography method, a suite of the pottery can be divided into FT-IR spec-
troscopy groups according to their mineral compositions. Finding a group of pottery with
a similar spectroscopic profile may indicate production from a single raw material and thus
a single place of production. On the other hand, the identification of several FT-IR spectra·
scopic profiles of pottery in an archaeological site may indicate imports from several work-
shops. Provenance studies attempt to find the pottery's geographical sources. The assessing
of the provenance of pottery production provides information regarding connections of the
site with the production regions, local or imported pottery, distribution of the vessels, and
probable pattern of trade or exchange connections between the site and adjacent regions and
thus the social context of pottery production (Tsetlin and Volkova, zon).

ACKNOWLEDGMENTS

This research was supported by The Open University of Israel's Research Fund (grant no.
31016). This support is gratefully acknowledged. The author expresses his appreciation to
Prof. Oded Navon for collaboration during his sabbatical year stay at the Institute of Earth
Sciences, The Hebrew University of Jerusalem. The author also thanks Dr. Yitzhak Paz of the
Israel Antiquities Authority for providing the Bronze Age pottery from Canaanite sites, and
Dr. Ayelet Gilboa of the University of Haifa for providing the Iron Age pottery from Tel Dor.

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 CHAPTER 29

RAMAN SPECTROSCOPY AND

THE STUDY OF CERAMIC
MANUFACTURE
Possibilities, Results, and Challenges

JOLIEN VAN PEVENAGE

AND PETER VANDENABEELE

RAMAN spectroscopy is a spectroscopic technique used to study many properties of mol-

ecules (Edwards eta!., 2005). Since the discovery of the Raman effect in1928, this technique
has developed tremendously and nowadays is applied in various research fields. In this chap-
ter we focus on the use of Raman spectroscopy for the study of ceramic manufacture. After
a short theoretical introduction about the Raman effect) its use in archaeological ceramic
research will be discussed in detail.

RAMAN SPECTROSCOPY: THEORETICAL APPROACH

The Raman Effect

The Raman effect was observed for the first time in 1928 in India by Sir Chandrasekhara
Venkata Raman (1888-1970) and Kariamanikam Srinivasa Krishnan (1898-1961) while
they were searching for an optical analog of the Compton effect (Singh, 2002). The
Raman effect is most easily described via the energy-level diagram in Figure 29.1. A more
elaborate description of the underlying theory of Raman spectroscopy can be found in
specialist monographs, such as: Edwards et a!. (2005), Long (2001) and Vandenabeele
(2013).
If monochromatic radiation, for which in Raman spectroscopy usually a laser is used as
a monochromatic light source, of energy hv is incident on a sample, part of the radiation is
transmitted without change but some of the radiation is scattered (Figure 29.1). This means
that the radiation is dispersed in all directions because of three different interactions that
might take place. In the first case (Figure 29.1a), a molecule is excited from the vibrational
ground state to a virtual energy level. Because the virtual energy level is not a stable energy
532 JOLIEN VAN PEVENAGE AND PETER VANDENABEELE

state for the molecule, it relaxes back to the original vibrational ground state. 1be scattered
light has the same energy as the incident light, and this elastic scattering effect is called
Rayleigh scattering (Grasselli and Bulkin, 1991; Lin-Vien eta!., 1991; Edwards et aL, zoos).
In addition to elastic scattering, inelastic scattering of the molecule occurs in a very small
portion of the molecules in the sample (approximately w- 6 to w- 8 ) (Edwards et aL, zoos; Lin-
Vien et aL, 1991). This inelastic scattering is Raman scattering, and comprises both Stokes and
anti-Stokes scattering.
In Stokes scattering (Figure 29.1b ), the molecule is excited from the vibrational ground
state to a virtual energy level, after which it relaxes to the first excited vibrational state. The
energyofthe incident light (E; hv 0 ) is therefore larger than the emitted light (E; h(v 0 - v,)).
In anti-Stokes scattering (Figure 29.1c) the molecule is excited from the first excited vibra-
tional state to a virtual energy level after which it relaxes to the vibrational ground state. Here,
the energy of the incident light is smaller than the emitted light (E; h(v 0 + v,)). Under equi-
librium conditions the number of the molecules in the vibrational ground state is always
much higher than that of any excited vibrational state (cf. Boltzmann distribution). Therefore
the intensity of Stokes scattering is higher than anti-Stokes scattering, making Stokes scatter-
ing the basis of Raman spectroscopy (Lin-Vien et aL, 1991; Edwards et aL, zoos). In a Raman
spectrum the intensity of the Raman-Stokes scattered light is presented as a function of the
Raman wavenumber (em-'). The Raman wavenumber, and thus the position of the Raman
band in the spectrum, is determined by the energy difference between the vibrational ground
state and the first excited state. Energy differences between the vibrational energy levels are
characteristic for functional groups, which define the structure of a family of compounds and
determine the chemical behavior of that molecule; for example the hydroxyl group in an alco-
hoL So, the position(s) of the Raman band(s) are material specific and can therefore provide

electronic excited state

vibrational
states ==================
{~'v6 : :.
virtual state

electronic groud state

vibrational
states {0'v6 =-:::±i:=====t~====:!i:==
a b c
Rayleigh Stokes anti-Stokes

FIGURE 29.1 Energy-level diagram explaining the different types of scattering.

 RAMAN SPECTROSCOPY AND STUDY OF CERAMIC MANUFACTURE 533

information about the sample analyzed. However, not all vibrational modes are Raman~
active. Only when there is a change in polarizability during the vibration can a Raman signal
be measured. In Figure 29.2, a Raman spectrum of calcite (CaCO,) is shown. The asymmetri-
cal stretch vibration of the C-0-C bond, and the in-plane deformation vibration of the OC=O
bond give Raman bands at, respectively, 1085 cm- 1 and 711 cm- 1•
On the one hand, the molecular structure can be identified by verifying to which molecu-
lar vibration the Raman bands in the spectrum correspond. On the other hand, a Raman
spectrum can be considered the fingerprint of a molecule. By comparing an obtained Raman
spectrum with those of reference materials, the unknown compound can often be identi~
fied Raman spectra of reference materials can be found in literature, or in specially designed
databases (Castro et aL, 2005; De Veij et aL, 2009; Vandenabeele, 20n). For the identification
of Raman spectra in the research field of ceramics, the Parma University database (<http:/ I
www.fis.unipr.it/phevix/ramandb.php>) and the RRUFFTM database (<http:/ /rruff.info/
>) are most well-known and used. Although open-access databases seem very useful for
spectrum evaluation, one must keep in mind that different instruments and experimental
parameters such as measuring time, number of accumulations, laser wavelength, status of
the material, etc. affect the Raman shift and may result in a different Raman spectrum for the
same materiaL Because not all databases are reliable and/or useful for identifying unknowns,
most laboratories and experts use their own databases of reference spectra to identify the
molecular structure of unknown samples. Spectrum evaluation in the field of Raman spec-
troscopy can be very time~consuming, especially when investigating ceramics whose het-
erogeneous nature and mixture of different minerals and phases often result in overlaying
bands in the Raman spectrum. This complicates the identification of unknown components
and, moreover, automated spectrum evaluation by software programs such as CrystalSleuth
becomes almost impossible.
So, Raman spectroscopy can be used to obtain qualitative information about the com-
position of a sample: the position of the Raman bands and their relative intensity ratios
enable identification. The intensity of the Raman bands is proportional to the amount of

120000
1085

100000

80000

""2'
·~
< 60000

"' 40000 281

20000 155

0 ~
1400 1200 1000 800 600 400 200
Raman shift (cm- 1)

FIGURE 29.2 Raman spectrum of calcite (CaC0 3).

534 JOLIEN VAN PEVENAGE AND PETER VANDENABEELE

the components that are present, so basically-if calibration is performed-quantification is

possible. But because the intensity of the Raman bands and their relative intensity ratios also
depend on the crystal symmetry and/or oxidation state of the component, Raman spectros-
copy is rarely used for quantification purposes (Vandenabeele and Moens, 2004).

Instrumentation
In Raman spectroscopy, usually a laser is used as monochromatic light source providing
the incident radiation. In the analysis of archaeological ceramics, several different types of
lasers are routinely used: argon+ -ion laser (514 nm), He-Ne laser (632 nm), krypton+ -ion
laser (476 nm), Nd:YAG laser (532 nm), diode laser (785 nm); each of them emitting light
of a specific wavelength. Before the laser light reaches the sample, it passes through differ-
ent filters (e.g. neutral density (ND) or holographic filters) and a microscope. Depending
upon the magnification of the objective, a particular spot size of the laser beam on the sam-
ple is obtained, sometimes down to a few micrometers in diameter. The resulting power of
the laser light on the sample depends upon the type of laser used, the type of objective
used, and the filters through which the laser light is passing. In the analysis of archaeologi-
cal ceramics, the laser power typically ranges from 0.7 m W to 10mW, and even to 20 mW
for portable instrumentation. To avoid thermal changes in the electrochemical structure
and bonding of the minerals, the laser power should be low (Goodall et al., 2009). The
measuring time is also very variable ranging from 100 s on powder pellets (Holclajtner-
AntunoviC eta!., 2012) to 78oo s for glaze analysis. After the laser light interacts with the
sample, the scattered light is detected by, for example, a charge coupled device (CCD)
detector. In this type of detector, before the scattered light reaches the detector, it might
pass through a band rejection filter, to clear it of Rayleigh scattering and to avoid detector
saturation. Then, each electrical signal is converted to a Raman wavelength and a Raman
spectrum is obtained.

Advantages and Disadvantages of Raman Spectroscopy

Raman spectroscopy is characterized by its high reproducibility and the obtained Raman
spectra have a high spectral resolution (- 1 cm- 1). It is also a non-destructive analytical tech-
nique; analysis can be conducted without destructive or invasive sample preparation and
the same sample can be used afterwards for other analysis. Raman spectroscopy has many
other advantages. No special coating or controlled atmosphere is required for Raman analy-
sis and the small spot size of the laser beam facilitates identification of individual minerals
and phases (Goodall et al., 2009). The high lateral resolution (c. r~m) is beneficial because,
depending on the sample, archaeological ceramics might be multilayered or have thin coat-
ings, such as slips or paints. The small spot size of the laser beam enables the analysis of each
individual layer rather than providing simply a bulk composition of the ceramic. However,
a small laser beam may also be a disadvantage for analysis of ceramics that are very hetero-
geneous in composition. For example, to determine the mineralogical composition of the
matrix of these ceramics, many measurements are required and/or a special sample prepara-
tion method to homogenize the material, such as pressed powdered pellets, must be used
 RAMAN SPECTROSCOPY AND STUDY OF CERAMIC MANUFACTURE 535

(RaSkovska et al., 2009; Tanevska et aL, 2009; Holclajtner-AntunoviC eta!., 20l2; MinCeva-
Sukarova et al., 2012).
In addition to laboratory~ based Raman spectrometers, mobile or portable instrumenta-
tion is also available. Portable instruments are typically used to investigate large objects with
dimensions precluding analysis with laboratory instruments. Further, mobile instrumenta-
tion can also be used to perform in situ Raman measurements. Analysis of precious objects
and artifacts that cannot be removed from the museum for study, for example. A practical
problem when performing in situ Raman analysis is interference of ambient light. Raman
measurements should be performed in dark environments because ambient light inter-
feres with the weak Raman effect. Therefore, in situ measurements come with some extra
challenges.
A disadvantage of Raman spectroscopy in general is that the weakness of the Raman effect
may result in problems with detection limits (Vandenabeele et al., 2012; Vandenabeele and
Moens, 2012). The Raman effect is weak, and during analysis, absorption and fluorescence
often occur, leading to a Raman spectrum of insufficient quality for phase identification.
Absorption occurs when the energy of the laser equals the energy difference between two
vibrational energy states, or the energy difference between the electronic ground state and
the electronic excited state of the molecule. After excitation of the molecule, the absorbed
energy is released as thermal energy. Consequently, the intensity of the scattered light is
highly diminished. Laser-induced fluorescence, on the other hand, occurs when the energy
of the laser light equals the energy difference between the electronic ground state and the
electronic excited state of the molecule. As a consequence, the molecule is excited to an elec-
tronic excited state instead of a virtual energy level with an energy smaller than the energy
of the electronic excited state. "!he absorbed energy is first released as heat in such a way that
the molecule relaxes to a lower vibrational energy level in the electronic excited state. 1ben,
the molecule relaxes from the electronic excited state to the electronic ground state emitting
fluorescence radiation. Fluorescence bands are much more intense than Raman bands, and
can literally "outshine" or overpower the weaker Raman signal. Therefore, fluorescence is
perceived as a disadvantage in Raman spectroscopy. Organic material, present at the sur-
face of ceramics as paints or tempers, often cause fluorescence. This interference cause by
organics can be ameliorated by irradiating the sample for some time with the laser so that
a higher quality Raman spectrum can be obtained (Colomban et al., 2004). This process is
called photobleaching. Another way to reduce or prevent fluorescence is by using a laser
with a different wavelength. This can also be done to avoid interference caused by absorption
(McCreery, 2000 ). Nevertheless, in some cases it is an advantage if the incident laser fre-
quency is dose to an electronic transition of the molecule, because it enhances the intensity
of the Raman signal. This phenomenon is called resonance Raman spectroscopy.

RAMAN SPECTROSCOPY TO STUDY CERAMICS

Archaeologists and cultural anthropologists study ceramics in order to identify and classify
these objects according to sociocultural and compositional criteria, manufacture technoloM
gies, and raw material sources. These classifications can be used to answer complex ques-
tions about past human behavior and interaction, such as how the perceived value of an
-
536 JOLIEN VAN PEVENAGE AND PETER VANDENABEELE
,,,,,,,,,,,

object relates to its transfer or trade throughout a region. Laboratory analyses to provide
accurate information regarding the chemical composition of the ceramics is required for
many of these classifications (Colomban et al., 2005; DeSantis et al,, 2012). Different ana-
lytical techniques, such as energy dispersive X-ray fluorescence (ED-XRF) and inductively
coupled plasma-mass spectrometry (ICP-MS), are used to study ceramics. They provide
information about the bulk elemental composition of samples and are, in addition, also able
to quantify those elemental compositions. To obtain information about the mineralogical
composition of the ceramics, other analytical techniques, such as X-ray diffraction (XRD)
and infrared (IR) spectroscopy, can be used (Goodall et al., 2009). Raman spectroscopy is
often used to identify both organic and inorganic molecular species (Parras et al., 2010 ), For
ceramic analysis, Raman spectroscopy is primarily used to study the mineralogy of ceramics
or to investigate the glassy phases of glazes.

Raman Spectroscopic Study of the Mineralogy

Optical microscopy of thin sections, SEM, and XRD are regularly used to examine mineral-
ogical composition in archaeological ceramics. Complementary to these techniques, Raman
spectroscopy provides direct information about the structural characteristics of mineral
phases, It can be time consuming (Minceva-Sukarova et al., 2012) but is the only analyti·
cal technique that can identify amorphous and glassy phases (e.g, graphite, carbon black)
(Ospitali et aL, 2005; Goodall et al., 2009; Minceva-Sukarova et al., 2012) as well as low con-
tent minerals undetectable by XRD analysis.
Raman spectroscopy is used to address several research queries. For example, regard-
ing manufacture technology, such as raw materials processing and paste formation, Raman
spectra of potential raw material sources can be compared with those collected from the
finished pottery. In addition, Raman spectra can be considered fingerprints of the ceram-
ic's molecular structure, and used in a diachronic study of pottery production in a particu-
lar region (Bersani et al., 2010 ). Further, some minerals, such as anatase (Ti0 2 ) or zircon
(ZrSi0 4) (Ayora-Caf\ada et al., 2012), may indicate a particular geochemical provenance for
the ceramics facilitating identification of trade routes and intersite relationships.
Production techniques and, more specifically, technology of manufacture (Colomban
and Truong, 2004) can be investigated in some detail by Raman spectroscopy. However, cau-
tion must be taken when addressing these issues, as mineralogical changes, due to use and/
or burial, can obscure or alter the mineralogical fingerprint of a ceramic (Marengo et al.,
2005). The presence or absence of certain mineral phases, such as diopside, anatase, or cal-
cite, may provide information about the firing temperature of the ceramics. For example, in
the Raman microspectroscopic study of Iberian pottery (Ayora-Caiiada et al., 2012), calcite
was used as a marker for the reconstruction of the firing conditions. Calcite was found to be
present in all the samples and its decomposition is often considered irreversible. It begins
to decompose at 6o0-700°C. Above 900°C this process is irreversible because the quick-
lime (CaO) that is formed reacts with the phases resulting from the dehydroxylation of clays
with the formation of calcium silicates. Therefore, the presence of calcite in Iberian pottery
suggests that the pottery was fired at low temperatures, probably around 850°C. However,
calcium carbonates could also be the result of post-depositional recarbonation processes,
if the sherds of ancient ceramics were buried in earth for thousands years under ambient
 RAMAN SPECTROSCOPY AND STUDY OF CERAMIC MANUFACTURE 537

co,
T>900"C

CaO

post-burial processes + phases resulting from

aluminosilicates+ dehydroxylation of clays
H20 +
calcium
C0 2 +
silicates

FIGURE 29.3 Formation and decomposition of calcite (CaC03).

conditions (Figure 29.3): Calcium silicates and aluminosilicates in contact with water and
carbon dioxide (CO,) decompose and produce CaC03 again.
Other minerals, such as hematite (a-Fe,03), magnetite (Fe 30 4 ) or maghemite (y-Fe,0 3)
may indicate firing in an oxidizing or reducing atmosphere: magnetite is converted to hema-
tite above 400°C under oxidizing conditions. Producing magnetite from hematite requires
temperatures of over l000°C under oxidizing conditions. On the other hand, under reduc-
ing conditions, hematite is converted to magnetite between 650-900°C; magnetite remains
the stable phase and is used to produce a black pigment. The colors of finished fired ceramics,
therefore, are strongly dependent upon and influenced by their firing conditions (Goodall et
al., 2009).
In certain cases, a mineralogical Raman study can also be used for relative dating pur-
poses. For example, in the investigation oflznik pottery byColomban et al. (2004a), Raman
signatures of hematite and associated phases cassiterite and quartz, were observed in the red
glaze. Red color is famous in the Iznik palette, and by extending the series of measurements
it could be demonstrated that the relative amount of associated phases is a criterion for dat-
ing. To answer research questions related to ceramic raw material provenance and relative
dating, investigation of pigments used for decoration can be meaningfuL Raman spectros-
copy is frequently used for the identification of pigments in, for example, illustrated manu-
scripts (De Reu et al., 1999; Klockenkamper et al., 2000; Vandenabeele et al., 20oob; Bersani
et al., 2oo6; Lee, zooS; De Laet et al., 2013) and paintings (Vandenabeele et al., zoooa, zooob,
2001; Ortega-Aviles et al., zoos; Edwards and Benoy, 2007; Edwards et al., 2014; Van de
Voorde et al., 2014; ). Therefore, this technique is perfectly suited for the analysis of painted
and glazed ceramics. Red pigments found on ceramics include red lead (Pb,O 4) (Jin et al.,
2012) and red ochre, a generic name for an earth pigment consisting of mainly hematite (a-
Fe,03) and silicates (Parras et al., 2010 ). Other pigments identified include carbon, malachite
(Cu,C03 (0H),), Chinese purple (BaCuSi,0 6), massicot (PbO), gypsum (CaS0 4 .zH,O),
Naples yellow (Pb(Sb03),/Pb3(Sb0 4),), hematite (a-Fe,03), magnetite (Fe30 4 ), and pyrolu-
site (MnO,) (Comodi et al., 2004; Goodall et al., 2009; De Santis et al., 2012; )in et al., 20t2).
Regarding the lead, tin, and antimony-based pigments, the band wavenumbers and rela-
tive intensities in the Raman spectra may vary according to their composition and the fir-
ing temperature (De Santis et al., 2012). Sometimes, no characteristic Raman spectrum is
obtained, especially when measuring green or blue glazes. This indicates that there are no
538 JOLIEN VAN PEVENAGE AND PETER VANDENABEELE

more mineral or pigment particles present in the glaze, and that the pigment is completely
dissolved in the glaze (Simsekand Geckinli, 2012).

Raman Spectroscopy to Study Glassy Phases

of Glazed Ceramics
Apart from the mineralogy of the pigments, Raman spectroscopy is also used to study the
glassy phase of a glaze. Typically, the Raman spectrum of a glaze is characterized by two ·
broad bands around sao cm- 1 and 1000 cm- 1• These bands originate, respectively, from the
v, bending vibration and the coupled v1 and v3 stretching vibrations of the Si0 4 tetrahedral
units that compose the glaze (Colomban et al., 2003, 2004b ). When aluminum, alkali, earth-
alkali and lead metallic ions are inserted in the Si0 4 lattice, the continuity of the Si04 net-
work is broken, and consequently the center of gravity and the intensity of the bending and
stretching mode are changed. The bending vibration, in particular, is sensitive to modifica-
tion of the tetrahedral network in the vicinity of metallic cations. The bending vibration is
the strongest mode for structures composed of highly connected SiO 4 tetrahedral units (e.g.
quartz). In contrast, stretching modes have a larger amplitude in structures of weakly con-
nected tetrahedral units (Colomban et al., 2003, 2004b; De Santis et al., 2012).
If the area under the bands of the 500 em·> complex (A500 ) is divided by the area under the
Raman bands at woo em·• (Aw 00), the polymerization index, IP' is calculated (Colomban et
al., 2003, 2004b ). The value of the IP ratio is strongly correlated to the polymerization degree
and thus characteristic for the composition of the glaze. Based on the IP ratio, the processing
temperature of glass structures, like glazes, can be estimated (Table 29.1) (Colomban eta!.,
2003).
In a Pb-based glassy matrix, for instance, the IP ratio is much smaller than in transparent
glazes. Note also that the center of gravity of the Pb-based glassy Si-0 stretching mode is ca.
950 em·', but that it is at ca. 1050-noo em·> in the K/Ca-based colorless glaze (Colomban
et al., 2003, 2004b; De San tis eta!., 2012).
In 2001, Colomban and Treppoz introduced five different stretching bands, whose con-
volutions produce the broad experimental band at about 1000 em·•. These five different
components are denominated as Q 0 , Q, Q,, Q3, Q 4 , and Q 5, and correspond, respectively,
to SiO 4 units with zero, one, two, three, and four bridging oxygen atoms (Col omban et al.,

Table 29.1 Based on the lp ratio, the processing

temperature of glass structures can
be estimated
Processing temperature (in oc} Polymerization index, IP

1400 ~ 7
1000 ~1.3

600 or less ~ 0.3

 RAMAN SPECTROSCOPY AND STUDY OF CERAMIC MANUFACTURE 539

/'·:''
3.5 ·V 2
A 3
'"'""·"·"· r·)·. 0 4
3

2.5
Porcelain L v 5
n 6
lil 7

§ 2
4:
"g
0: 1.5

Vmax Si-0 stretching

FIGURE 29.4 Plot of the polymerization index as a function of the main Si-0 stretching
component wavenumber (Redrawn from Colomban, 2006).

2003, 2004b; DeSantis et al., 2012). Knowledge of the components mentioned above allows
classification based on the glaze structure. 1his can be done in several ways. For example, to
classify different types of glassy silicates the I, index is plotted as a function of the position of
the main Si·O stretching component wavenumber (i.e. the peak maximum wavenumber):
from top to bottom, classification is a function of tbe melting/processing temperature, rang-
ing from porcelain at the top to low-temperature-processes silicate glasses at the bottom.
From left to right, classification is carried out as a function of the main fluxing agent. This is
depicted in Figure 29.4 (Colomban eta!., zoo6).
In the study of Kutahya wares, the On components were used to discriminate between
different ceramic production processes which are debated among scholars. As a lot of infor·
mation about the production process remains within the micro/nanostructure of the sam~
ples, the On components were used to understand the production process and classify the
objects. The study shows that the production homogeneity can be represented by plotting
the area of each component On as a function of their peak positions. Furthermore, the simi-
larity between composition and nanostructure of glazes could be deduced from the com-
parison of the 0, center of gravity and relative area ratios of the On components (Colomban
et al., zoos).

FUTURE PROSPECTS

In many publications concerning pottery analysis, ceramics are clustered according to their
chemical composition using different statistical methods, such as principal component anal-
ysis (PCA) or linear discriminant analysis (LDA). PCA is used to reduce the dimensions
-
540 JOLIEN VAN PEVENAGE AND PETER VANDENABEELE

of multivariate problems. It is an unsupervised pattern recognition method because no

assumptions are made about underlying data distribution. The correlation among a large
number of variables is expressed in terms of underlying factors, called principal components
(PCs). These orthogonal variables are a linear combination of original variables with the first
PC explaining the largest portion of variance, the second PC the second-largest, and so on.
LDA, on the other hand, is a supervised discriminant analysis method. In this classification
method, the variances between categories are maximized and the variances within catego-
ries are minimized (Carrero et al., 2010). In practice, to execute multivariate data analysis,
quantified compositional data for the ceramics is reported as elements or element oxides,
acquired using analytical techniques such as ED-XRF or ICP-MS. Raman data can also be
analyzed using these data processing methods. For the distinction of copper phthalocya-
nines in paint layers, for example, Defeyt et al. (2013) used micro- Raman spectroscopy in
combination with chemometrical analysis. Copper phthalocyanine is often identified as an
important pigment (PB15) in twentieth-century artworks. It is used in different polymorphic
forms and identification of it can retrieve information on the production process of the pig-
ment at the moment. Using LDA with intensity ratios as variables, the crystalline structure
of a PB15 pigment can be predicted in unknown paint samples (Defeyt et al., 2013). However,
multivariate data analysis is rarely done in combination with Raman spectroscopy, but it has
been proven effective. This provides opportunities and avenues for future research concern-
ing pottery analysis.

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 CHAPTER 30

X-RADIOGRAPHY
OF ARCHAEOLOGICAL
CERAMICS

INA BERG AND JANET AMBERS

HISTORY

IN 1895, Wilhelm Rontgen discovered a new type of radiation, which he termed "X-rays;'
while experimenting with vacuum tubes. These rays proved to be more penetrative than light
and thus could be used to produce images of dense materials. The first X-ray image ever pub-
lished was that of Rontgens wife's hand with her ring clearly visible on her finger (Rontgen,
1896). The scientific community rapidly recognized the potential of the technique and almost
immediately began to use X-rays to illuminate a wide variety of medical problems (Posner,
1970 ). Rontgen was awarded the Nobel Priz.e in 1901 in recognition of his important discovery.
The technique's power was by no means limited to medical uses and it quickly became
an invaluable tool in art and archaeology, where it has since been applied to a great vari-
ety of materials, including human and animal bones, metals, ceramics, paper, paintings,
and soils (for a recent summary see Lang and Middleton, 2005). The earliest application of
X-radiography to ceramics dates to 1935 when Titterington published a radiograph of seven
sherds from North American Indian burials in order to illustrate differential proportions
of inclusions. A decade later, Digby employed the technique to investigate a defect in the
construction of a Peruvian stirrup-handled pot (1948). However, it was only in 1977> when
Rye laid down the fundamental rules of ceramic X-radiography, that the analytical poten-
tial of this technique was fully appreciated (1977; 1981). A comprehensive summary of the
technique and its application to ceramics was published in the 1990s (Carr, 1990; Carr and
Riddick, 1990) and further expanded and updated by Berg (zoo8).

RADIOGRAPHY AND CERAMIC TECHNOLOGY

Radiography offers many advantages for the study of ceramics which make it a very effec-
tive technique for archaeologists and conservators alike, whether used on its own or in
 X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 545

conjunction with other methods such as microscopy or conventional destructive prov-

enance analyses. Although almost all published radiographic studies of ceramics focus on
clay vessels, the underlying technological principles make it a suitable investigatory tech-
nique for almost any kind of clay object. Its advantages are manifold as it provides access to
the internal structure of an object, is non-destructive, can be used on both fragments and
complete objects, is comparatively rapid and cheap, and suitable medical or industrial facili-
ties are easily and generally available worldwide.
X-radiography is most commonly applied to cultural materials to answer a number of
questions, particularly:

identifrcation of the object and its condition;

identification of the material(s) present;
identification of manufacturing method(s);
identification of joins, faults, breaks, repairs, and reuse;
identification of finishing methods and decoration;
.. identification of forgeries.

In the case of archaeological ceramics, radiography is used extensively to answer many of

these questions, particularly to study condition and repairs to inform conservation treat-
ments and questions of authenticity. However, two of these themes-namely, the identifica-
tion of materials and of manufacturing methods-have received by far the greatest attention,
with work specifically concentrated on the characterization of clay fabrics through inclu-
sions or tempers and the identification of manufacturing details (Carr, 1990 ). These two sub-
jects are discussed in more detail in the following section.

Characterizing Clay Fabrics

Under the right conditions, that is when the clay body and inclusions are of different
radiodensities and vessel walls are not too thick, X-radiographs can be used successfully to
characterize ceramic fabrics by determining the size, proportion, type, and general min-
eralogy of inclusions and/or tempering materials. Scholars have been able to distinguish
between classes of minerals, such as felsic, mafic, and opaque, by considering the radio-
graphic density and morphology of the particles, and the presence, number, and angle of
their crystal faces. More specific attribution of minerals is often problematic, especially
when inclusions/particles/grains have a similar chemical composition and exhibit similar
morphology and radiodensities (e.g. chert, quartz, pure sandstone) (Carr and Komorowski,
1991). Grog, for example, is most visible when it is of different clay from the surrounding clay
body (Foster, 1985). In contrast, organic inclusions (such as straw, wood, sponge, insects,
seeds, shell) and the burnt-out voids left by them are easily recognizable, since the density of
the ceramic body is significantly different from that of air.
Once inclusions have been characterized, their volumetric proportion and (size) distri-
bution within the vessel can be measured and used to determine fabric groups (Rye, 1977;
Braun, 1982; Maniatis et a!., 1984; Foster, 1985; Blakely eta!., 1992). Blakely and colleagues
tested the potential of radiography to assign vessels to fabric groups, and the technique was
able to successfully divide their sherd assemblage of Pompeian red ware into two major
fabric groups. Petrology and heavy mineral analysis were subsequently able to confirm the
546 INA BERG AND JANET AMBERS

validity of these two groups (Blakely et al., 1989). In a related study, X-radiographs were
used to successfully determine whether body sherds found in close proximity to each other
during excavation belong to the same vessel or to different ones, providing certainty where
macroscopic analysis is ambiguous (Carr, 1990: 21, 1993: 103-105). However, success of X-
radiography for establishing fabric groups is variable, as demonstrated by Adan-Bayewitz
and Wieder (1992), and depends upon the exact nature of the fabric(s) under investigation. It
seems most prudent, therefore, to consider radiography as a complementary tool rather than
a replacement for petrography and chemical analyses.

Identifying Vessel Formation Procedures

First used by van Beekin 1969, X-radiography has since established itself as a powerful tech-
nique for the identification of primary forming methods, in particular differentiating among
pinching, drawing, coil-building, slab-building, molding, and wheel throwing. It was Rye
who first recognized that "the application of pressure to plastic clay causes mineral parti-
cles, voids, and organic fragments to take up a preferred orientation'' which affect the entire
ceramic body. The resulting alignment and distribution of inclusions, as well as the shape
and orientation of voids, is characteristic of each forming method, and these features are
not normally obliterated or obscured by secondary forming/shaping or decorative tech-
niques (1977: zo6, 1981; Carr, 1990; Berg, zooS). Much innovative X-ray work in this field
was carried out in the 198os and early 1990s. However, waning technical support for xerora~
diography (see the section entitled 'Xeroradiography') in the late 1990s has led to a notice-
able interruption in research activity. It is only now, with a better appreciation for the power
of imaging software programs and increasing availability of industrial and medical X-ray
equipment, thatX-radiographic research into ceramics is once again gaining momentum.
Many scholars have successfully employed radiography to gain a better understanding
of manufacturing techniques (see e.g. van Beek, 1969; Foster, 1983; Ellingson et al., 1988;
Carmichael, 1990, 1998; Henrickson, 1991; Nenk and Walker, 1991; Vandiver et al., 1991;
Philpotts and Wilson, 1994; Vandiver and Tumosa, 1995; Levi, 1999; Giannoulaki et al., zoo6;
Berg, 2009; Laneri, 2009; Berg and Ambers, zona; Corfield, n.d.), but the two most detailed
case studies currently available were undertaken by scholars working in the Near East
(Glanzman, 1983; Glanzman and Fleming, 1986; Vandiver, 1987, 1988). In their diachronic
study ofBaq'ah pottery, Glanzman and Fleming were able to show that, contrary to the com-
mon assumption of an evolutionary sequence from hand-building techniques to the potter's
wheel, the Baq'ah LB I wheel-throwing tradition was replaced by a coil-building tradition
in the LB II and Iron lA periods. Vandiver, on the other hand, employed xeroradiography
to reconstruct a specific forming technique, called sequential slab-building, in widespread
use in the Zagros region around 3000 sc. Not only was Vandiver able to identify the tech-
nique in general, but she was also able to determine the precise shape, size, and sequence
with which each slab was applied to form a vessel (1987). Some of the most intriguing case
studies have utilized X-radiography to detect hidden vessel parts and added sections, such as
the whistling mechanism in Peruvian pots and the fake spout of Aegean stirrup jars (Digby,
1948; Leonard et al., 1993).
Secondary forming techniques, such as scraping, trimming, smoothing, and adding sec-
tions, are more difficult to identify radiographically because tbey do not generally involve
 X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 547

severe enough modification of the clay to be reflected in an X-radiograph (Berg, 2008).

1hese secondary modifications and technologies are, therefore, best identified macroscopi-
cally. 1he exception to this rule is the paddle and anvil technique which applies so much
pressure to the preshape that it can obliterate all radiographically visible attributes of the
primary forming technique (Rye, 1981). Similarly, severe turning of the entire vessel is often
identified by the complete lack of evidence/traces of the original forming technique com-
bined with thin vessel walls.

THEORETICAL BACKGROUND

1he use of radiography in the study of ceramic composition and forming techniques is
based on the distribution, alignment> and nature of inclusions and voids within the fabric.
In terms of simple compositional studies this is self-explanatory: materials which differ in
radiographic density from the clay body can become visible, and hence can be analyzed
and interpreted through X-radiographs. 1he use of radiography to look at ceramic forming
techniques is rather more complex. Pressure applied during the formation and shaping of a
vessel frequently creates characteristic alignments and orientations of inclusions and voids
that become radiographically identifiable within the vessel fabric. Figure 30.1, based on the
pioneering work of Rye (1977, 1981), provides a summary of the characteristics whicb might
be expected for different forming techniques. Radiography reveals these alignments non-
destructively. It should once again be emphasized that the success of radiography in iden-
tifying manufacturing techniques is dependent upon the visibility of these features; that is,
they must have different optical densities from the matrix material, as well as the amount of
secondary reworking. We advocate, therefore, that small-scale trials or pilot projects always
be carried out on unknown or previously unradiographed ceramic types prior to any major
commitment of resources.
Pinching-forming shapes by squeezing clay between fingers and thumbs-is probably
the simplest of the ceramic forming techniques. It does not result in the type of dramatic
orientation of inclusions produced by other forming methods, but can still leave diagnostic
traces in the vessel fabric. Figure 30.1a illustrates these features: in cross-section inclusions
lie parallel to the surface while in plan view no horizontal or vertical orientation is visible.
1he surface may also show indentations from the pinching motion.
Figure 30.1b illustrates the distribution patterns expected for coil- or ring-built vessels. It
is extremely difficult to attain perfect cohesion for every coil joint, however expert the potter,
and despite careful secondary worldng to smooth out and strengthen these joins, in most
cases some evidence will survive somewhere within the vessel fabric. As a result, coil joins
are often visible as voids between the coils and are typically roughly concentric on the base
and roughly horizontally parallel on the vessel sides. joining techniques, such as overlap-
ping, smearing, or crushing individual coils, are sometimes applied to strengthen coil joints.
In these cases it can be necessary to vary the angle of the X-ray shots to capture the joins and,
sometimes, even to resort to the "thick section" method of examination (described below in
"Tips and Tricks") to capture proof of coiling. In addition, the coils themselves, having been
prepared as long rolls prior to vessel formation, may exhibit a degree of horizontal parallel
orientation with inclusions sometimes visible in the X-ray image (Figure 30.2).
548 INA BERG AND JANET AMBERS
~~ ~~-----------

(a)Q f!!;~
~
\tt!Y
(b)

6 -
.

@ .
~
~

(d)

(e)

FIGURE 30.1 Characteristic X-ray features of the main pottery forming techniques (after
Rye, 1981; Carr, 1990: figure 1; Middleton, 1995: figure 4.8), showing, from left to right, vessel,
distribution of voids and inclusions in the vessel side, distribution of voids and inclusions
in the vessel cross-section. Techniques shown are (a) pinching, (b) coil building, (c) wheel
throwing, (d) slab building, (e) secondary working using the paddle and anvil technique.

FIGURE 30.2 Inclusion alignment in a clay coil. Normal view (left) and cross-section
(right). Enhanced positive radiographic image. Exposure parameters: Faxitron, 0.5 mm
focal spot, 6o em focus-to-film distance, 70 kV, 150 s, 3 rnA.
 X~RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 549

Wheel-thrown vessels do not exhibit joins but the combined upward and rotational
movement associated with pulling the walls of a vessel results in a spiral orientation of
voids and inclusions (Figure 30.1c). In cases where a vessel is complete, X-rays are able
to pass through both the near and far walls, and the resultant X-radiography will show
superimposed images of both sides of the vesseL Wheel throwing, therefore, can reveal
itself in the radiograph as either a series of diagonal lines in the vessel's surface or as two
sets of diagonal lines in apparently opposing directions (this effect can be avoided by plac-
ing film inside a complete or near complete vessel in order to capture only one side). The
initial suggestion by Rye that the angle of these lines reflects the speed of the wheel is not
supported experimentally (Berg, 2008), but the same study did show that it is possible,
in some circumstances, to differentiate between wheel-made ceramics, where the entire
forming process is carried out on a turning wheel, and wheel-shaped or wheel-finished
vessels, where items initially made by other techniques are then finished and improved on
a fast wheeL
Joins between flattened sheets of clay are the primary radiographic evidence for slab-built
vessels (Figure 30.1d). The orientation of inclusion in these sheets is dispersed and unaligned
as a consequence of flattening of the clay sheets.
Other manufacturing techniques, notably molding, are more difficult to identify radio-
graphically. For molding, the nature of the method means there is little or no development of
preferred particle orientation within the clay, but thickening of the clay along the lines where
the separate parts of the molds meet frequently occurs, and it is sometimes possible to suc-
cessfullyidentify mold-made ceramics in this way.
A wide range of secondary forming processes are used in ceramic construction in order to
increase strength and resistance or simply to improve appearance. They are seldom detect-
able by radiography and do not normally impact the visibility of primary forming techniques
(Berg, 2008), except in cases where a large proportion of the wall thickness is removed. The
one notable exception is the paddle and anvil technique, whose use may make the identifica-
tion of the primary forming method more difficult. The effects on alignment and orienta-
tion of particles and voids in the vessel created/modified by the paddle and anvil technique
are shown in Figure 30.1e. This technique, designed to thin and shape vessel walls, consists
of beating one side of the vessel wall (usually the exterior) with a paddle, while the inside is
supported with the smooth hard surface of a tool or implement, often a pebble. This "beat-
ing" causes localized distortions of voids and inclusions in the vessel walls, and the resultant
variation in thickness and distinctive star~shaped cracks around large mineral particles are
dearly visible in X-radiographs and are among the easiest ceramic features to identify radio-
graphically. In contrast, very severe turning of the entire vessel may potentially be identifred
by the total lack of traces of the original forming technique and thin vessel walls, as dem-
onstrated in an unpublished study of Bronze Age Cypriot vessels investigated by one of the
authors (Ambers).
Based on our experience with ancient vessels) together with experimental data from rep-
lica vessels, a firm identification of forming techniques should be possible for approximately
70% of vessels within an assemblage. Success rates will be lower when the vessel walls are
very thick, when clay body and inclusions have a similar radiodensity, or when the pots have
been heavily turned.
-
550 INA BERG AND JANET AMBERS

METHODOLOGY

Historical Development
The earliest X-radiographic investigations of ceramics (van Beek, 1969; Rye, 1981) used
conventional film radiography and met with only limited success. In order to characterize
archaeological ceramics it is necessary to locate and identify small particles with densities
only minimally different than an already radiographically light matrix. With skill and care
such subtle changes can be identified on unmodified X-ray films, but the process is not easy
and requires considerable expertise. The development of a novel radiographic technique in
the 1970s, xeroradiography, made the identification of such small changes in density much
more accessible, and was followed by an explosion in the number of ceramic studies depen-
dent on radiography published.

Xeroradiography
Xeroradiography is an X-radiographic technique in which the image is collected on an alu-
minum sheet coated with a uniformly deposited film of amorphous selenium, rather than
on a photographic film or a digital imaging plate, within an otherwise conventional radio-
graphic setup. The plate is electrically charged before use, and during exposure this charge
dissipates differentially in proportion to the dose of radiation it receives, thereby generating
a latent image which can be fixed onto paper by processing with oppositely charge particles
(usually in the form of a blue colored powder), as a variation of the Xerox photocopying
process (Boag, 1973; Lang and Middleton, zoos). While this method cannot produce high-
resolution images, it has other advantages which established its importance for a range of
medical applications, most notably mammography. Xeroradiography has a wide exposure
latitude, is virtually impervious to scatter, and, because of the way in which the dry toner
responds to electrical fringing between high- and low-charged areas, shows a pronounced
edge enhancement effect (Figure 30.3). These characteristics make it particularly suitable for
the examination of small differences in density, particularly if they have sharp, well-defined
edges. Originally developed for medical examination, xeroradiography was rapidly taken
up by the archaeometric community for a number of purposes, but most particularly for
the study of ceramics (see e.g. Vandiver, 1987). Xeroradiography is now effectively obsolete,
as it has long been replaced in medicine by techniques which require lower doses of radi-
ation. Instead radiographers have turned to digital image manipulation to extract similar
information from radiographic images, as discussed in detail in the section entitled "Image
Enhancement" (O'Connor eta!., zooz).

Modern Practice
A wide range of X-ray equipment, which can broadly be divided into medical and com-
mercial/research setups, is now available to archaeologists. Medical units can be found in
 X~ RADiOGRAPHY OF ARCHAEOLOGICAL CERAMICS 551

FIGURE 30.3 Xeroradiographs of two stirrup jars showing both the blue color and edge
enhancement inherent to the technique. The scratch across a) is an unfortunate result of the
use of ageing equipment. a) Stirrup jar with solid false central spout from mainland Greece
(BM registration number G&R1978,0701.4); b) Cretan stirrup jar with hollow false central
spout (BM registration number G&Rr857,0825.2).

hospitals, private clinics, and veterinary surgeries (Figure 30-4a), while commercial/research
machines can be found in industrial settings, museums, and universities (Figure 30-4b). The
key difference between them is that medical setups are designed to minimize the radiation
dose to living tissue, and are, therefore, only designed to permit short exposure times. As
a consequence, the voltage (kV) has to be proportionately greater to achieve penetration,
resulting in images with reduced contrast. However, in industrial and research settings the
imperative to minimize patient dosage does not exist. This means that exposure times can be
increased and the kV kept low in order to achieve high-contrast images. For this reason, if
the opportunity to work with a commercial/research setup is available, this is to be preferred
over a medical facility.
The advantages of using radiographic equipment at medical facilities, on the other hand,
are their relative abundance, comparative ease of access, and potential portability (many
large animal veterinary practices and some hospitals have mobile equipment). If medical
equipment is to be used, it is best to avoid specialist mammography units, because mam-
mography film is generally only available in very small sizes and also tends to be too respon-
sive to very small thickness changes, making it overly sensitive for ceramic analysis. 'TI1e
truth, however, is that it is possible to work with most commercial, research, and medical
X-ray units and achieve a reasonably detailed image.
One further choice exists when selecting X-ray equipment: whether to use digital or con-
ventional wet( -film) processing. At the time of writing there are few qualitative differences

')il;ig( ','' --
 •
552 INA BERG AND fA NET AMBERS

FIGURE 30.4 Examples of types of radiographic equipment available. (a) Portable medical
Sirio no/loo CR system; (b) Faxitron single-cabinet X-ray unit.

between the two; currently available instrumentation digital image quality is as good as that
of film and the speed of technical development is such that digital may soon overtake conven-
tional film radiography. Digital equipment has several practical advantages: the image can sim-
ply be downloaded without having to be scanned; the latitude of exposure is greater; the lack of
processing time means digital work tends to be quicker than film radiography; and, while the
initial outlay for equipment is higher, there are no recurrent costs for film and chemicals. "There
are currently two types of digital systems available, which differ in the image collection method
used: CR (computed radiography) and DR (direct radiography).ln CR, a reusable phosphor
plate is used in place of film in a conventional system, while in DR the image is captured on a
fixed plate and transmitted directly onto a computer screen. DR systems are currently consid-
erably more expensive, but, at present, the image quality of the two systems is similar.
An archaeologist's choice of system will most likely be governed by availability and train-
ing, but looking into the future, chemical processing is slowly being phased out in all areas,
and digital X-ray machines will soon become the norm. A radiographic imaging technique
called computed tomography (Cf or CAT) may occasionally be available to researchers. In
addition to presenting a frontal view of an object, like regular X-rays, CT can also "slice"
through an object, providing the researcher with cross-sectional views.

Image Enhancement
Whatever the initial image collection method, the minimal differences in radiographic
density between ceramic bodies and the voids and inclusions within them mean that some
form of image enhancement is necessary prior to interpretation of the radiographs. In xero-
radiography, edge enhancement was an integral part of the method, but for conventional
X-radiography edge enhancement must be artificially produced by digital manipulation of
 X-RADIOGRAPHY Of ARCHAEOLOGICAL CERAMICS 553

the image. In order to do this, the images must first be in a digital format and of the highest
resolution possible. With the increasing availability of digital radiography no interim stage
may be necessary, but, given that archaeology tends to be both poorly funded and conducted
in areas with limited resources, at the time of writing, most radiography of ceramic materials
will have been recorded on film.
Low-cost methods of film digitization exist (films can be scanned on office-style flat-
bed scanners with transmission capacity or placed on a light box and imaged with a
standard digital camera), but by far the best results are obtained using specialist X-ray
scanners (O'Connor and Maher, 2001; Lang et al., zoos). These are designed to maxi-
mize the information collected from film radiographs and have high dynamic ranges
(dynamic range is defined as the range of optical densities that can be recognized in the
image), and high resolution (resolution is the number of pixels per unit length in the
image; for most specialist equipment the pixel pitch will be so microns (c.s12 pixels per
inch) or better) and a bit depth of 12 or more (bit depth controls the number of shades of
gray which can be distinguished within the image; in an 8-bit system zs6 shades of gray
can be defined, in a 12-bit system 4,096, and in a 16-bit system 6S,S36). Such specialist
equipment is very expensive and its purchase is not cost effective for most museum and
academic departments. However, demand for the storage of industrial images means
that commercial scanning services are readily available at reasonable rates, particularly
when judged against the cost in time and effort of producing high-quality radiographic
images in the first place.
Regardless of how the digital image is produced, it is important that it is generated and
stored in an accessible and widely supported format, partly for ease of publication by the
researcher, but also, and crucially, for archiving purposes; much archaeometric data has
been lost over the years owing to the use of data formats which have become redundant.
Most digital radiography or radiograph scanning equipment produces data in both propri-
etary and generic formats. For archaeometric images, it is important that a widely available
generic and uncompressed format is selected for archiving. At the time of writing (2013), this
will be either as TIF or DICOM files. DICOM is a lossless data format originally devised for
the distribution of medical images but now adopted into the industrial world in the form of
DICONDE. It is possible that both these formats may eventually be superseded, but they are
currently so prevalent that it is difficult to foresee a time when conversion programs for these
formats are no longer available.
Once an adequate digital image has been generated it must be enhanced to make the
edges of the included materials visible for interpretation. One way to achieve this is first
to detect and then enhance the edges, a process generally carried out using a kernel-based
algorithm. A detailed study of suitable edge detectors (O'Connor et al., 2002) suggested
that a Kirsch edge detector was the most suitable for archaeometric work. While most com-
monly available imaging programs, such as Adobe's Photoshop and Corel's PaintShop Pro,
have the capacity to run such specialized filters as add-ons, they are not generally included
in the off-the-shelf version. However, experimentation by the authors has found that in the
majority of cases the use of the Unsharp Mask filter, originally devised to increase the reso-
lution of photographic images and conventionally included in most digital imaging pack-
ages, provides a perfectly adequate and more accessible alternative to these more expensive
add-on features.
554 INA BERG AND JANET AMBERS

FIGURE 30.5 Radiographs of a Middle Minoan amphora (BM registration number

G&R1906,m2.90) from the British Museum. All radiographs were recorded on Kodak
Industrex MX film in a hard plastic cassette with 0.25 mm lead sheets on either side of the
film. (a) Whole side of vessel, unenhanced image. Exposure parameters: Siefert DSr, o.s mm
focal spot, I m focus-to-film distance, 70 kV, 25mA mins. (b) Image from 4a, enhanced using
Adobe Photoshop Unsharp Mask filter. (c) Detail oflower body from sb showing diagonal
voids characteristic of rotative kinetic energy. (d) Detail of central zone from sb showing
parallel joins characteristic of coil forming and evidence of secondary working. (e) Detail of
upper body from sb showing evidence of coil forming.

A dramatic example of the successful use of a scanned film radiograph, enhanced with
Unsharp Mask, is given in Figure 30.5. Here a Middle Minoan III oval-mouthed amphora
(BM registration number G&R 1906,m2.90) was radiographed using Kodak Industrex
MX film. The film was then digitized using an Agfa RadView scanner with a so micron
pixel size and 12-bit resolution, and the resultant image enhanced using the Unsharp
Mask filter within Adobe Photoshop. Figure 30.5a shows the unenhanced scanned image,
while 30.5b shows the same image with an Unsharp Mask filter applied. Figures 3o.sc,
d, and e illustrate individual details of the lower, center, and upper body of the vessel,
individually processed for the greatest clarity. In Figure 30.5c, clear diagonal voids can be
seen representative of evidence of the rotative kinetic energy of wheel throwing. Parallel
joins in Figure 30.5d show that this zone was produced by coil forming, and the localized
distortion indicates that there was secondary reworking of this area. Figure 30.5e, the
~------------------------
'•%!

X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 555

shoulder at the top of the amphora, also reveals parallel joins indicative of coil build-
ing, but here there was no secondary treatment, thus making the coil joins more easily
recognizable.

RADIOGRAPHY OF CERAMICS-
PRODUCING THE BEST RESULTS

Crucial for the radiographic study of archaeological ceramics is the generation of a high-
contrast radiograph. In order to achieve this, the kV should be kept low and the exposure
time long. In work carried out by the authors, using either a Faxitron cabinet with a 3mA
fixed tube current or a Siefert DSr 320 kV industrial X-ray tube, voltages between 55 and
70 kV were found to produce the best images of ancient and modern ceramics with a range
of wall thicknesses, although such parameters will vary between equipment and between
film and digital setups. The exposure chart in Table 30.1 provides some basic guidance for
Faxitron users using standard industrial-type film. Exposure times will be considerably
shorter for digital capture and other X-ray setups will require experimentation to determine
the most suitable exposure parameters.
It is important to note that exposure time and kV are directly related to the thickness of
the ceramic object-the thicker the vessel, the longer the exposure and/or the greater the kV.
None of the many clays and tempering materials tested in experiments by the authors have
showed any deviation from this basic rule. To find the correct exposure for each pot, sim-
ply measure the thickness at several points along the vertical axis of a pot; vessels typically
change thickness most radically from base to rim. Select the exposure time and range that
best fits with the thickness range of the majority of the area to be imaged. In circumstances
where the pot has drastic thickness changes, one will have to take several images at different
exposure parameters to capture the entire vessel accurately. It is important to remember,
however, that one must double the wall thickness when X-raying a complete vessel to ensure
that the X-ray beam penetrates both sides of the object.
While it is always best to position objects at the center of the focal spot of the X-ray tube,
in order to keep geometric distortion to a minimum, several small ceramic objects of similar
thickness can be imaged together in the same exposure without loss of quality, helping to
keep costs low and conduct a project speedily. Larger objects may each require their own
plate. X-ray translucent supports can be used to prop up objects, prevent them from rolling
off their spot, and align them as parallel as possible to the horizontal surface of the film, cas-
sette, or imaging plate being used. For most exposures, pieces of bubble-wrap or plastizote
are suitable supports. The object should be in as much direct contact with the cassette as
possible and cassettes can be either solid or flexible. In most circumstances, a solid cassette
will suffice, but flexible cassettes have advantages for the examination of complete vessels
because they can be bent to fit inside objects, allowing an image to be collected for a single
side of a vessel. Because of the low energies employed in ceramic radiography, the use of fil-
ters (lead, aluminum, etc.) to remove low-energy scatter and sharpen the image, essential for
the radiography of denser objects, is unnecessary for ceramics.
556 INA BERG AND JANET AMBERS

Table 30.1 Exposure times and kV for clay objects using

a Faxitron cabinet X-ray machine with a 0.5
mm focal spot. 60 em focus-to-film distance,
3 mA, and Agfa Structrex 04 Film. The kV
shown here only present a guide-radiographs
should always be taken using the lowest
possible kV to improve image contrast
Clay thickness 55 kV 70 kV
(mm)

19 150 sec
18 150 sec
17 150 sec
16 120 sec/150 sec
15 120 sec/150 sec
14 105 sec/120 sec
13 105 sec/120 sec
12 90 sec/1 05 sec/120 sec
11 120 sec 90 sec/105 sec/120 sec
10 105sec/120sec 90sec
9 105 sec/120 sec 90sec
8 105 sec/120 sec 90sec
7 90 sec/1 05 sec
6 90 sec/105 sec
5 75 sec/90 sec
4 75 sec/90 sec
3 75sec

Tips and Tricks

Experience has shown that there are a number of tips and tricks that can increase the likeli-
hood of producing good images, the quality of the images, and/or increase visible detail, and,
as a result, our ability to analyze and interpret a ceramic object confidently.

(1) The inclusions and clay body are normally sufficiently different in radio-density to
allow successful interpretation of features. Despite this, it is highly recommended
that a pilot study of the assemblage be conducted to avoid disappointment and/or
 X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 557

wasted time and resources, because some ceramics have characteristics which make
their analysis difficult. These difficulties include: inclusions and clay body with simi-
lar radio-densities, for example grog; large and abundant inclusions that obscure
subtle features; the vessel walls are very thick, for example large storage vessels; and/
or the vessel was heavily turned, as was the case in the above-mentioned Bronze Age
Cypriot pots.
(2) When radiographing a complete or largely complete vessel for the purpose of deter-
mining forming technique, it is always advisable to take two views: one from above
(a plan view) and a side view. This is because some voids, such as the spiral void
arrangement of wheel-thrown pots, are sometimes only or more visible in one view
than the other. There does not seem to be a discernible and persistent pattern as to
which view will provide the clearest view of these features. Consequently, it is only by
taking both views that an accurate identification is possible (Figure 30.6).
(3) Always base interpretations only on clearly visible patterns. When determining a
forming technique, there is always the potential danger of assigning meaning to a ran-
dom or unrepresentative alignment of voids or inclusions. One way to counter this
tendency is to turn the radiograph through 90 degrees and look for the alignments
again. If you find alignments along this rotated axis, then it is most likely that they are
not true alignments and the radiographs do not provide a clear indication of how the
vessel was made. If there is any doubt about the interpretation of features in the radio-
graph, analysts should err on the side of caution. Also, since different people perceive
black and light areas on radiographs differently, it is sometimes helpful to reverse the
grayscale of a radiograph, making previously light sections darker and dark sections
lighter.

FIGURE 30.6 Radiographs of a bell-shaped handled cup (Middle Minoan I) from Knossos
(BM registration no G&R1950,uo6.r6) Taken from the side (a) and above (b). The diagonally
stretched voids indicate that rotative kinetic energy (RKE) was used in the making of this
vessel and hence that the main body is wheel-thrown. The handle was pulled and its bottom
attachment only lightly pressed onto the body. The details of the handle can only be seen in
a, while the spiral pattern of inclusions in the main body is far clearer in b. Exposure param-
eters for both exposures: Siefert DSr, 0.5 mm focal spot, I m focus-to-film distance, 6o kV,
20 rnA rnins, Kodak Industrex MX film. Enhanced using Adobe Photoshop Unsharp Mask.
558 INA BERG AND JANET AMBERS

( 4) In cases where it is possible to conduct destructive analysis, thick-sectioning,

a variation on the standard X-ray method, can be used to attain a more detailed
understanding of vessel formation. Thick-sectioning was pioneered by Vandiver,
who used it to reconstruct the precise size of each clay slab and building sequence
of slab-built vessels (1987: plates 5-7; Vandiver et al. 1991: figures 8-11). Thick-
sectioning involves cutting a vessel or sherd vertically into thin slices with a radio-
graph being taken of each slice's cross-section. The resulting images display features
diagnostic of the chosen forming technique and often provide clues about the
building sequence.
(5) It is absolutely essential that any radiographic interpretation is based on a deep and
thorough understanding of formation processes as well as the characteristic radio-
graphic fingerprint of each technique. We therefore strongly recommend that schol-
ars work together with a practicing potter to create a control group of modern replicas
against which they can compare radiographs of archaeological ceramics.

CASE STUDIES

To demonstrate the power of radiography as a technique for the study of archaeological

ceramics and to illustrate its potential contribution to the development of a more detailed
understanding of sociocultural patterns and changes, we provide a summary of three case
studies of objects in the collections of the British Museum.

Case Study 1: the Cretan Bronze Age

In zoo6, the authors collected X-ray images of twelve open and closed Middle Bronze
Age vessels with a firm Cretan (Knossian) provenance from the British Museum's collec-
tion (Berg and Ambers, zona). Analysis of the radiographs indicated that two vessels, a jug
and an amphora, were produced by coiling, and a jar, a jug, an amphora, and two cups were
manufactured by wheel throwing; no forming technique could be conclusively determined
for four vessels, an amphora, a cup, a heavily restored jar, and a jug. The most exciting find-
ing, however, was that one amphora (BM registration number G&R 1906,1112.90) was made
using three different techniques in sequence (Figure 30.5): the diagonally stretched voids
around the lower body indicate that this section was wheel-thrown using rotative kinetic
energy (Figure 30.5c). The middle section or vessel body is characterized by parallel joins
indicative/diagnostic of coil-building, although these are partially concealed by second-
ary shaping visible as the differential thickness of the wall (Figure 30.5d). This secondary
working is also apparent as elongated vertical lines on the radiograph. These vertical lines
probably represent drawing marks, although there is no evidence of preferential vertical ori-
entation of the inclusions or voids to confirm this, and there is a chance that this feature
results from the use of the paddle and anvil technique using a rod-shaped paddle. The ves-
sel's shoulder was also made using coils) but did not receive any secondary treatment, leaving
the coil joins more easily recognizable (Figure 30.5e).
 X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 559

At its most basic, this case study demonstrates the great variability in forming techniques
employed by Bronze Age potters on Crete. On a more detailed level, it hints at a degree of
specialization within the potting tradition of Crete with small, open vessels generally being
wheel~thrown, while large, closed vessels are often handmade. This observation was sub-
sequently tested in a larger X-ray-based project and found to apply throughout the Cretan
Bronze Age and across all of Crete (Berg 2009, 2015).
Most intriguing, however, was the recognition that the potters sometimes combined sev-
eral methods to manufacture a single vessel. Additional examples of vessel formation using
a combination of techniques were identified during the large-scale X-ray study, as well as
in the literature. Two important points about ceramic manufacture emerge from analysis
of these vessels: first, when the wheel is employed on these large vessels, it is utilized for the
basal and lower body sections which are comparatively easy to make. Second, the height of
the wheel~thrown sections is approximately 16 em, the maximum average height achieved
using this technique by potters across Crete. It is possible that this height restriction was
a consequence of limitations in the design of the potter's wheel, making it unable to store
momentum for sufficiently long periods oftime to throw large vessels in one sequence (Berg,
2015). Rather than modify or develop a better potter's wheel, Cretan potters employed an
alternative technique, wheel-shaping (termed "wheel-coiling" in recent literature), that
allowed them to construct vessels in stages, using a preshape made by coiling, and subse-
quently modify the shape and appearance of the pot with rotative kinetic energy (for the
wheel-coiling technique, see Courty and Roux, 1995; Roux and Courty, 1998).

Case Study 2: Aegean Stirrup Jars

The stirrup jar is a distinctive vessel shape from Bronze Age Greece which first appeared in
the Middle Bronze Age and reached its greatest popularity in the Late Bronze/Mycenaean
period. These vessels are characterized by a central, false spout closed off with a disk. Two
handles reach from this spout to the shoulder where a second, and functional, pouring spout
is positioned. Large undecorated stirrup jars functioned as transport containers for olive oil,
while smaller, decorated versions were used to store perfumed oils. Owing to the desirability
of their contents, stirrup jars were produced in many workshops both inside and outside
Greece and traded widely throughout the Mediterranean. Analysis of thirty-nine jars in the
British Museum by Leonard and his colleagues in 1993 used NAA to investigate vessel prov-
enance, XRF and XRD to determine the composition of the paint, and xeroradiography to
establish whether individual manufacturers and/or workshops could be identified by their
differential use offorming techniques (Leonard et al., 1993).
The radiography results were illuminating and two different methods of manufactur-
ing stirrup jars could be documented. In one tradition, the vessel and fake spout were built
in one sequence, resulting in a hollow fake spout. '!he other tradition attached a solid fake
spout, thrown as a separate piece, to the completed vessel during the leather-hard stage
(Figure 30.3). These distinct manufacturing methods were shown to be indicative of differ-
ent regional potting traditions, with Attic and Rhodian pots favoring the solid fake spout
method and Cretan potters manufacturing vessels in a single process.
An important result of this study is the reminder that similar vessel shapes can be cre-
ated using very different formation techniques and manufacturing processes, and that the
560 INA BERG AND JANET AMBERS

transfer of practical knowledge can create local or regional forming traditions. Therefore, it
is valuable/essential to identify these traditions and technologies using X-radiography.

Case Study 3: Mycenaean Pottery

Our knowledge of production equipment, forming techniques, and organization of pottery
production in Late Bronze Age mainland Greece, during the Mycenaean period, is surpris-
ingly limited. This is partly owing to the dearth of archaeological evidence from this period
that relates to ceramic manufacture; for example, only two wheel heads survive from the
Middle Bronze Age. The lacuna is partly also a consequence of research traditions and pri-
orities uninterested or engaged with questions related to ceramic manufacture in general
and forming techniques in particular. For example, most archaeologists never explicitly state
or appear to investigate manufacture technologies and formation techniques utilized to cre-
ate Mycenaean ceramic assemblages; and yet there is a tacit assumption that almost all ves-
sel shapes and wares were mass-produced by wheel throwing (Berg, 2013: table 1). It is only

FIGURE 30.7 Radiographs of a Mycenaean krater (BM registration number

G&R1898,120L112) taken from the side (a) and above (b). The vessel has undergone extensive
modern restoration with the long straight lines representing adhesive joins and the speckled
area near the center of the rim being modern infill. Nonetheless, clear evidence survives of
the use of coil building in the form of numerous elongated voids along the coil joins with
rotative kinetic energy applied subsequently creating irregular rilling. The coil joins are
particularly clear in the image taken from above. Exposure parameters for both exposures:
Siefert DS1 tube, 0.5 mm focal spot, I m focus-to-film distance, 6o k\1, 20 rnA mins, Agfa
Structrex D7 film. Enhanced using Adobe Photoshop Unsharp Mask
 X-RADIOGRAPHY OF ARCHAEOLOGICAL CERAMICS 561

with reference to the earlier Middle Bronze Age, during which it is generally accepted that
a wide variety of potting technologies and methods were in use, that scholars list forming
techniques in their catalogue entries.
In order to throw some light upon this under-researched aspect of Mycenaean potting
traditions and to investigate the existence of other forming techniques, the authors con-
ducted a pilot study of Mycenaean vessels in the British Museum's collections (Berg and
Ambers, zonb). The results are as follows: three vessels are wheel-thrown (two bowls and
a small jar), one vessel is handmade (a miniature jug), and three vessels are wheel-shaped
(two kraters and a bowl) (Figure 30-7). Two alabastra and a rhyton are manufactured using
a combination of handmade and wheel-made techniques. These vessels demonstrate the
great variability in forming techniques and/or potting traditions employed by Mycenaean
potters. Like potters in the preceding Middle Bronze Age, it is now confirmed that
Mycenean potters also utilized a wide range of techniques and methods for ceramic man-
ufacture and frequently combined several methods to produce a single vessel. Thus, the
tacit assumption that all Mycenaean pottery was wheel-thrown has been demonstrated
to be inaccurate by this radiographic analysis. The consequences of this research are far-
reaching and potentially paradigm-shifting because it imposes a reassessment of our
understanding of pottery production in this period, alerts scholars to the need for detailed
ceramic analysis, and reminds us always to test our assumptions against the archaeological
record.

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 CHAPTER 31

ORGANIC INCLUSIONS

MARTA MARIOTTI LIPPI

AND PASQUINO PALLECCHI

INTRODUCTION

CERAMIC artifacts are made with clay hardened by kiln firing. The general term "clay" indi-
cates a mixture of one or more clay minerals (hydrous aluminum phyllosilicates) containing
small amounts of other mineral phases and organic compounds. Clay deposits may also con-
tain microfossils, such as pollen, diatoms, and other animal and plant remains.
One of the important considerations for ceramic manufacture is the performance of the
clay during firing. If the right balance between clay minerals and inclusions is not maintained,
ceramics can slump or fail during firing. To avoid this, temper is often added to the clay.
Tempers may consist of inorganic, non-plastic materials, such as minerals, rock fragments,
and grog (crushed pottery and firebricks), and/or animal and plant matter. The mixture
of clay and temper improves both the plasticity of the paste and the thermal properties of the
vessel. 1he type and amount of temper used depend upon the manufacture technology used
to produce the vessel and its ultimate use/function. The selection of a specific organic temper
may depend upon local availability of resources, ease of access to recycled materials, and/or
be dictated by cultural factors and intended usage of the resulting artifact.
In this text, organic inclusions are regarded as remains of biological matter; that is, por-
tions of organisms or even entire small organisms, which are trapped in ceramic paste.

THE ORIGIN AND NATURE OF

THE ORGANIC INCLUSIONS

Organic inclusions may occur naturally in the raw materials used to manufacture ceramics
or they may be intentionally added to the clay paste by potters. During the firing, organic
compounds undergo a partial or complete destruction, creating pores in the ceramic fabric.
These pores make the vessel permeable and resistant to temperature changes and therefore
suitable for cooking and as food storage containers (Maggetti, 1994). Minute charred organic
 l
566 MARTA MAKH.HTI LIPPI AND PASQUINO PALLECCHI

materials or their heat-resistant mineral components are often found in these pores and can
be extremely useful in the identification of the type of organic material included in the paste.
Biological remains, when present, can be detected in the paste of ceramic artifacts and
sometimes even on their surface: they appear as small spots or pits and their size is usually so
small that they are hardly visible to the naked eye. In most cases, only magnifying lenses and
microscopes can detect the presence ofbiological remains and reveal their shape. When the
observation of the morphological features of organic inclusions in ceramic paste does not
permit identification, microanalytical investigations can determine chemical composition
and reveal important information about the type of temper employed. The study of organic
inclusions in ceramics is, therefore, a promising source of information about ancient envi-
ronments, sourcing of raw materials, and ceramic manufacturing techniques.
When we study organic inclusion in ceramic wares, one of the first logical question is
whether the inclusions were present in the raw material; that is, the natural deposit from
which the clay was taken. Were the inclusions accidentally trapped in the paste during the
kneading process and, therefore, present in the environment where the pottery was pro-
duced? Or rather, were they deliberately added to the paste in the form of temper to improve
the plasticity of the clay? In some instances, the high concentration and type of inclusion
leave us ill no doubt, but it is not always easy to find a definite answer to these questions.

Organic Inclusions Occurring in Raw Materials

Organic inclusions that naturally occur in clay deposits and therefore may be found in
ceramic paste can be entire microscopic organisms or fragments and/or parts of macro-
scopic plants or animals. A good example is the pottery of 'Thailand's Ban Chiang region
(c.36oo BC-200 AD), where fre'shwater diatoms and sponge spicules were detected in ceramic
wares. Tempers of different composition were intentionally added to Ban Chiang pottery
throughout its history: since freshwater diatoms and sponge spicules are always found in the
ceramic paste of wares from all periods in spite of diverse temper combinations, this sug~
gests that they were present in the clay deposits of local lakes that supplied the raw material
(McGovern, 1989).
Diatoms are unicellular algae belonging to Bacil/ariophyta, widely distributed in damp
and aquatic habitats. Their cell wall (called frustule) is composed of two overlapping thecae
or valves: the larger one is called epitheca and the smaller hypo theca. The frustule is mostly
made of silica (hydrated amorphous silicon dioxide, SiO,.nH,O ); it has a peculiar shape with
sculptures, that is, surface relief, and perforation patterns, which are valuable in systemat-
ics. When the algae die, the frustules sink and are preserved in sediments at the bottom of
water bodies. Some types of diatoms only survive within a restricted range of ecological
parameters, making diatom analysis useful for the environmental reconstruction of ancient
artifacts. Beside diatoms, many other microscopic organisms may be preserved in clay sedi-
ments and survive the firing process, such as, for example, foraminifera, ostracods, radio-
laria, and silicoflagellates (for references, see Quinn and Day, 2007).
Sponge spicules are siliceous or calcareous structural elements produced by sponges in
freshwater, brackish, and marine environments. Siliceous spicules, which occur in a wider
morphological variety than the calcareous ones, are divided in megascleres and microscleres
depending upon their size. Once sponges are dead, their organic elements decompose and
 ORGANIC INCLUSIONS 567

FIGURE 31.1 Fan-shaped phytolith from modern rice (r mm).

their spicules accumulate at the bottom of water bodies: chemical composition, symmetrical
axes, shape, and dimensions of these spicules are useful tools for the identification of the
sponges.
Phytoliths are another type of organic inclusion commonly found in ceramic paste: the
term refers to all mineral (generally siliceous) plant deposits and often disarticulated
remains surviving the decomposition of organic matter (Figure 31.1). In growing plants,
silica may be deposited inside the epidermal cell walls, in intercellular spaces, or inside
the cell lumen: the latter deposits are more properly termed silica bodies. Silica deposits
have distinctive shapes useful for plant identification. An International Code for Phytolith
Nomenclature was published for standardizing phytolith classification and descriptive
parameters (Madella et al., 2005). Phytoliths may occur naturally in clay sediments used
for pottery manufacture, or their presence in ceramic wares may result from the intentional
use of vegetable temper. The quantity of phytoliths in the artifact generally provides clues
as to their origin: when phytoliths appear in negligible amounts they are usually found in
clay deposits. Conversely, if they reach significant quantities they were most likely added
together with the temper.
Unusual organic findings in ceramic are the well-preserved palynomorphs that were
discovered in half-burnt potsherds from a Chalcolithic-Early Historic site in West Bengal,
India (Ghosh et al., 2006). The palynomorphs include algal remains, spores, and pollen, pre-
sumably coming from the surrounding area. It is interesting to note the presence of fossil
disaccate pollen grains (cf. Striatopodocarpites) of Permian origin. The preservation of the
pollen grains is thought to be due to the short duration of the firing process.
Organic inclusions may also be accidentally trapped in the clay paste during the knead-
ing process: in this case their presence is infrequent. An example of accidental inclusion is
the barley caryopsis (Hordeum vulgare) found in a potsherd from the Caverna dell'Aquila at
Finale Ligure, Italy (Arobba and Caramiello, 2006). '!he caryopsis was completely burnt out
during the firing, leaving a void in the paste. It is proposed that the barley was present at or
around the location of ceramic manufacture.
S68 MARTA MARIOTTI LIPPI AND PASQUINO PALLECCHI

FIGURE 31.2 Thin section of rice~ tempered ceramic from Sumhuram, Sultanate of Oman:
dark (above) and bright (below) rice lemmas/paleas. "Ihe bright one was more severely
affected by oxidation during firing (1 mm).

Intentionally Added Organic Materials

A large variety of organic materials were used as tempering agents in archaeological ceramics.
During firing, some types of organic tempers are preserved in a carbonized state (Figure 31.2),
while others are completely destroyed, leaving only impressions in the paste and pits on the
surface of the artifacts. These impressions-the negative imprints of the organic inclusions-
result in tiny holes that increase porosity of the ceramic body and make the artifacts lighter
and more permeable than those where mineral tempers were employed. When organic tern-
per contains mineral components, such as cereal chaff or mollusk shells, these are more easily
preserved during firing than organic compounds such as mollusk bodies.
The deliberate addition of a specific temper often introduces a small amount of"contami-
nation" into the paste. For example, since weeds are harvested together with crops, cereal
chaff normally incorporates weed seeds; their quantity depends on the degrees of weed
infestation in the fields (Harvey and Fuller, 2005).
Organic tempers may be divided into two main groups: plant temper and animal temper.
They may be used alone or mixed with other organic or inorganic tempers.

Plant Tempers
Plants used as tempering agents include numerous species, but generally consist ofbyprod-
ucts of the cereal crop processing waste and include different portions of the plant: stalks,
husks, and ear bristles. The use of this tempering technique appears to have been quite com-
mon in the Prehistoric Old World, and survived to recent times in restricted areas: cattail
fuzz was still used as ceramic temper in Afghanistan, near Kandahar, during the second half
of the twentieth century (Matson, 1974); in Palestinian pottery, the tempering ingredients,
threshing-floor straw, and cattail fuzz together with animal dung, shells, or sand, were added
 ORGANIC INCLUSIONS 569

during wedging and worked into the clay to improve workability and reduce shrinkage
(johnston, 1974).
The use of cereal chaff as ceramic temper has been attested in many Asian archaeologi~
cal sites. It is related to cereal farming and, consequently, availability of cereal processing
byproducts. On the other hand, since pottery was widely used in trade, the presence of cereal
chaff in wares does not necessarily indicate local cultivation, but may indicate the geographi-
cal area of production of the ceramic artifacts. The local provenance of the wares may be
verified by comparing the mineral composition of the ceramic paste with those of the clay
deposits occurring in the area. Otherwise, local cereal cultivation may be identified by
means of pollen analysis or detection of cereal phytoliths in the soil.
The use of cultivated cereal chaff for tempering ceramic is first documented in southern
China in w,ooo cal BP, where rice husks (Oryza sativa) were used as temper in Neolithic
pottery of the lower Yangtze River region. Among other plant remains the ceramic contained
fan-shaped rice phytoliths (Jiang and Liu, 2006). In Northern India, rice chaff-tempered
pottery dating between c.2500-10oo BC was recovered in several Neolithic sites (Bellwood et
al., 1992; Fuller, 2006). At Khok Phanom Di in Thailand, pottery from the second half of the
second millennium BC was found to contain foreign rice temper: although rice Was naturally
available in the area, apparently the local pottery industry did not exploit it. Indeed, petro-
graphic analysis indicates that clay was sourced north of the area, in the upper Bang Pakong
Valley (Vincent, 2003). A similar situation also occurred in Bali, where rice husk-tempered
pottery appears to have been imported from India, although rice was grown locally and is
attested by phytoliths in the soil (Bellwood et al., 1992).
Rice-tempered ceramics were discovered at several locations outside the area of ancient
rice cultivation, such as the Red Sea and coastal region of the Arabian Peninsula (Figures 31.2
and 31.4a); these findings indicate the existence of trade routes throughout the area around
the Indian Ocean (Mariotti Lippi et al., 2011; Tomber et al., 2011). In the Arabian Peninsula,
cereal chaff was found in ceramic fragments from the first millennium BC at Qala'at
al-Bahrain: since three grains of barley were also found impressed in the pottery, the chaff
was tentatively identified as two-row hulled barley (Hordeurn distichon). The provenance of
the object is unknown (Willcox, 1994).
Cereal chaff-tempered ceramics were also found in Sahelian Africa. Listed in chronologi-
cal order from Neolithic to Iron Age, the dominant taxa are Sorghurn, Setaria, Panicum, and
Pennisetum (Fuller, 2013). Most interesting, ceramics tempered with Sorghum husks were
recovered at Essouk-Tadmakka in Mali (c.11o0-1300 AD); as the site bore no evidence of sor-
ghum processing or consumption, this confirms the hypothesis that the wares were imported
to Essouk-Tadmakka from the Niger Bend, where stylistically similar pottery was produced
(Nixon et al., 2011). In Europe, the use of cereal chaff seems to have been be uncommon;
plant fragments, possibly Triticum sp. chaff, were however found in Early Neolithic clay figu-
rines, in Hungary (Kreiter et al., 2014), while unidentified chaff dating to sooil BC, was found
in pre-Roman Iron Age vessels in Sweden (Stilborg, 2001).
In addition to cereal byproducts, other plants were intentionally collected for temper-
ing ceramics. A few meaningful examples are listed here by geographical area. For centuries
in far East Russia (Asia), coarsely chopped grass was added to the clay for ceramic vessels
(Miermon, 2006; Ponkratova, 2oo6); conifer needles were used with similar purposes in far
East Russia during the Neolithic (Ponkratova, 2006). Sizeable fragments of stems and leaves
of sedge (Cyperaceae), horsetail (Equiseturn), and burdock (Arctiurn lappa, Asteraceae family)
570 MARTA MARIOTTI LJPPI AND PASQUINO PALLECCHI

were found in Neolithic ceramics from South Sakhalin (Zhushchikhovskaya and Shubina,
zoo6).ln Africa, leaf fragments of sedges (Cyperaceae) and impressions of other wild plant
materials were observed in pre-Pastoral and Pastoral sherds at Gobero (south Sahara). The
use of these vegetable fragments suggests the intentional gathering of wild plants for ceramic
production and indirectly the absence of crop byproducts (Fuller, 2013). In Europe, a mixture
of mosses, mostly Neckera crispa, was commonly used for tempering ceramics in France and
Belgium during the Neolithic (Constantin and Kuijper, 2002). In South America, particularly
in Amazonia, one of the most common organic tempers consisted of ashes and microchar-
coals made by burning the bark of trees belonging to several genera of the Chrysobalanaceae
family, particularly Licania spp. The barks of these plants contain silica bodies in parenchyma-
tous and epidermal cells, and often their cell walls are also silicified (Cronquist, 1981; De Walt
et al., 1999). Native populations living in the Amazon have used this material as temper for
generations (Evans and Meggers, 1962; Costa et al., 2009, 2011).
It is important to mention that most plants used as temper contain phytoliths and are
therefore so-called Si-accumulating plants: in other words, they are capable of absorbing
silicon from soil solutions (more precisely mono-silicic acid) and accumulating it as silica.
Si-accumulating plants most commonly used for temper are Equisetum; Poaceae cere-
als and grasses; sedges (Cyperaceae family); Asteraceae. Silica is also present in the bark of
Chrysobalanaceae and the needles of gymnosperms (Hodson et al., 2005). InPoaceae, silicon
dioxide (silica) can reach 15% of the plant's dry weight (Neethirajan et al., 2009). When these
plant tempers are used in pottery making and burn out during firing, their phytoliths may be
preserved in the voids, thus allowing the identification of the plant.
Finally, organic inclusions in ceramics may also be due to the use of biochemical sedimen-
tary rocks as tempering agent. For example, the addition of diatomite to the paste introduces
algal microfossils (i.e. diatoms) in the ceramic.

Animal Tempers
Many organic tempers are animal in origin: bones and shells (Figure 31.3a) are the most com-
mon. Bone-tempered ceramics were spread through Europe during the Neolithic and Bronze

FIGURE 31.3 Shell-tempered ceramic from Sumhuram, Sultanate of Oman: (a) fracture
surface showing shell fragments (stereomicroscope); (b) EDS spectrum indicating the pres-
ence of calcium in the animal material.
 ORGANIC INCLUSIONS 571

Age (Stilborg, 2001; Freudiger-Bonzon, 2005). Before being used in ceramic manufacture,
bones were subjected to a heat treatment, a necessary precursor to crushing or grinding them
into minute fragments. In the ceramic artifact, these fragments generally have an angular out-
line and a smooth surface: at high magnification, their histological features and canals may be
visible. When these diagnostic characteristics are not present, the tiny fragments are often insuf-
ficient to determine the type and origin of the bone used. Bone-tempered ceramics have a high
phosphorus content, much higher than the lowvalues of natural clay(P ,05 = 0.1-0.5 wt.%);how-
ever, the high phosphorus pentoxide content is not sufficient to attest the use ofbones as temper,
more generically indicating the employment of animal temper (Freudiger-Bonzon, zoos).
An unknown and unusual temper of animal origin was found in the Neolithic ceramics at
Quadrate di 1orre Spaccata, near Rome (Italy). Petrographic analysis revealed voids in the
shape of parallelepipeds and energy dispersive X-ray spectrometry (EDS) analysis indicated
high phosphorus values, both suggestive of animal temper. According to Pallecchi (1995),
these voids likely result from the charring of organic matter, possibly meat, which was cut or
processed to produce a regular pattern.
Crushed shells of freshwater and saltwater mollusks are often found in pottery from the
Neolithic period onward. For example, large surface pits with a peculiar shape were found
on the exterior and on the breaks of Neolithic pottery from Sakhalin Island (northern
Pacific). The shape of the pits recalls mollusk shell fragments: indeed, small shell fragments
are sometimes found in the pits. Morphometric analysis of the pits enabled the identifica-
tion of several types of mollusks still growing in rivers, estuaries, and coastal waters of the
area (Zhushchikhovskaya and Shubina, zoo6). Among them, the most frequent species is
Corbicula japonica, which has a very fragile shell. The consistently high phosphorus content
of these wares suggests that both mollusk shells and bodies were used as temper: the shells
prevented the clay from cracking during drying and firing, while the bodies were used to
increase the porosity of the artifact (Zhushchikhovskaya and Shubina, zoo6).
Prehistoric Oceanic pottery was tempered with a wide variety of organic materials.
Among them were calcareous sands composed primarily of biogenic reef debris, such as
the remains of corals, mollusk shells, foraminifera, and so on (Dickinson, zoo6), and burnt
coral, used to temper pottery in the Yap Islands, Micronesia (Intoh, 1988).

FIGURE 31.4 Fracture surface of a potsherd from Sumhuram, Sultanate of Oman: (a) rice
chaff fragment (stereomicroscope); (b) EDS spectrum indicating the presence of silicon in
the plant material.
572 MARTA MARIOTTI LIPPI AND PASQUINO PALLECCHI
l "
~~

I
[j

FIGURE 31.5 Renaissance ceramic tempered with wool (polarized 1 mm).

Sponge spicules have been found in Iron Age ceramics from Africa (inland Niger delta)
and South America, especially in the Amazon Basin (Evans and Meggers, 1962; Costa et a!.,
2009; Nixon, 2009; Costa, 2011). In these ceramics, spicules often have parallel orientation
and occur in clusters. This particular orientation and grouping, rather than the overall num-
ber of spicules in a vessel or sherd, suggests that sponge fragments were intentionally added to
the paste, and excludes the possibility that the spicules were originally in the deposits where
the clay was collected.
Many other animal tempers are occasionally found in clay wares worldwide: feathers, fish
scales, dung, fibrous materials such as baleen, wool (Figure 31.5), and animal fur; for example,
deer and horse hair. (London, 1981; Miermon, 2006; Ponkratova, 2006, Kiryushin eta!., 2012).
A remarkable application of animal material in ceramic manufacture consists of using animal
hair as a framework during the shaping of vessels with the coiling technique: bunched hairs
are arranged as filler in the seams between the coils and added to the paste, coating the ves-
sel before baking. An example of this technique is the use of horsehairs in comb-patterned
ceramics recovered at Tytkesken-2 in Russia. This tradition was also widespread in western
Siberia from the early to the last Neolithic period (Kiryushin eta!., 2012).

LABORATORY METHODOLOGIES

In order to identify organic inclusions in archaeological ceramics it is necessary to

observe and identify their structure and micromorphology with instruments of sufficient
magnification to detect diagnostic features. Generally, an initial screening of the material at
low magnification is the first step in order to identify the potsherds potentially containing
organic inclusions. A simple magnifying lens (magnification 6-15x) held close to the eye might
be sufficient to notice discontinuities in color and reflectivity or pitting in the vessel walls, all
potential indicators of temper. However, owing to their small size, the identification of organic
 ORGANIC INCLUSIONS 573

inclusions requires greater magnification, achieved by using a stereomicroscope (magnifica-

tion commonly up to 6ox) or even a compound light microscope (LM) (magnification up to
100 ox), Both these microscopes utilize the interaction of the objects with visible light; however,
they provide different information about the material: the former is useful for identifying the
general tridimensional shape and micromorphology of the organic inclusions, while the latter
allows us to see their inner structure and micromorphology.
The stereomicroscope is used for a variety of analyses over the course of the analysis
because it allows a rapid s~rface screening of the specimen. The instrument is easy to use
(even though many researchers utilize it under suboptimal conditions), does not require
a previous preparation of the specimen to be examined, and allows direct observation of
objects of rather large size, such as potsherds. Observation under LM, on the other hand,
always requires laboratory preparation of the sample or specimen. Since light must pass
through the sample in LM, the thickness of the specimen must be minimal, usually ranging
from 1 to 10 ~m for biological specimens and 30 ~m for minerals. When the thickness of the
sample exceeds these dimensions it is necessary to cut it in sections prior to viewing. The sec~
tions are then placed on a slide and covered with a coverslip, using aqueous or non-aqueous
solutions as mounting medium. When analyzing ceramics, the thin sample Sections are
attached to a flat slide with epoxy resin, abraded to reach optimal thickness (25-30 ~m), At
about 30 ~m of thickness, all the sample components are translucent and can be observed
under LM. The sample section is covered with a coverslip, again using epoxy resin as mounting
medium. The presence of the coverslip unfortunately excludes any successive microanalysis.
Although polarizing light microscopy is successfully employed in petrographic analysis, it
is generally not useful in the study of organic inclusions, which lose their original optical
properties with charring. Moreover, organic inclusion might turn into cavities during com-
bustion and later appear simply as dark areas in the thin sections.
When we observe material cut into thin sections all the components appear two-dimensional
and their shape depends on the inclination of the cutting plane, Only by <malyzing the same
object sectioned along different cutting planes and collating the information can the object's
original three-dimensional shape be reconstructed. Finally, the sample material must be
recorded as photographs; it is important to keep in mind that a reference scale is a fundamental
element of any photograph or reproduction of the materials analyzed under a microscope.
Scanning electron Jnicroscopy (SEM). A three-dimensional view of organic inclusions,
at a higher magnification than can be achieved under a stereomicroscope, is possible by SEM.
In addition, SEM analysis facilitates a more detailed surface analysis of inclusions because of
its very high resolution (Figure 31.6). SEM observation requires mounting the specimens on
metal stubs, usually 12.7-32 mm in diameter, using conducting double-sided adhesive tape
or other conductive adhesives. Some samples can be observed directly with SEM, although
generally they need to be covered by a thin layer of conducting material to present a suitable
image. This is usually achieved using a sputter coater, which covers the specimens with a thin
layer of gold or carbon (usually ranging from 15 to 30 nm thick) inside a vacuum chamber.
When the organic inclusions are burnt out in the kiln, cavities with well-defined shapes
can be seen in place of the charred biological materials: the negative surface of these pits can
be examined by SEM after cleaning, using compressed air or gentle brushing to remove dust
and carbon from the surface) and coating with a conductive material. Some of these impres-
sions may be cast with silicone elastomers at low viscosity such as polyvinyl siloxane (Fuller
et aL, 2007). The benefit of these casts of ceramic pits is that they are three-dimensional
 p

574 MARTA MARIOTTI LIPPI AND PASQUINO PALLECCHI

FIGURE 31.6 Rice-tempered ceramic from Sumhurarn, Sultanate of Oman: epidermis of

the rice husk with evident silicized tubercles (SEM).

replicas of the original organic inclusions incinerated in the firing of the pottery. Once
morphological observations of the organic inclusions are finished, they need to be compared
to modern reference materials. This comparison will depend upon the geographic and eco~
logical region of ceramic manufacture and is often best and most accurately conducted by a
specialist. When fresh reference material is not easily available, specimens kept in museum
collections can be used. The laboratory procedures depend on the nature of the material and
are provided in the manuals oflaboratory techniques and specific literature.
EDS analysis. Many SEMs are equipped for EDS analysis, a technique used to identify the
elemental composition of a sample. This information is rarely conclusive, but often indicates
the nature of the inclusion when it is unidentifiable on a morphological basis. As mentioned,
a high phosphorus content usually indicates animal material while silicon is more easily
found in plants. Siliceous sponge spicules are a well-known exception. Calcium may occur
in animals and plants (Figures 31.3b and 31.4b).
Radiography. X-radiography may be used to obtain quantitative measurements of size, den-
sity, and orientation of temper particles. In fact, when organic tempers are burnt out, the voids
appear as darker areas in X-radiographies (Braun, 1982). Radiography allows all useful data to be
simultaneously detectable even when analyzing a large area. It may be directly performed with-
Ollt any previous preparation of the sample, but may render the ceramic unsuitable for further
analysis, such as thermoluminescence analysis and radiocarbon analysis.

INTERPRETATION OF RESULTS
AND IDENTIFICATION OF THE INCLUSIONS

Interpretation of the microscopic and microanalytical data is a fundamental part of the anal-
ysis of organic inclusions. We must, first of all, keep in mind that in microscopy we are not
observing real objects, but their images. The strllcture of the original object must therefore
 ORGANIC INCLUSIONS 575
--
be deduced with care from the images we collect. The appearance of a specimen depends in
large part on sample preparation techniques and the characteristics and operational condi-
tions of the instruments. In other words, the same object produces different images when
subjected to different laboratory procedures or observed under different instruments and
conditions. Consequently, interpretation of the images must take into consideration the dif-
ferent procedures and instruments employed in the analysis of the specimen.
The interpretation of scanning electron micrographs, for example, is not easy despite their
high resolution and magnification. Multiple images of the same specimen must be taken
from different angles and orientations (in relation to the detector) or with different mag-
nifications in order to accurately characterize its shape, size, and structure. Imaging speci-
mens at high voltages may result in deceptive phenomena such as transparency or artificial
brilliance of spiky elements such as spines. A non-corrected astigmatism of the instrument
may produce incorrect shapes of the sample's minute features and decrease resolution. Thus,
researchers need to have good knowledge of technical procedures used to prepare the speci-
mens and understand the functioning of the instruments to maximize performance.
The identification of organic inclusions involves naming organisms or parts thereof
through comparative analysis of existing classification. Numerous micromorphological fea-
tures have taxonomic value and permit the identification of the organisms. The same mor-
phological characteristic can have or not have taxonomic value depending upon the group
of organism under consideration, therefore it is critical to refer to and/or have knowledge of
the specific literature in order to understand the significance of a particular feature. In the
case of chaff, for example, a detailed SEM analysis of the glumes' surface allows us to observe
whether it is smooth or wrinkled, as well as to examine the morphology of epidermal cells,
the presence or absence of trichomes and papillae, and their morphology; all of these fea-
tures are useful for identification of the species of cereal. On the other hand, by analyzing
thin sections of these same samples, we may detect other taxonomically relevant features,
such as the number, arrangement, and form of the vascular bundles, the disposition of scle-
renchyma, and the section outline of the glumes.
As indicated, direct comparative analysis of the organic inclusion with reference materi-
als and exemplars is critical. When the comparison is performed by means of photographs
or micrographs, it is essential that magnification and preparation techniques be explicitly
stated.
Sometimes, scientists avail themselves of scientific texts that include diagnostic keys. The
keys indicate which characteristics must be investigated in order to attribute a specimen
to a precise taxon (i.e. group of organisms). Diagnostic keys are extremely useful but not
always applicable: organic inclusions in samples are very fragmentary and rarely exhibit all
the characters necessary for identification. Furthermore, keys presuppose a detailed knowl-
edge of the group under examination and a command of specific and specialized terminol-
ogy. In addition, because identification of an organism is accomplished by referring to an
existing classification, it is important to use classification systems that are widely accepted
and commonly used, in order to make the identification unambiguous and unequivocally
comprehensible.
During analysis of a sample it is important not to disregard those characteristics that are
not immediately useful for identification because they may provide supplementary infor-
mation about the organism and, indirectly, the ceramic. For example, when analyzing thin
sections, the occurrence of transversal sections of small stems with large intercellular spaces
576 MARTA MARIOTTI LIPPI AND PASQUJNO PALLECCHI
--

suggests that the plants were growing in an aquatic environment: the anatomical and his-
tological characteristics of the plant are in fact adapted to the environmental conditions
in which the species grow. The recognition of aquatic environments provides information
about the production area of the archaeological ceramics of interest, and/or indicates raw
material selection.

WHAT Do ORGANIC INcLuSIONs TELL Us?

Tempers are added to a ceramic paste so that the resulting vessels and artifacts will posses
specific qualities and characteristics. The selection of a particular temper may depend upon
local manufacturing traditions, abundance or availability of the material, or technological
strategy. Different pastes are often associated with specific wares and/or functional classifi-
cations and easily identifiable macroscopically. Tempers, therefore, can tell us not only about
technology and tradition of ceramic manufacture in a given culture area or time period but
also potentially provide information about the geographical/ecological origin and deposi-
tional environment of the raw material, agricultural practices, and so on.

Geographical Area and Depositional Environment

Organic inclusions may be derived from remains naturally contained in the raw material
used for pottery manufacture. Alternatively, organic matter may be intentionally added to
the clay paste by the potter. In either case tempers indicate a geographical area and/or envi-
ronment, but there are significant differences in the archaeological interpretation of natu-
rally included and intentionally added organic material. It is reasonable to assume that raw
materials were collected relatively close to the place where the potter worked, and therefore
clay itself may contain organic remains that are characteristic of the environment where it
was deposited. Examples are the sponge spicules or diatoms that have been found in ceramic
vessels from Thailand (McGovern, 1989 ). In cases such as this, where these organic materials
were not intentionally added to the paste, inclusions provide information about the type of
sedimentary depositional environment from which the clay was sourced. Information can
be more or less accurate depending on the nature of the remains: diatoms, for example, are
generally good indicators of environmental parameters and may also reveal the origin of
the clay. However, some diatoms can live in a wide range of environmental conditions, while
others are extremely sensitive to one or more environmental parameters, such as pH, salin-
ity, water depth, and so on. In these cases, diatoms are more precise indicators of sedimen-
tary depositional conditions.
When organic materials are deliberately added to the clay as tempers, they often provide
information about the environment where the vessels were manufactured because, like the
raw clay materials, tempering materials are generally collected close to the site of pottery
production. Therefore, these inclusions are indicative of the geographical area where those
species were present. For example, a particular type of cereal chaff included in a ceramic
paste, clearly points to countries/regions of manufacture where that cereal was grown.
On the other hand, the finding of ceramics tempered with chaff of cereals that were not
 ORGANIC INCLUSIONS 577

FIGURE 31.7 Karnataka rice winnowing in South India.

locally grown suggests that those ceramics were produced in a different place and traded.
Additionally, environmental information related to location of manufacture may also come
from crop processing byproducts and local "contaminants" occasionally incorporated into
the paste during ceramic manufacture, such as weed seeds appearing together with the chaff
temper. These seeds provide evidence of surrounding wildlife, climatic condition, and some-
times eating habits of ancient populations.

Agricultural Practices
Plant inclusions in ceramic fabrics have played an important role in studies of prehistoric
plant use, cultivation, and domestication. As a matter of fact, analyses of crop remains or
impressions (grains and chaff) in pottery have provided important data about the diffusion
of cereal cultivation in prehistoric times and allowed us to detect morphological charac-
teristics that reveal stages of domestication. For example, pottery tempered with rice husks
that were shorter and wider than those of wild rice demonstrated that the beginning of rice
domestication was associated with the origins of sedentism in southern China (Jiang and
Liu, 1994).
In cereal processing, chaff is the result of winnowing, which follows either threshing
(separating the spikelets from the straw) or milling and pounding (separating the husk from
the grains) (Figure 31.7). 11re waste resulting from the winnowing after threshing and after
milling and pounding is different: the first contains light seeds and fragments of stems and
leaves; the second mainly husks and heavy seeds (Harvey and Fuller, 2005). It is generally
the second waste, a result of dehusking, which is used for tempering ceramics. In addition to
the husk, other byproducts of winnowing/crop processing, such as plant fragments, seeds,
leaves, or stems may occur as "contaminants" in ceramics.
Regarding animal remains, the small bone fragments used as temper are difficult to
identify, and thus generally offer little information about livestock. On the other hand,
the occurrence of other remains, such as fish scales and bones, wool, or animal hair, may
improve our knowledge of ancient populations' economic strategy and exploitation of
resources.
578 MARTA MARIOTTI LIPPI AND PASQUTNO PALLECCHI

Chronological Data
Organic inclusions in ceramics may provide chronological data about the artifacts by means
of accelerator mass spectrometry (AMS) dating. Carbons of different origin may be present
in archaeological ceramics: carbon from the organic compounds of clay deposits relate to
the age of sediment formation, and can be used to identify potential raw material sources/
clay beds; carbon inclusions deliberately added as temper, however, provide information
about the date of manufacture. The presence of carbons from two different sources and time
frames in the same sample can skew AMS dating of a ceramic, reporting dates older than the
real manufacture period.
Before preparing samples for radiocarbon dating it is convenient to evaluate the abun-
dance of organic inclusions. This information may be gathered by observing the thin sec-
tions or using other methods capable of furnishing quantitative data on inclusion density
and distribution. The size of the sample to be dated is dictated by the amount and the nature
of the inclusions and also original firing temperature and condition, which can cause carbon
oxidization.

CoNCLUSION

The study of ceramic wares means coming into contact with ancient cultures, local traditions,
manufacturing techniques, and trade history. Modern research methodologies supply inter-
esting information about natural and cultural factors that influenced the production of ceram-
ics. With regard to the specifics of organic inclusions, these can occur naturally in the clay or
be added intentionally to the ceramic paste. Inclusions naturally occurring in the raw material
offer information about the depositional environment of the basin from where the clay was
extracted and, in some instances, they represent a sort of fingerprint of a specific clay deposit.
When organic inclusions were intentionally added to the clay paste as tempers, they provide
clues about potting technologies and traditions which evolved in different geographical areas.
Moreover, since tempers are usually selected among available materials near the site of pottery
production, they may allow us to identify geographical areas of ceramic manufacture, possibly
even giving evidence of economic strategies, agricultural practices, and resource exploitation.
Finally, as ceramic "ingredients" are linked to the natural environment from which
they came and maintain its traces, the interpretation of these traces can add considerably
to our understanding of the relationship between humans and their environment in the
historical past.

ACKNOWLEDGMENTS

The authors wish to express their gratitude to Pro£ A. Avanzini (University of Pisa), the
Archaeologists of IMTO (Italian Mission To Oman), and the Adviser for Cultural Affairs,
Sultanate of Oman, for the opportunity they all provided to study pottery recovered in
 ORGANIC INCLUSIONS 579

Sumhuram. TI1e authors are also grateful to Dr. Roberta Panzanelli for her critical reading,
comments, and improving of this text, and to Dr. Alice Hunt for the improvement of the
original English text.

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 PART VI

ASSESSING VESSEL
FUNCTION
 CHAPTER 32

FORMAL TYPOLOGY OF
IBERIAN CERAMIC VESSELS
BY MORPHOMETRIC
ANALYSIS

ANA LUISA MARTINEZ-CARRILLO AND

JUAN ANTONIO BARCELO

INTRODUCTION

PoTTERY sherds are one of the most well-documented materials in archaeological investi-
gations, often providing critical information that contributes to the reconstruction of the
historical sequence of a site and/or culture (Orton et al., 1993). The study and analysis of
ceramics constitutes one of the most common and important archaeological activities, the
first step of which consists of classifying thousands of excavated ceramic fragments and
selecting for further analysis those that contribute to the elucidation of form, function, and
chronology.
The study of archaeological ceramics means giving continuity to an archaeological
research that has tried diverse classification approaches since the origins of the discipline,
none of which can be considered valid.
The different criteria used in the elaboration of typologies do not contribute to homog-
enize the analysis of the pottery shapes, since the election of criteria depends on each
researcher. The most used criteria have been the morphometries, functional, statistical,
technological, and contextual. Taking this division into account, the criterion used in this
research is morphometries because, within this scope, methods and techniques of analysis
coming from graphical computer science can be applied and can be useful for classifying
pottery shapes according to degrees of similarity.
In this chapter a formal typology oflberian vessels is exposed. The method to characterize
and classify wheel-made pottery by its profile using mathematical morphology is explained.
The proposed method is also a decision support system because it can suggest to the archae-
ologist the classes that vessels might more likely belong to.
)86 ANAL. MARTiNEZ-CARRILLO AND JUAN ANTONIO BARCEL6

The present chapter has been structured as follows: definition and evolution of the con-
cept of type in the classification of ceramics, description of the area of study and the analyzed
data, an explanation of the methodology of analysis, the results that are obtained, and finally
conclusions.
li
%

CLASSIFICATION IN ARCHAEOLOGY AND li

!i
THE CoNcEPT oF TYPE II
I'
'The increasing number of excavations since the nineteenth century and the need to establish
typologies related to stratigraphical chronologies helped to establish descriptions, typologi-
cal sequences, and the determination of fossil guides.
I
i
~~

The multiplicity and diversity of criteria regarding ceramic classification have produced,
since the second half of the twentieth century, much typological discussion by authors such
as Adams or Orton (Adams, 1988: 44-42; Orton eta!., 1993: 21-26).
Generally the objectives of a classification are the arrangement and cataloging of mate-
rial, the relative dating of archaeological contexts, and the establishment of parallelisms with
materials documented in other zones. The accomplishment of a typology is an empirical
practice) oriented to facilitate the interpretation but isolated and without theoretical exposi-
tions with which to sustain itself.
The trouble is that such a discussion has been handicapped by some misunderstandings
regarding the meaning of the words typology, classification, clustering, and similarity.
Let us begin with the idea of similarity. As a quantitative property, similarity can be
defined as the operation of assigning numbers which represent the degree of identity or cor-
respondence or equivalence between pairs of entities, based on the perception of repeated
patterns.
Finding similarities depends on our ability to recognize patterns and distinguish one
object from another. Hence, the selection of variables, properties, and attributes used to
describe the material evidence of a social activity in the past is crucial.
Each defined variable and its attributes must be reasonably likely to have influenced con-
duct that occurred in the past, or the physical limitations of such conduct. We must remem-
ber that in many cases certain combinations of attributes are not culturally significant, and
represent stochastic regularities that result from the random selection of variables (Bell,
1994; Bisson, 2ooo).
Formally, the similarity between an object A and an object B is a function of the common
features to A and B, those that tend to A but not to B, and those that differentiate B from
A (Tversky, 1977).
Thus, we obtain a magnitude of similarity counting the number of common elements that
relate to non-common elements: the more elements that are shared and the fewer elements
that are unique to each of them, the higher the value of this ratio (similarity) will be. Thus,
the intensity of the similarity depends not only on what is common to both, but also what
is unique to each.
The statistical significance of this similarity is based on finding if two or more attributes
that appear together in a single definition of identity do not match randomly. Once this
 TYPOLOGY OF IBERIAN CERAMIC VESSELS BY MORPHOMETR1C ANALYSIS 587

similarity index has been calculated, a "metric space similarity" for the properties or fea~
tures can be built, appearing as vectors of metric coordinates, and the similarity is expressed
in terms of the distance between the entities that make up the space: the closer, the more
similar they are. Thus, objects with short distances between them are more alike than
those with longer distances, and are therefore grouped within the same cluster. It follows that
the similarity is a reflexive relation, because all share their own characteristics. Second, the
similarity is a symmetric relation, because if x shares properties withy, then y will share the
same properties with x. Finally, the triangle inequality states that the strength of the similar-
ity between two objects A and C cannot be greater than the sum of the similarities of each
with an object B.
Sometimes we may begin to think that similarity is less a result of the proportion of com-
mon elements in two objects than a function of certain properties or the preeminence of
visual features. In that case, the importance and contribution of each property, charac-
teristic, or attribute can be specified by giving "weights" that are specific to each feature
(Tversky, 1977).
Clustering is the process of grouping input samples in similarity classes that partition the
input space, so that diversity may be explicitly recognized and encoded. The starting point is
the formal description of each object as an ordered set of features. "Similar" objects are those
that have nearly the same values for different features. Thus, one would like to group samples
to minimize intracluster distances while maximizing intercluster distances, subject to the
constraints on the number of clusters that can be formed.
Classification is a form of categorization where the task is to take the descriptive attri-
butes of an observation (or set of observations), and from this to label or identify the
observation within a different phenomenological domain. The descriptive attributes may
themselves be drawn from different data domains, each domain effectively contributing
an axis to a combined feature space of all possible object descriptions. Hence, the task of
the classifier is somehow to partition this feature space into disconnected regions, each of
which represents a particular class, cluster, or pattern. The goal in a classification problem is
to develop an algorithm which will assign any artifact, represented by a vector x, to one of c
classes (functional assignments). The problem is to find the best mapping from the input
patterns (descriptive features) to the desired response (classes). Some finite or infinite set of
patterns (binary or real value vectors) are partitioned into classes, and a particular problem
is specified by a set of selected training patterns, which are given together with their corre-
sponding class names. The goal is to classify all patterns as correctly as possible. The problem
is dividing the set of possible input vectors into two sets, one for which the output is positive,
and the other for which the output is negative. The classes will be said to be linearly separable
when the separation of different input-output patterns is better than if no decision rule was
used. In the other case, when it seems there is no clear decision rule to separate examples
from counter-examples, we say that classes are not separable.
Archaeologists have been confounding clustering with typology. In fact, typologies are
classifications that are a deductive logical construction. Typological tasks are a kind of super-
vised learning problem, on the grounds that the known instances of a cause-effect relation~
ship are like information given by a teacher or supervisor. In this way, we learn to classify
visual and non-visual data as members of contrasting explanatory categories through trial
and error with corrective feedback (the teacher). We can formalize this inferential task in
terms of a kind of"automated learning:'
588 ANAL. MARTiNEZ-CARRILLO AND JUAN ANTONIO BARCEL6

Given: a descriptive language (LE) for known occurrences or examples; a language for
possible hypotheses (LH) (i.e. potential learning results); a set of positive examples (occur-
rences of a certain concept in the population); a set of negative examples (occurrences that
do not belong to the concept); a predicate "cover;' which indicates whether a given concept/
l
hypothesis covers/describes a given occurrence; an acceptance criterion (measure) which
evaluates hypotheses;
Find: a hypothesis in LH fulfilling the acceptance criterion. The partial order ofLH can be
used to prune the search.
Concept learning problems have the same form, except that target outputs are either "yes"
or "no"(or "true"=I and "false"=o). Inputs that map onto "yes" are treated as positive exam-
ples of a particular concept. Inputs that map onto "no" are treated as negative examples (i.e.
counter-examples). The process of finding a solution to such a problem is naturally viewed as
the process of calculating the communalities among positive examples. As such, it is a varia-
tion of the philosophical theories that see induction as a process involving the exploitation
of similarity.
Differences from the classical statistical or clustering approach are obvious. In a clustering
approach, a set of groups (and not "types") will be modeled by first describing a set of proto-
types, then describing the objects using these prototypical descriptions. In such an unsuper-
vised or self-organized task, the goal is to identify clusters of patterns that are similar, thus
identifying potential generalizations.
Archaeological explanation is then based on the assumption there is a structure to the
input space, such that certain patterns occur more often than others, and therefore these
explainations look for patterns that generally occur and those that do not. The trouble is that
with clustering approaches we are not discovering how to instantiate a specific meaning on
the basis of some perceptual information. Whereas "typology" involves learning some map-
ping between observed values of shape, texture, and/or composition, and their hypothesized
meanings, much simple clustering can be viewed as learning a mapping between observa-
tions and themselves. It is important to understand the difference between clustering and
classification, and between learning and partitioning or clustering. A good functional clas-
sification should impose structure and also reveal the structure already present within the
data. The outcome from a clustering of a set of archaeological objects may have little mean-
ing, since the resulting clusters are not associated (by design) with any functional assign-
ment arising from the domain of study (although they may be as a consequence of inherent
structure in the data).
The first explicit application of these approaches in archaeology was undertaken by David
Clarke (1968) and Doran and Hodson (1975), who developed a polythetic concept of archae-
ological culture that allows for more reliable limits to be observed in physical traits of mate-
rial culture. If for most archaeologists a recurring feature was enough to establish an ethnic
or cultural distinctiveness, Clarke demanded a more rigorous definition based on statistical
calculation of the similarity between archaeological populations (sites, territories) from a
majority of observable features, where there were none more important than others. All con-
tributed to the rigorous calculation of similarity.
The curve of the similarity function of each object type could note possible limits of a cul-
tural area. This rule allowed Clarke to differentiate mltural similarities and exchange effects
(Clarke, 1968). For this author, the important aspect was the complex set of recurrent groups,
 TYPOLOGY OF IBERIAN CERAMIC VESSELS BY MORPHOMETRIC ANALYSIS 589

without clear boundaries overlapping cultural features, as a measure of central tendency

(mean or mode), with no distinct boundaries or cultural groups enclosed.
Therefore, in the establishment of a typology it is necessary to define clearly the concept of
type, since its meaning varies in space and in time. Every type has to show two basic proper-
ties: identity and meaning. In addition, a type is defined in relation to a specific classification
that partially indicates the rules by which it is formulated. Furthermore, a typology is a sys-
tem and not only a collection of types, so it must be coherent as a system.

FROM VISUAL DATA TO TYPES

Fundamental to a type-variety method of classification is the definition of a type by a pattern

of modes (Gifford, 1960). In other words, a type is a group of diagnostic sherds or vessels
sharing a set of similar recurring attributes among many other variant attributes. The types
are derived from "discovered" patterns found during a comprehensive analysis of an entire
ceramic assemblage.
'!here are several approaches possible in order to construct a ceramic typology of a geo-
graphic region (Gifford, 1960; Dunnell, 1971; Whallon, 1982; Rice, 1987; Adams and Adams,
1991; Banning, 2ooo; Read, 2007 ). Most ceramic typologies tend to emphasize either ware
type or vessel shape. In the studied area (the upper valley of the Guadalquivir River), mor-
phologically based typologies have predominated (Pereira, 1989 ).
But what is "shape''? Attempts at formally defining the term are often based on the idea
of a "single;' "distinct;' "whole;' or "united" visual entity. In other words, it is the structure
of a localized field constructed "around" an object (Koenderink, 1990; Small, 1996; Costa
and Cesar, 2001; Leymarie, 2011). Therefore, the shape of an object located in a space could
be expressed in terms of the geometrical description of the part of that space occupied by
the object, as determined by its external boundary-abstracting from location and orienta-
tion in space, size, and other properties such as color, content, and material composition
(Rovetto, 2011). Consequently, the idea of shape should be understood as a process by which
our mind "builds" a definition of some observable input (Barcelo, 2010; Leymarie, 2011).
Within this paradigm, the shape of things appears to be a physical representation of the con-
tent of information associated with each thing. The word "information'' itself comes from
the Latin "in forma;· meaning "in shape;' and implies that "information" is what you need to
know in order to put things into a proper shape (Gammaitoni, 2011).
To characterize completely the shape of an object means to be able to recreate the whole
geometry of the same object, using only the measurements made over its interfacial bound-
aries. However, even though in some cases a set of measurements may satisfy archival propH
erties, it may as well fall into a redundant set of measures (Read, 2007).
The fundamental building block for a proper representation of archaeological shapes lies
in the identification of attributes. Dunnell (1971: 49) defines an attribute as a "unique and
non recurrent quality of a specific instance in the phenomenological field:' In other words,
an attribute is the smallest measurable value of a particular feature of an object. In a classifi-
cation, specific attributes are selected to address the particular problem of the classification
and become the defining features of a class. In a grouping, it is the goal of the researcher to
590 ANAL. MARTiNEZ~CARRILLO AND JUAN ANTONIO BARCEL6

identify the significant attributes that cluster around an average. A group will contain an
l
I
aggregate of these attributes that share a measurable similarity in occurrence (i.e. a pattern).
Unfortunately, there is no universal method for searching for informative visual marks.
TI1ey can be extracted from any archaeological record almost ad infinitum, but one usually
fails to formalize the significant criterion for what is intrinsically "visual:' An additional dif-
ficulty is that different visual features will almost definitely be of importance for different
explanations (Shelley, 1996).
To cope with this problem, archaeologists have traditionally assumed that there is a
roughly fixed set or vocabulary of"supposed" descriptive visual regularities shared by a sin-
gle population of objects, which are also distinctive enough. This way of identification-based
explanation seems a tricky way of solving any archaeological research problem.
The approach adopted here is to follow current computational theories of visual percep-
tion to ameliorate the analysis and explanation of visual marks. Computer vision has been
defined as a process of recognizing elements of interest in an image, and it can be described
as the automatic logical deduction of structures or properties of the three-dimensional
objects from either a single image or multiple images and the recognition of objects with the
help of these properties (Kulkarni, 2001).
Traditionally, archaeologists have referred to diameters and heights when speaking about
shape, forgetting important parameters such as surface area or volume. The conventional
method for capturing artifact morphology has been to take linear measurements with cali-
pers at fixed loci along an arbitrary line of maximum bilateral symmetry, generally defined
as length (DeBoer, 1980; Pobe!ome eta!., 1997; Mara and Sablatnig, 2005; Steine, 2005; Lycett
eta!., 2006; Rush meier eta!., 2007).
Such linear measurements, however, are absolute quantities reflecting only size. No geo-
metric information is provided on the relative position of the various breadth and thick-
ness measurements. Consequently, the variables sampled constitute an abstract collection
of relative size measurements, approximating the artifact's morphology (see discussion in
Crompton, 1995; Meltzer and Cooper, zoo6).
Much more efficient fOr shape encoding are descriptions based on relational indexes
(Russ, 2006). There are many other relational indexes specific to particular categories of
archaeological evidence. In the case of pottery, the work by Ericson, Read, and Burke (1972)
pioneered such approaches, introducing measures based on the calculation of the center of
gravity in order to study the relationship between shape and equilibrium, associated with the
assumed function of a pottery vase as container. To locate the center of gravity, Bishop et al.
(2005) suggest looking for the intersection of the length of the major and minor axis of the
ellipse with the same normalized second central moments as that part of the object-that is,
the vessel's mouth, its body, or its base.
Measuring the degree of symmetry is another shape parameter that has relevance for
studying the form-function relationship of an archaeological artifact. A very simple
approach would be to divide width measurements into a left and right measurement, and
measure them along the major axis of the object divided into ten or more segments. '!he
idea is to consider changes in the object's width at equally spaced intervals down its length.
When displayed as a histogram, changes of width of the point appear as bars above (expan-
sion) and below (contraction) a centerline. Families of similar points should produce
repeated and recognizable patterns in the change in width with respect to length in the case
 TYPOLOGY OF IBERIAN CERAMIC VESSELS BY MORPHOMETRIC ANALYSIS 591

of pottery objects (Wilcock and Shennan, 1975; Richards, 1987). In such a way, the degree of
curvature-a shape parameter-of the outline can be estimated.
Polynomial expressions (or their equivalents, Bezier curves/B-splines) provide a math-
ematical expression for the representation and interpretation of the geometry of the outline
of an object. Polynomial interpolation has a long history in archaeology, especially in the
case of pottery studies. Hall and Laflin (1984) used a system based on B-splines for convert-
ing digitized silhouettes of ceramic vessels into one or more mathematical curves (Smith,
1985; Kampe! and Sablatnig, 2003; Gilboa et al. 2004; Mom, 2005, 2006; Saragusti et al. 2005;
Nautiyal et al., 2006; Karasik 2008; Maaten et al., 2009 ).

A CASE-STUDY: SPATIAL-TEMPORAL CONTEXT

OF THE DOCUMENTED POTTERY AND THE
METHODOLOGY OF DIGITIZATION

The selected ceramic material for this morphometric analysis comes from different archaeo-
logical settlements located in the provinces from jaen, Granada, and Cordoba, and they per-
tain to the Iberian period. The combination of different archaeological sites with different
chronologies makes the accomplishment of a diachronic and synchronous study possible,
allowing the contrast of materials from different archaeological sites with different chronol-
ogies. The sample for the analysis has been made of 1,133 complete forms whose chronology
goes from the seventh century nc to the second century AD, belonging to 16 different archae-
ological sites in the area of Andalusia (see Table 32.1 and Figure 32.1).
This area has been well documented, with many excavated sites and research projects
(Ruiz et al., 1983, 1984; Chapa et al., 1997), which have published their results in printed
reports and specialized reviews.
The Iberian period has become a subject of intense ceramic typological debate with regard
to the relationship of certain vessel types to subperiods and their association with ethnic
groups. The main research that is oriented to produce a morphological typology of Iberian
vessels in this area has been carried out by Pereira (1989).
Since the early 1900s, print has been the primary medium for dissemination of archaeo-
logical excavation data. The backbone of all comparative theories, models, reconstructions

Table 32.1 Vessels in the study

by context
Context W Vessels

Cemetery 982
Settlement 121
Sanctuary 30
TOTAL 1133
592 ANAL. MARTfNEZ-·CARRILLO AND JUAN ANTONIO BARCEL6

100 200 300

Kilo meter~

FIGURE 32.1 Mapofthestudyarea.

of archaeology, and history still remains the published material contained within books and
journals. Traditional publication makes it extremely difficult for the reader/user to analyze
artifacts in any technical manner. Although there has been increasing interest in the digiti-
zation of the archaeological record to help circumvent this limitation, methods for making
these critical databases easily available to fellow researchers and the public are still in their
infancy.
Researchers' ability to analyze their own data against comparative data from other exca-
vations has been a consistent obstacle to testing their theories critically and for developing
comprehensive interpretative models. What is critically needed during the current period
of advancing computer technology is digital tools and methods that are able to query large
archaeological datasets in ways that conventional print data cannot (Smith eta!., 2012).
The documentation and traditional reconstruction of archaeological ceramics are based
on the profile of the vessel; that is, the section of the fragment that contains the rotation axis.
The analyzed ceramics are wheel made and therefore symmetricaL The extraction of the pro-
file is fundamental to be able to establish a classification according to the form.
The test material comes from publications. First the drawings have been digitized, in
order to match the graphical documentation. The process of digitization of the images of the
ceramic drawings can be divided into the following steps:

Digitization of the drawings of publications.

Vectorization of the contours.
Separation of the profiles for later computer processing.
Export of the drawings of the profiles to a raster format without compression; in this
case the test has been realized with PNG file formats.
 TYPOLOGY OF IBERIAN CERAMIC VESSELS BY MORPHOMETRIC ANALYSIS 593

CRITERIA OF THE MORPHOLOGICAL ANALYSIS

Once the ceramic material has been digitized, a preliminary classification of all the
complete shapes is made. The selected criteria for the description of the ceramic shapes
are both descriptive and metric, such as the presence/absence of each of the compo-
nents which form a pottery vessel (rim, neck, and body), their proportion, and the shape
of the body. In total five basic forms (globular, ovoid, conic bi-frustrum, cylindrical,
and lengthened shapes) were identified to describe the ceramic bodies in this study
geometrically.
Following this preliminary classification, eleven groups (representative profiles are shown
in Figure 32.2) were defined:

1. Shapes in which the body predominates over the other parts of the vessel. The shape
of the body is oval.
2. Shapes in which the body has a conic bi-frustum form. Contact between the different
body parts is discontinuous.
3. Shapes with developed, parallel walls, neck and globular body.
4. Shapes with developed, divergent walls neck and globular body. This shape is also
named chardon vessel.
5. Shapes with cylindrical body. Also known as kalathos.
6. Lengthened shapes.
7. Shapes with profile in the form of an S.
8. Shapes with globular body. Contact between the different body parts is continuous.
9. Shapes with globular body and a largely developed rim.
10. Shapes with semi-spherical body.
11. Shapes with semi-spherical body and reversed rim.

2 3 4 5 6

7 8 9 10 11

FIGURE 32.2 Profiles of the eleven classes of vessels determined by preliminary descriptive
analysis.
594 ANAL. MARTi NEZ-CARRILLO AND JUAN ANTONIO BARCEL6

THE COMPARISON APPROACH: THE MATHEMATICAL

lI
"'
MORPHOLOGY

Once the formal classification has been made, the morphological criteria are codified in
order to be later recovered and compared, providing a tool to help the archaeologist find the
most similar classes to a given shape in a profile database, thus facilitating the classification
of newly found materiaL In this chapter the method will be applied at the level of Group.

Morphological Filtering
Mathematical morphology (Matheron, 1975) is based in set theory, and provides a powerful
approach to numerous image-processing problems (Haralick et aL, 1987). A morphological
description of a binary image is the set of two-dimensional vectors representing the coordi-
nates of all the foreground pixels (black in this case). One shape within an image can be repre-
sented as a random setA, where the probability that a point x belongs to the A is p ~ P(x e A).
Given a set of points W representing the entire image, the above probability can be
approximated by:

_ area(An W)
p ~ --'--c:-::c-'- Equation 32.1
area(W)

Furthermore, e.,, d-r, or, and cTare defined as the associated probabilities (Equation 33.1)
to the erosion, dilation, opening, and closing respectively of the point set A by struc-
tural element T. It can be clearly stated that ey :5odr :5o or :<; c-r. Varying the size ofT, four
curves are obtained from a given shape A (Figure 32.3). These curves are monotonic
with respect to the size of T, and represent the surface ratio variation between the area
covered by the initial shape and the result of each morphological operation with differ-
ent sizes ofT.
1be defined curves, computed with different structural elements, are used to obtain a
characteristic vector for each profile in the database, starting from a binary image represent-
ing the shape of the corresponding vesseL Similarity between two profiles will be computed
as the Euclidean distance between the associated vectors. The process is described in the fol-
lowing sections.

Profile Classification
In order to assign the most similar class to a given profile, a preprocessing stage where we
split the profile into several parts is applied and characterized by means of a vector obtained
by sampling the morphological curves.
Morphological curves allow a characterization of a given shape, but as global methods
they sometimes fail to incorporate spatial information. In order to mitigate this, the profiles
 TYPOLOGY OF IBERIAN CERAMIC VESSELS BY MORPHOMETRIC ANALYSIS 595

Dilation
Closing
--Opening
---- - Erosion
---~----------­
2
/~-----~"~--""""

Fs-~·
0~~~~~~~~~
0 10 20 30 40 50 60 70 80 90
Radius
FIGURE 32.3 Erosion, dilation, opening, and closing characteristic curves of a profile of
the database, using an isotropic (circular) structural element, normalized by the area of the
profile.

Body

FIGURE 32.4 Segmentation of a profile into rim, body, and base.

have been split into several parts and the characteristic curves have been computed from
each of them. Given a profile, dis defined as the length of the line segment joining the upper
point of the profile rim u with the lowest point of the base v (Figure 32.4). Furthermore,
pis denoted as the lowest profile point located at the rotation axis. Three subprofiles are then
defined:

Rim. Points whose distance to u is lower than d/3.

Base. Points whose distance top is lower than the distance between v and p.
Body. The rest of the points.
596 ANAL. MARTfNEZ-CARHILLO AND JUAN ANTONIO BARCEL6

Serialization and Classification

Starting from a given profile p, several suggestions (or possibly just one) about the class in
which the profile best fits are provided to the user. This will allow the building of a decision
support system for the archaeologist.
Given a profile p, a serialization of a profile database of k elements is a set:

Equation 32.2

D={(a,,c,), (a,,c,)},

where c1 the class of the i-th database profile, and d1 his Euclidean distance top. This set is
increasingly ordered by distance values, namely d1 :<; dj fori < j.
The classification process is defined to give to the user n possible classes (suggestions)
for p, using the m most similar profiles (neighbors) in the database. Experiments with
different values for n and m are carried out. The algorithm to obtain a set S of n sug-
gestions using m neighbors from the set D of serialized elements in the database is the
following:

1. s" 0
2. D={(d,,c,), ...(d,,c,)},J, :<;d/<fi<j
3. While lSI< n, repeat.

RESULTS

The results obtained are shown with one, three, and five suggestions, with respectively one,
three, and five neighbors in the classification stage (Table 32.2).
Tables 32.3 and 32-4 show normalized confusion matrices, with one suggestion and one
neighbor with two different subprofile combinations: rim with body + base, and rim with
body. Each row contains all the profiles of a single class, while each column contains all the
profiles that the method assigns to the corresponding class.
Although the results are numerically very similar, in percentage terms the results using
body+ base subprofiles (Table 32.3) are slightly better. However, the method using only the
body subprofile presents fewer computational requirements, as the starting shapes contain
fewer foreground pixels.
We can note also that the proposed method classifies wrongly many class 2 (biconical
trunk) and class 9 (globular with large rim) profiles as class 8 (globular), but not conversely.
This is possibly because of the small size of classes 2 (forty-seven samples) and 9 (twenty-two
samples) versus class 8 (293 samples), together with the fact that these three classes are mor-
phologicallyvery similar.
In all of our experiments, similarity between two profiles has been computed as the
Euclidean distance between their associated vectors. Firstly, we show the first ten nearest
 TYPO!.O(;y OF IBERiAN CERAMIC VESSELS BY MORPHOMETRIC ANALYSIS 597

neighbors of some sample profiles, along with the measured similarity for each one (Figure
32 .5). As can be seen, the recovered profiles correspond with the typologies defined by
experts in the percentages shown in Tables 32.3 and 32-4.

Table 32.2 Classification rates obtained by the

method with one, three, and five
suggestions and one, three, and five
neighbors
Suggestions Neighbors · rim-body+base rim-body
86,14% 87,70%
3 84,73% 84,20%

5 85,17% 84,47%

3 97,97% 97,71%
3 97,35% 97,71%

5 97,00% 97,74%

5 99,21% 99,210/o
3 99,12% 99,38%

5 99, 120/o 99,210/o

Table 32.3 Normalized confusion matrix resulting from the application

of the method to the database, using two subprofiles: rim and
the combination of body with base
Rim-Body+Base
-----
1 93.33 0 0 0 0 0 0 6.67 0 0 0
2 0 34.04 2.13 0 0 0 4.26 59.57 0 0 0
3 0 1.33 74.67 4.00 1.33 1.33 2.67 13.33 1.33 0 0
4 0 0 0 70.00 0 10.00 10.00 10.00 0 0 0
5 0 0 0 0 96.43 1.79 0 1.79 0 0 0
6 0 0 1.92 0 3.85 80.77 0 13.46 0 0 0
7 0 2 2.00 0 0 0 84.00 2.00 4.00 6.00 0
8 0 4.78 2.39 0 0 1.02 0.34 9010 1.02 0.34 0
9 0 0 0 0 0 9.09 0 45.45 40.91 4.55 0
10 0 0.27 0 0 0 0 0 0.27 0.27 95.98 3.22
11 0 0 0 0 0 0 0 0 0.80 19.20 80.00
2 3 4 5 6 7 8 9 10 11
 598 ANAL. MAHTiNEZ-CARRILLO AND JUAN ANTONIO BARCEL6
-..-~-· ···-- -~-------~--~-
1
Table 32.4 Normalized confusion matrix resulting from the application of the I
method to the database, using the rim and body subprofiles.
Rim- Body
-~---~,.---·-----~----~----------

1 83.33 0 0 0 0 3.33 0 13.33 0 0 0

2 0 42.55 0 0 0 0 4.26 53.19 0 0 0
3 0 2.67 72.00 4.00 0 1.33 2.67 16.00 0 0 0
4 0 0 0 80.00 0 0 10.00 10.00 0 0 0
5 0 0 0 0 100.00 0 0 0 0 0 0
6 0 0 1.92 0 3.85 78.85 0 13.46 1.92 0 0
7 0 0 0 0 0 2.00 86.00 4.00 2.00 6.00 0
8 1.37 3.41 2.39 0 0 1.37 0.34 89.42 1.37 0.35 0
9 0 0 0 0 0 9.09 0 40.91 45.45 4.55 0
10 0 0.54 0.27 0 0 0 0 0 0.27 94.37 4.29
11 0 0 0 0 0 0 0 0 0.80 19.20 80.00
2 3 4 5 6 7 8 9 10 11

7,79 8,98 9,96 10,36 10,59

0.. .

11,38 11,61 11,64 11,66 11,77

FIGURE 32.5 A given ceramic (first row) and the ten most similar shapes, with the measure
of the distance (second and third rows).
 TYPOLOGY OF IBERiAN CRRAMIC VESSELS BY MORPHOMETRIC ANALYSIS 599

CoNCLUSIONs

A new method is proposed to classify vessel profiles, based on well-known mathematical

operators that capture most of their morphological features, allowing the identification of
the most similar profiles in a database, and to provide the archaeologist with a range of sug-
gestions in order to classify newly found vessels. Through this methodology for measuring
the similarity between ceramic profiles it is possible to search for parallels in a particular
region, in this case the upper valley of the Guadalquivir River (Spain). In addition, it is pos-
sible to assign a chronology to a new vessel and to investigate if there is a morphological
evolution of pottery shapes over a certain time, which in our case includes the Iberian period
(sixth century Be-first century AD).
A binary image of the profile shape has been used, without the need of further processing,
such as subpixel contour estimation. The vector characterization captures the morphologi~
cal features of the profiles.
It would be interesting in future to apply our comparison method to obtain an automatic
clustering of the database, and compare the resulting classes to tbose defined by the experts.
The proposed technique can also be used with other similar database profiles, in order to
better test its robustness and applicability.
Finally, other shape and contour comparison methods, which have shown good results
in similar pattern recognition related problems, can be adapted to our decision support
scheme, improving the quality of the suggestions.

ACKNOWLEDGMENTS

This work has been supported by the Excellent Projects Program of CICE (regional gov-
ernment), the European Union ERDF funds under research project Po7-TIC-o2773, the
Computer Graphics and Geomatics Research Group (TIC-144) of the University ofJaen, and
the Andalusian Economics, Innovation, Science and Employment Council under project
TIC-7278.

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 CHAPTER 33
.........................................................................................................

MECHANICAL AND THERMAL

PROPERTIES

NOEMI s. MULLER

INTRODUCTION

PoTTERY products have been used in many different activities in the past-from the trans-
portation and storage of goods, to the thermal treatment of materials (whether connected to
food preparation or pyrotechnical processes), and the construction of buildings and installa-
tions. The popularity of ceramics for those applications is not only because of the widespread
availability of raw materials and the plasticity of the clay paste, which facilitates manufacture
of virtually any shape, but also the physical characteristics of the finished products. Ceramic
vessels are chemically inert, can be exposed to heat, and are durable. Unlike stone or wood,
however, ceramics are a synthetic, man-made material. 1he physical properties of ceramics
are different from those of their raw materials, which undergo a series of transformations dur-
ing the manufacture process. The selection and the preparation ofraw materials (Chapter 7 in
this volume) affects the finished ceramic's material properties, and different steps in manufac-
ture (e.g. refining of the raw clay, clay mixing, addition of temper, firing regime) potentially
influence and alter the physical properties of the finished product. It is for this reason that
a main concern of the study of mechanical and thermal properties is the assessment of the
influence of manufacture on the physical properties of archaeological ceramics.
Nearly sixty years ago, Anna Shephard noted that "all physical properties are influenced in
some measure by both composition of material and technique of manufacture" (Shephard,
1956: 137), and that in particular the "resistance to breakage offers a practicable means of
judging the serviceability of a vessel, and strength is a significant property that would be
useful in comparative studies if it could be measured satisfactorily" (Shephard, 1956: 130 ). In
the same volume, she presented results from both measurements of experimental briquettes
and bars cut from archaeological sherds. It is, however, only in the 1980s that the subject
began to receive more widespread attention, as a result of the work of a group of primarily
North American researchers. Braun (1983) emphasized that pots are also tools-implements
made to be used for certain activities-and, thus, that their morphology and composition
are constrained by their intended contexts and conditions of use. Ceramic performance was
defined as the ability to withstand physical stresses introduced during use without failure,
-
604 NOEMI S. MULLER

as well as their suitability to be used for processes such as storing, transporting, heating,
lI
or cooling. Since potters would employ particular techniques to achieve "characteristics of
utility;' he argued that the study of the relevant attributes would provide the archaeologist
with the means of explaining technical variation rather than just describing it Subsequently,
Bronitsky (1986) provided not only an extensive overview of testing procedures for a variety
of physical properties which he deemed relevant to the use of the finished vessel and to assess
the contribution of different materials and techniques to vessel durability, but he also sum-
marized archaeological applications that had been conducted up to that date. More recently,
Tite et al. (2001) outlined both the underlying principles governing the response of ceramic
materials to mechanical and thermal stresses, and reviewed published experimental data on
the role of tempering and firing for the physical properties of ceramic materials.
In some of the earlier research, there is a propensity to consider the measurement of phys-
ical properties and material performance as a means of assessing the "fitness of techniques"
and "expertise of potters;' and documenting progressive technological development towards
ideal paste recipes. Accordingly, in these studies, the interpretation of ceramic technologies
tended to be limited to functional or material explanations. However, the factors affecting
potters' choices are many and varied, and studies emphasizing adaptation and development
towards an "ideal"' ceramic recipe cannot easily explain discontinuities in pottery produc-
tion when fabrics have their origin in the technological practices of different human groups
(Kilikoglou et al., 1998: epilogue). Sillar and Tite (zooo) further emphasized that pottery
technology is firmly embedded within wider environmental, economic, social, political, and
ideological contexts and practices, and that it would be impossible to account for any tech-
nological choice without combining consideration of both material properties and overall
context in which these choices were made. In this sense, rather than explaining techno-
logical choice, the study of physical properties provides a baseline against which the role of
cultural and other factors can be considered, and ultimately aids appreciation of the complex
dynamics behind the potters' technological choices.

Influence of potters' choices (e.g. tempering, clay selection, firing) on material performance:
Ceramic manufacture influences the composition, microstructure, and texture of archaeological
ceramics, and these in turn influence mechanical and thermal properties and thus a ceramic's
affordance to be employed in different activities.

MATERIAL PROPERTY STUDIES

FOR ARCHAEOLOGICAL CERAMICS

Questions related to the mechanical and thermal affordances of archaeological ceram-

ics usually arise from a detailed study of a particular ceramic assemblage, and frequently
include inquiries about whether or not observed changes and variations in manufactur-
ing practices are related to their mechanical and thermal properties, and whether or not
differentiation observed in manufacture for specific ceramic products, used in particu-
lar activities, may be related to different functional requirements. Pottery types that have
been examined include mainly transport vessels and cooking pots, but also metallurgical
 MECHANICAL AND THERMAL PROPERTIES 605

ceramics and pyrotechnical installations, as well as ceramics used in construction. It must be

emphasized that there is not much meaning in assessing mechanical and thermal properties
of archaeological ceramics outside a firm archaeological framework and without particular
archaeological questions. The destructive nature of the measurements and the potentially
significant investment in term of effort in order to manufacture adequate experimental bri-
quettes should further advise against testing just for testing's sake.
When testing the mechanical and thermal properties of archaeological ceramics, two dif-
ferent avenues of inquiry are open to the analyst. Physical properties can be tested directly
using the archaeological material, or parameters of interest can be studied through systemat-
ical testing of experimental briquettes. Material testing is normally destructive and requires
multiple samples with a defined geometry. Moreover, archaeological ceramics have fre-
quently undergone alteration during use and burial, which potentially alter their mechanical
and thermal properties. For these reasons, testing of archaeological material proves, in many
cases, problematic. Therefore, the systematic testing of experimental briquettes is usually
preferred. However, in order to retrieve information and arrive at conclusions relevant for
the archaeological ceramics of interest, the latter approach necessitates a thorough under-
standing of the archaeological ceramic fabrics, in terms of their composition, texture, and
microstructure. On the other hand, studies conducted on experimental briquettes facilitate
the elaboration of trends observed in manufacture and contribute to a deeper understanding
of the ceramic materials, relevant beyond particular case studies.
The selection of relevant parameters (tempering, firing) for briquette manufacture must
be based on the archaeological ceramics studied, which should be carefully analyzed prior
to briquette formation. Owing to their influence of texture and microstructure on physical
properties, the nature, size, amount, and spatial arrangement of aplastic inclusions and pores
in the archaeological· samples and microstructure of the ceramic matrix are of particular
interest. Ceramic petrography (Chapter 15 this volume) lends itself, in particular, to the study
of these features, and can be combined or supplemented with examination of the ceramic
microstructure using scanning electron microscopy (Chapter 31 this volume). Moreover,
porosity, which is of paramount importance both for mechanical and thermal properties,
can be studied using mercury intrusion porosimetry or by image analysis methods.
The selection of material tests depends upon the type of ceramic studied. Many archae-
ological ceramic objects such as transport vessels, cooking pots, crucibles, tuyereres, and
water jars, but also ceramics used in construction, such as water pipes, roof tiles, or bricks,
require advanced mechanical or thermal properties. Since different uses create different
demands on a material and produce different types of mechanical and thermal stresses
which it needs to withstand, different physical properties are relevant for a ceramic depend-
ing on the activity it is used for. For example, thermal properties, such as thermal conduc-
tivity, are important for pyrotechnical ceramics, while resistance to mechanical stress is
essential for transport vessels (Table 33.1).
This chapter examines how technological choices during manufacture affect the physical
properties of archaeological ceramic materials. Beyond the particular material properties,
however, the shape of a vessel also influences its behavior. Using the material properties of
ceramics as a basic parameter, the influence of shape can be assessed, for example, by com~
puler modeling. These models can subsequently be assessed by manufacturing replica ves-
sels and using them in simulated experiments. In general, however, both approaches, that
is computer modeling and tests on replica vessels, require a thorough understanding of the
6o6 NOE.:vu s. MULLER

Table 33.1 Examples of material requirements placed on different ceramic

products; illustrating the variability of demands placed on different
types of ceramics (the list is by no means exhaustive)

Ceramic Requirements
product
Transport Good resistance to mechanical stresses, no leaks of fluid contents
vessel
Crucible Good resistance to thermal stresses (up to >1000°C). thermal conductivity (low for
internal heating, high for external application of heat)
Cooking Good resistance to thermal stresses (up to c.500°C), thermal conductivity (high for
vessel external application of heat. increasing heating effectiveness, but low beneficial for
retention of heat and slow simmering of foodstuffs)
Water jar Good resistance to mechanical stresses, open porosity (cooling effectiveness)
Bricks, roof Good resistance to mechanical stresses, low thermal conductivity (insulating
tiles properties). frost resistance

material's response to thermal and mechanical loads in order to provide meaningful results.
In some cases, researchers have set out to assess material properties directly on replica ves-
sels or have attempted to design "behaviorally relevant" testing methods (see Skibo, 2013,
for an overview). Indeed, experiments on replica vessels do provide important insights, and
it is crucial to be aware that differences which are measurable in a laboratory setup are not
necessarily perceived or indeed perceivable by the potters or consumers of the pots. Owing
to the complexity of relationships among potters' technological choices, material properties,
and the performance of a vessel when exposed to mechanical and thermal stresses, a thor-
ough understanding of the influence of technological parameters on the material's response
to defined thermal and mechanical loads is indispensable to fully appreciate the behavior of
replica vessels.

SUGGESTED METHODOLOGY FOR RESEARCH

INTO MECHANICAL AND THERMAL AFFORDANCE

As outlined above, it is not usually recommended to conduct tests on archaeological sam-

ples, and, if this is done, alterations to the material during use, discard, and burial which
might affect thermal and mechanical properties must be taken into account when interpret-
ing data. Moreover, if material testing is performed on archaeological samples, it should
always be accompanied by textural, compositional, and microstructural analysis of the
archaeological material, using petrographic analysis at the very least, in order to be aware of
potential reasons for differences observed in the measurements of physical properties. This
supplementary information not only allows for a more meaningful interpretation of results,
but potentially will also give rise to issues of interest for further inquiry.
 MECHANICAL AND THERMAL PROPERTIES 607

In general, however, mechanical and thermal properties are preferably assessed through
the systematic study of appropriate experimental briquettes. In the absence of published
studies relevant for the particular archaeological case study, this research strategy results in
an experimental program that can be divided into three tasks: (1) characterization of the
archaeological material; (2) manufacture of experimental briquettes and determination of
physical properties of these briquettes; and (3) interpretation of the data, in view of the par-
ticular archaeological case study.

(1) From Archaeology to Experiments:

Characterization of the Archaeological Material
and Design of Experimental Briquettes
Archaeological questions related to the affordance and suitability of utilitarian ceramics for
different activities typically arise from observed changes and variations in their manufac-
turing technology. If such patterns pertaining to provenance, raw material selection, and
manufacturing techniques are identified in an assemblage, the archaeological ceramics need
to be characterized and classified into compositional groups which relate to different pro-
duction technologies and raw material provenance. For relatively coarse utilitarian pottery,
determination of compositional groups is best accomplished using thin-section petrogra-
phy. The mineralogical and morphological identification of coarse, aplastic inclusions facili-
tates, in many cases, not only distinction oflocal and imported pottery but also a recognition
of changes in potting traditions over time. Furthermore, by uncovering shape and orienta-
tion of inclusions and pores, petrographic analysis reveals additional characteristics. While
they are in many cases not immediately relevant for tackling questions of provenance or raw
material selection, these are of paramount importance in view of the ultimate aim of such a
study; the assessment of the materials' physical properties and the archaeological ceramic's
affordances. Additionally, ceramic petrography can provide rough estimates for ancient fir-
ing temperatures and for vitrification stages.
It some cases it might be advisable to perform additional analyses on a subset of sam-
ples using complementary analytical techniques. For example X-ray diffraction techniques,
scanning electron microscopy, or Fourier transform infrared spectroscopy, potentially pro-
vide further information about the nature of raw materials, or on firing regimes, while Hg-
porosimetry or image analysis methods provide additional information on porosity. It must
be carefully considered, however, whether the potential supplementary information pro-
vided by these methods justifies additional effort, time, costs, and materiaL
It should be emphasized that for the assessment of material properties, it is not the exact
firing temperature that is important, but the microstructure and the degree of vitrification
in a ceramic's groundmass. 1bese features can usually be adequately assessed, by examining
the groundmass's optical activity in thin section, especially when results are corroborated
by examining selected samples under the scanning electron microscope. 1be identifica-
tion of particular clay minerals and high temperature phases-besides their use for firing
temperature estimations-generally appears not to contribute much to an assessment of
material properties. There are exceptions to this, however. High-temperature phases have
been postulated to be the underlying reason for technological choices in the manufacture
608 NOEMJ S. MULLER
1
of metallurgical ceramics (Martinon-Torres et al., 2oo6). Nevertheless, it would appear that
examining the archaeological material by thin-section petrography will, in a first instance,
1
deliver results which are sufficient for a subsequent assessment of the fabrics' affordance.
Once the variations and changes in ceramic fabric have been documented, the key param-
eters which may influence material properties (and ultimately vessel performance) can be
identified, in order to assess their impact on a ceramic's performance in relevant experimen-
tal briquettes. A general understanding of the basic principles of mechanical and thermal
properties is advisable when designing an experimental program, as it aids the singling out
of potentially critical parameters and thus determines the focus of the experimental part.

(2) Determination of the Influence of Manufacturing Parameters

on Material Properties: Tests on Experimental Briquettes
The influence of the manufacturing parameters of interest on the physical properties relevant
to the functional type under study can be assessed on experimental briquettes. This step is not
always required: in cases where the parameters of interest have been assessed previously on
relevant model materials, the results of those studies can be used as a basis for comparison.
It is important to manufacture the experimental briquettes under controlled conditions. In
particular, the grain size of the matrix material needs to be controlled and standardized. The
removal of aplastic inclusions, larger than 30 ~m, from the raw clay through sieving and levi-
galion, results in a material fine enough not to introduce undefined tempering effects. In any
case, both the composition and grain size of raw materials used, as well as forming methods
and firing regime employed, should be reported in detail. In order to facilitate meaningful
interpretation of the material tests on experimental briquettes, it is imperative to examine
the texture and microstructure of the tested ceramics. This includes determination of struc-
tural features which are recognizable with an optical or polarizing microscope, including the
size, amount, and orientation of pores, as well as those which become apparent only under
the electron microscope, mainly the vitrification of the ceramic groundmass.

(3) Data Interpretation and Evaluation

Based on their petrographic description, the affordances of ceramic materials can be
assessed. The outcome of the material tests on the experimental briquettes-alongside lit-
erature sources and potential computer modeling and tests on experimental vessels (see
Further Tests andExperiments)-provide the baseline against which variability and changes
in fabrics observed in an archaeological assemblage can be discussed. When doing so, it
seems advisable to exercise caution for various reasons. It should be considered, for example,
whether differences in material properties could potentially have been perceived by con-
sumers. It is also important to remember that the various mechanical and thermal material
properties are not independent properties; they all depend upon the composition, texture,
and microstructure of a ceramic. The addition of temper to a fine clay paste, for example,
increases the ability of a material to dissipate energy and results in an increase in tough-
ness, while simultaneously causing a decrease in strength, as the temper particles introduce
 MECHANICAL AND THERMAL PROPERTIES 609

flaws into the material. Thermal shock resistance, since it is dependent upon a material's
ability to withstand crack initiation and propagation, is linked tightly to strength and tough-
ness. Because of this, changes in manufacturing procedures must always be viewed bearing
in mind this complex interplay; carefully evaluating the effects of technological choices on
an array of potentially significant material properties. Furthermore, the performance of a
ceramic material during manufacture (e.g. shrinkage or workability) is important and can
be a decisive factor in the selection of particular materials or practices. Last, but by no means
least, the contexts of ceramic production and the multitude of other factors that influence
technological choice must be taken into account, to be able to make valid suggestions about
the underlying reasons and mechanisms when interpreting differences in manufacturing
techniques observed in an archaeological case study.

(4) Further Tests and Experiments

Once the material properties are defined, computer modeling can be used to assess, for
example, the influence of shape. Foregoing material tests are indispensable for computa-
tional analyses because they not only deliver the required material input, but also provide the
means to assess the impact of the calculated stresses on the objects studied (see Kilikoglou
and Vekinis, 2002). Computer modeling using, for example, finite element analysis provides
insights which cannot be obtained by material tests alone, and is thus a logical addition to the
investigation of the physical properties of the ceramic materiaL Computer models provide
insight into the performance of a ceramic object under stringently defined conditions and
facilitate systematic assessment of constraints (both shape factors and external constraints).
Finally, findings can be tested and validated in experiments on replica vessels.
For experiments on replica vessels a bottom-up approach is recommended. It is not only
important to distinguish between material properties, morphology of a vessel, and its per-
formance with respect to a specific activity, but a thorough understanding of the influence of
technological parameters on the physical properties of the ceramic material is prerequisite for
understanding vessel performance, and should forego experimentation on replica vessels. The
influence of vessel morphology and constraints (e.g. weight of vessel content, loading mode,
or temperature constraints), which introduces additional parameters, should be taken into
account once the relationships between manufacturing practices, microstructure, and physical
properties of the ceramic material have been disentangled. Only in this way can the macro-
scopic observations gained in experimental studies on vessel replicates be fully appreciated.

PRINCIPLES, TEST METHODS, AND THE INFLUENCE

OF CERAMIC MANUFACTURE ON MECHANICAL
AND THERMAL PROPERTIES

Strength, toughness, and thermal shock resistance are used most often in the archaeological
literature to assess the suitability of a ceramic to be used for particular activities (e.g. Tite
610 NO EMI s. YIDLI,ER

eta!., 2001). More recently thermal conductivity has received increased attention (e.g. Hein
et al., 2008, 2013). Fracture strength is a measure of the amount of stress a material can be
exposed to before cracks initiate. For ceramics which show unstable fracture the initiation of
a crack is usually equivalent to material failure, but in some ceramic materials a propagating
crack can be arrested. Therefore, assessing only the strength of a ceramic does not necessar-
ily provide information on when it will lose its structural integrity. Toughness is a measure of
the intrinsic fracture energy required for crack initiation, and of the energy that is absorbed
during crack propagation. If a material can absorb energy through mechanisms such as
deflection and arrest, cracks can be stopped before they lead to failure. Thermal shock resis-
tance describes the ability of a material to withstand rapid changes in temperature, and is
related to the ability of the material to resist both crack initiation and propagation. Thermal
conductivity, finally, is a measure of the heat transfer in a material under a particular tem-
perature gradient.
The following sections present principles and test methods for each of these properties
and provide a brief summary of factors that influence these characteristics in archaeological
ceramics. Besides strength and toughness, which are connected to the ability of the ceramic
material to resist mechanical stresses, a ceramic's ability to resist thermal stresses-focusing
on thermal shock resistance-and thermal conductivity are also discussed. All of these
properties are significant for many ceramic objects used in the past (see Table 33.1).

Strength
Fracture strength describes a material's ability to withstand an applied force without initi-
ating a crack For archaeological ceramics, it is usually tensile strength which is assessed.
Clay-based ceramics are much stronger under compression than in tension, so that if they
fracture they usually do so in tension, and-apart from ceramics used as building material-
compression is usually not considered relevant for archaeological pottery.
Mechanical stresses can be static or dynamic stresSes. Pottery is exposed to static
stresses, in other words stresses which remain constant over time, for example from weight
loads when stacked or used as a container. Dynamic or impact stresses arise in a material
when it is dropped or hit and the material is forced to absorb energy over a very short time
span. Impact that would cause fracture in archaeological ceramics is usually accidental and
can be avoided by careful handling. Moreover, impact stresses are in many cases so severe
that no conceivable practical strength increase would have prevented fracture (Dinsdale,
1986). For these reasons, differences in impact strength are rarely meaningful or "behav-
iorally relevant" when examining the performance of a utilitarian vessel in archaeological
contexts. To study the influence of different manufacturing parameters on strength and the
resistance of a material to crack initiation, it is therefore normally adequate to examine its
response to static stresses and examine fracture strength in tension.

Theoretical Considerations
In theory, the strength of a material depends on the energy that is required to break atomic
bonds and create new fracture surfaces. The actual strength of ceramics is, however, much
 MECHANICAL AND THERMAL PROPERTIES 611

lower than this theoretical strength owing to the presence of flaws. Structural imperfections
are present in every real material. Composite materials, such as archaeological ceramics, are
especially susceptible to high flaw concentrations. These flaws range from pores to grain and
phase boundaries. The role of flaws in tbe reaction of ceramic material to an applied external
stress a can be quantified following the approach Griffith developed based on the work of
Inglis (see Kingery et al., 1976, or Davidge, 1979 ). Inglis showed that the maximal stress at the
tip of an elliptical crack is:

Equation 33.1

where a is the applied stress, p the radius at the crack tip, c the length of a crack at the surface,
and 2c the length of an internal crack.
From Equation 33.1, it follows that an external applied stress a creates increasing maxi~
mal stress at the crack tip (""'"') for increasing sharpness of a crack, that is, decreasing
crack tip radius. Flaws can therefore be considered as stress raising agents, which act to
amplify stresses locally. If the stress "m'" at the crack tip exceeds the strength of the mate-
rial, the crack starts to grow, as there is virtually no elastic deformation in ceramics, and,
in the case of unstable fracture, leads to catastrophic failure without the need to apply
further stress.
The strength of materials such as ceramics with a multitude of microstructural imperfec-
tions that can act as fracture nuclei (e.g. inclusions, pores, microcracks) is not an intrinsic
material property but strongly dependent on those pre-existing flaws, on their distribu-
tion and concentration. It should also be noted that because of the dependence of strength
on specimen dimensions and loading method, only strength measurements that have
been made under similar conditions should be compared with each other. Moreover, it is
expected that the values for strength determined on different pieces of the same material will
show some scattering, as the maximum stress that can be applied to a test bar is a function of
the size and radius ofits flaws.

Measurement of Fracture Strength

Strength is related to the maximum force that can be applied to a specimen without a
crack initiating, and is defined by the highest stress experienced within the materials at the
moment of rupture.
To assess the fracture strength of a ceramic, usually the transverse rupture strength (TRS)
is determined from three-point bending tests on un-notched, rectangular test bars. Under
bending, compressive stresses arise in a test bar at the inside of the bend, and tensile stresses
at the outside. Since ceramic materials are much stronger in compression, fracture initiates
in the part of the specimen which is exposed to tensile stresses, and thus this test is an indi-
rect way to assess the tensile strength of a ceramic. Tensile strength of ceramics is rarely mea~
sured directly owing to the difficulty of precise alignment of the holding grips and the high
susceptibility of results to misalignment. While this is less critical for ductile materials which
are able to "self-align'' to a certain degree during testing, brittle materials can fail well below
their material strength if tested in this way.
612 NOEMI s. MULLER

'Io assess the TRS, a force is applied to the test specimen at a constant crosshead speed, and
the load, as a function of displacement, is recorded. The loading rate should be sufficiently
slow so that quasi-static response of the material is obtained. Fracture strengthcrfcan then be
calculated using standard bending mechanics analysis as:

3PnaxS
(5 = - ' 2- Equation 33.2
! 2bd

where P"'"'is the maximal load, s the span of the support rods, b the width, and d the height
of the specimen.
Failure initiates at the tip of the maximum size flaw and multiple tests and special statis-
tic methods are usually required owing to random size, orientation, and location of flaws.
However, for day-based ceramics, simple averaging of results has been shown adequate to
obtain reliable results (Kilikoglou eta!., 1998) and testing of three to five specimens appears suf-
ficient when the fracture surfaces are examined visually and data of samples with macroscopi-
cally identifiable flaws in fracture surface and are excluded from the calculation of the mean.

Influence of Ceramic Manufacture on Strength

A series of studies have investigated the influence of manufacturing parameters, in particu-
lar tempering and firing on the transverse rupture strength of clay-based ceramics. The main
principles are briefly summarized here; more extensive discussions can be found in Tite et al.
(200!).
In general, higher firing temperatures result in an increase in transverse rupture strength.
The vitrification in the fired ceramic matrix results in much stronger bonding than is the
case with the only loosely connected clay particles in a low-fired ceramic. Therefore, it is
expected that changes in the degree of vitrification and microstructure as observed under a
scanning electron microscope will be reflected in strength values. This accounts also for dif-
ferences observed between calcareous and non-calcareous base clays fired to the same tem-
peratures. While in general increasing firing temperatures result in an increase in strength,
the typically earlier onset of vitrification in calcareous clays results in an earlier onset for this
increase in strength in calcareous ceramics as compared to non-calcareous ceramics fired
to the same temperatures. Moreover, in calcareous ceramics, the development of a stable
cellular structure, typically between c.Sso-wso'C, results in an apparent plateau of strength
levels over the relevant temperature range. Finally, in very high fired ceramics, the develop-
ment of an extensive glassy phase accompanied by a reduction in porosity (and thus flaw
concentration) correlates with a further increase in strength.
The addition of aplastic inclusions to a ceramic paste results in a reduction of transverse
rupture strength. This reduction is more pronounced with an increasing amount and, to
some extent, an increasing grain size of the temper particles. As noted above, the strength
of a material depends on the concentration and size of the flaws it contains. The addition of
aplastic inclusions results in matrix damage during firing and drying and introduces new
types of flaws in the ceramic material. The observed decrease in fracture strength in tem-
pered ceramics is a result of the consequential increase in overall flaw population.
The influence of the mineralogical and elemental composition of temper material on
fracture strength is less clear. Tite et a!. (2001) have summarized strength data obtained on
..--------------------------- MECHANICAL AND THERMAL PROPERTIES 613

different temper types, but point out that different setups and manufacturing parameters
make a comparison of results between different studies difficult. It appears, however, that
quartz inclusions result in weaker materials than other types of inclusions. 1his is because of
differences in the microdamage that aplastic inclusions introduce during firing, and its influ-
ence on fracture strength. Microcracking of the surrounding ceramic matrix and debonding
of particles are more pronounced with quartz inclusions owing to the relatively high thermal
expansion coefficient of the mineral. In the absence of a systematic assessment of the influ~
ence of different temper types on fracture strength, it remains, however, unclear whether
there are significant differences between other types of temper.
Owing to the profound influence of flaws on fracture strength, if the temper material
undergoes structural alterations during firing which result in an increase in flaws, such as
the burning out of organic temper, the result will be a weaker ceramic. On the other hand,
if firing results in the fusion of an inclusion with the surrounding matrix so that it effec-
tively becomes part of the matrix, then the negative effect of tempering on fracture strength
is likely to be lessened, because the result is a material with fewer imperfections.
In terms of temper shape, it appears that bulky temper particles reduce strength more
than platy temper (Miiller et al., 2010). This is due to the relative amount of flaws, both
microcracking and porosity, that these two temper shapes introduce into the ceramic during
manufacture. High amounts of bulky temper result in elongated shrinkage pores, parallel to
vessel walls, an effect which is observed to a much lesser extent with aligned platy temper,
since, in this case, the fabric can better accommodate matrix shrinkage. Moreover, owing
to differences in stress fields, the overall volume fraction of a ceramic that is susceptible to
developing microcracks during firing is much smaller for platy than bulky particles, result-
ing in comparatively fewer flaws and higher fracture strength for materials manufactured
using platy temper particles.

Toughness
Toughness or fracture energy is a measure of the energy required to break a material and
encompasses both the energy required for crack initiation and for subsequent propagation
of a crack through a material. The total fracture energy thus consists of two parts; namely, the
intrinsic fracture energy, which is the energy that is needed for the onset of fracture-that is,
for the crack to start growing-and a dissipation part, which describes the material's ability
to absorb energy during crack propagation through processes such as crack deflection and
arrest.
For archaeological ceramics, toughness is important because it is linked with their abil-
ity to maintain structural integrity when exposed to mechanical loads. Since flaws, which
act as stress concentrators and are potential origins of a crack, are ubiquitous in pottery, it is
important that a crack, once initiated, is stopped effectively before leading to fatal fracture.

Theoretical Considerations
The behavior of a ceramic under applied loads is reflected in its fracture mode. For archae-
ological ceramics, it is usually distinguished between stable and unstable fracture. When,
after crack initiation, a crack propagates through a material, without application of further
6l4 NOEMI s. MULLER

load (Figure 33.1, curve a), a material is said to show unstable (or brittle) fracture. On the
other hand, when, after crack initiation, additional energy is required in order to drive a
crack though a material and break the specimen completely (Figure 33.1, curve c), this is
referred to as a stable fracture. In a ceramic with stable crack propagation during fracture,
cracks can be stopped before they lead to failure as energy is absorbed through mech-
anisms such as crack deflection, bifurcation and arrest, temper fracture, or pull-out. In
between the two, semi-stable fracture (Figure 33.1, curve b) is also observed (see also Tile
et al., 2001). For archaeological ceramics, stable fracture is usually associated with highly
tempered and low-fired ceramics, while unstable fracture is observed in high-fired, fine
ceramics.
For materials with unstable crack propagation during fracture, where only the energy
required to initiate a crack plays a role, the energy required for fracture is given by the intrin-
sic fracture energy Grc as:

G = K:c Equation 33-3

~< E

and can be determined by measuring K~c and Young's modulus E independently. Kk is

defined as the critical value of the stress intensity factor at a crack tip that is necessary to pro-
duce catastrophic failure under simple uniaxial loading. It can be shown that:

Equation 33-4

where 2c is the length of an internal crack, Gt the stress at which fracture occurs, and Y a
dimensionless geometry factor.
The stress intensity factor K10 also called fracture toughness, is frequently used in
engineering applications and when tabulating material data. It should be noted that in
discussions about the mechanical performance of archaeological ceramics, the term
"toughness" frequently designates the total energy required for fracture. In the case of
unstable fracture this is determined solely by G 10 but in the case of stable fracture it
encompasses both intrinsic energy and energy required to propagate a crack through the
material (G d;,).

FIGURE 33.1 Typical load-displacement curves for different types of fracture observed in
archaeological ceramics: (a) unstable; (b) semi -stable; (c) stable.
 MECHANICAL AND THERMAL PROPERTIES 615

MEASUREMENT OF TOUGHNESS
············································································

1• Toughness is typically measured in four point bending tests under slow loading rates on bars
in which a standard fault (notch) has been introduced for comparability. The critical stress
1· intensity factor K" can be calculated as (Kilikoglou et al., 1995):

Equation 33·5

where P,"" is the maximal load, t the depth of the notch, (s,-s,) the difference in the span
support rods, b the width and d the height of the specimen, and F(a) = 1.122- 1.12ra + 3-74 a'
+ 3.873 a 3 -19.05 a 4 + 22.55 a 5 and a= t/d.
In order to account for finite notch width K" values are divided by a factor of 1.25. The
intrinsic fracture energy ( G1cl can then be calculated using Equation 33-3- Young's modu-
lus (E) can be estimated from the gradient of the linear part of the compliance corrected
i; load-displacement curve just before failure, or be determined from compression experi-
f
ments. For stable crack propagation during fracture, the area under the load displacement
curve after onset offracture (Figure 33.1) provides a measure of the additional energy dis-
sipated during crack propagation (Gdiss) that contributes to fracture energy in stable frac-
ture through processes such as crack deflection, bifurcation and arrest, temper fracture, or
pull out.

Influence ofManufacturing Parameters on Toughness

It is difficult to make general statements, since different manufacturing parameters influence
both intrinsic and dissipation energy, sometimes in opposite ways. It is clear, however, that
both aplastic inclusions and vitrification affect fracture mode and toughness of archaeologi-
cal ceramic materials.
Unstable crack propagation during fracture is typically observed in fine, untempered
ceramics which have been fired to temperatures above the onset of vitrification. Only when
the firing temperature is kept below the onset of vitrification do these materials show some
energy dissipation during crack propagation. However, it should be noted that while frac-
ture strength generally appears to increase with increasing firing temperature (over-fired
material excluded), the impact of firing conditions on fracture energies cannot be general-
ized, as the toughness of a material is also critically dependent upon the amount and kind of
aplastic inclusions it contains.
A shift towards a more stable fracture is observed as the amount of aplastic temper mate-
rial increases. For quartz tempered calcareous ceramics fired to 950°C, the change frotn
unstable to stable crack propagation during fracture occurs when the ceramics contain 20%
temper (Kilikoglou et al., 1995). In highly tempered ceramics, a signifrcant amount of energy
is needed to propagate the crack through the ceramic, resulting in comparatively large con-
tribution of Gdiss to overall fracture energy. Thus, the addition of temper can greatly increase
the overall fracture energy or toughness of archaeological ceramics. Toughness increases as
the amount of aplastic inclusions increases, because the rigid inclusions provide the ceramic
616 NO :EM IS. MULLER

material with additional means of energy dissipation through crack deflection, bifurcation,
and arrest. With platy particles, pull-out processes are also expected.
However, caution is required when generalizing the influence of tempering on frac-
ture toughness. For very high-fired ceramics containing phyllitic inclusions, for example,
toughness has been observed to decrease compared with lower fired ceramics. This can
be explained by weakening of the phyllite inclusions at high temperatures, combined with
the enhanced bonding with the matrix at such temperatures (Muller et al., 2015). In high-
fired ceramics, the particular temper particles effectively become part of the matrix, and can
no longer contribute to energy dissipation, thus losing the temper's toughening effect. For
very low-fired ceramics, greater toughness has been observed for platy temper material than
for more equant inclusions (Feathers and Scott, 1989; Muller et al., 2010), a phenomenon
explained by the observation that energy dissipation processes such as temper pull-out are
more effective for platy particles.

TOUGHENING MECHANISMS AND

THE ROLE OF QUARTZ

'The contribution of energy dissipation during crack propagation can be significant in

archaeological ceramics, and the generally high toughness of ceramics with a large amount
of aplastic inclusions is due largely to their toughening component Gdiss• which accounts
for the energy that is required for crack propagation. Owing to the critical role energy dis-
II
sipation plays in toughness, it is expected that a ceramic which provides effective dissipa-
tion mechanisms will have a relatively high toughness. Examples of dissipation mechanisms
in archaeological ceramics include crack deflection, bifurcation or arrest, fracture of tem-
per particles, or pull-out mechanisms. Thus, aplastic inclusions, weak temper-matrix
boundaries, microcracks and zones of microdamage, and pores are all expected to increase
a ceramic's ability to stop a propagating crack. In this regard the role of quartz temper as
a toughening agent for archaeological ceramics has been emphasized by Kilikoglou et al.
(1995). Quartz tempering introduces zones of microdamage around particle grains, owing
to a thermal expansion coefficient which exceeds that of the matrix and which is further
accentuated by the volume increase due to quartz alpha to beta phase transition at c.573"C.
Accordingly, a fourfold increase in toughness has been observed in ceramics containing 20%
I
I
quartz inclusions compared to untempered ceramics with the same matrix material.

Thermal Shock Resistance

Thermal shock resistance describes the ability of a material to withstand stresses arising from
sudden changes in temperature, and is considered relevant for ceramics which are exposed
to heat during use, such as cooking ware or crucibles. While it is usually thermal shock that is
discussed) it is important to keep in mind that thermal stresses can also originate from tem-
perature gradients that occur when one part of a vesseUs exposed to a different temperature
than another, such as when a cooking vessel is placed on a fire to boil fluid contents.
...------------------------
·~y::T~'

---
MECHANICAL AND THERMAL PROPERTIES 617

At first sight thermal shock resistance seems a more easily accessible concept than
strength or toughness. Unfortunately, owing to the complexity of the underlying mecha-
nisms, this is not the case. Furthermore, thermal shock resistance is not a material prop-
erty but a complex parameter: it depends not only on ceramic manufacture, since it is
dependent on different material properties such as thermal expansion coefficient, thermal
conductivity, strength, or toughness, but, importantly, also on how a ceramic is used or the
condition of shock. A general rating of different materials in terms of their thermal shock
resistance is therefore not possible: an assessment of different ceramic fabrics in view of
their thermal shock resistance when used in cooking processes, for example, cannot be
transferred to ceramics used in pyrotechnical applications, which are typically exposed
to much greater changes in temperature. Finally, when examining vessels, the influence of
shape in terms of wall thickness and curvature plays an important role; generally speak-
ing, sudden changes in both parameters are undesirable (Dinsdale, 1986).

Theoretical Background
When considering thermal stresses, both the origin of the stresses and response of a mate~
rial to those stresses are important. In Unrestricted archaeological ceramics, different ther-
mal expansion coefficients of ceramic matrix and aplastic inclusions, or differential thermal
expansion in an object, owing to temperature gradients, can lead to internal stresses. When
looking at the response of a material to thermal stresses, both crack initiation and crack
propagation play an important role.
Besides potential stresses from different thermal expansion coefficients of different
phases restrained within the same ceramic body, stresses due to non-uniform expansion
or contraction caused by temperature gradients within the ceramic (Davidge, 1979) are
also important for archaeological ceramics. Temperature gradients arise when different
parts of an object are exposed to different temperatures, or if an object is exposed to sud-
den changes in temperatures. In the latter case, owing to finite thermal conductivity of a
ceramic, the surface which is in contact with the cooling or heating medium adopts its tem-
perature, while the core is initially still at the previous temperature. Since volume elements
are constrained in the same body and cannot freely expand or contract, this results in inter-
nal stresses.
Analogous with what has been discussed for strength and toughness, theoretical
approaches to examining the response of a material to thermal shock involve assessment of
both the conditions for fracture initiation and the degree of damage sustained by investigat-
ing crack propagation (Kingery et al., 1976). Hasselman (1969, 1970) developed a series of
thermal stress resistance parameters to assess the suitability of ceramics to resist thermal
shocking under different conditions. A crack will initiate when the thermal stresses reach
a material's strength. Thus, for the initiation of fracture in a ceramic which is subjected to a
very sudden change in temperature (in this case it can be assumed that heat transfer within
the material is negligible, and thermal conductivity does not play a role), the thermal stress
resistance parameter R has been defined as:

a(l- v)
R Equation 33.6
Ea
618 NO EMI s. MULLER

where a is the tensile strength, E Young's modulus, v Poisson's ratio, and a the thermal
expansion coefficient of the materiaL In other words, in order to avoid crack initiation, high
strength, but low Young's modulus and thermal expansion coefficient are beneficial.
On the other side, when considering crack propagation, an example of a relevant thermal
stress resistance parameter is:

R"" Equation 33-7

Thus, in order to avoid crack propagation low strength, high Young's modulus and high frac-
ture surface work y are beneficial.
It should be noted that materials which fracture in an unstable way (e.g. a high fired fine
ceramic, such as porcelain) have a different response to thermal shock than ceramics with
stable fracture (e.g. low-fired coarse earthenware). The former experience an abrupt strength
loss at a critical temperature difference Ll·" (Hasselman. 1969 ), while the latter, which
provide effective energy dissipation mechanisms, exhibit a more gradual loss in fracture
strength owing to more controlled crack propagation (Davidge, 1979 ). Accordingly, there are
two different strategies for optimizing thermal shock for typical archaeological fabrics: for
ceramics which show unstable crack propagation during fracture, it is normally considered
best to avoid crack initiation. Therefore, for these materials high strength would be beneficial
for increased thermal shock resistance. For ceramics with stable fracture, which typically
have lower strength, it seems more important that crack propagation is effectively stopped;
that is, it can be argued that high toughness is beneficial for thermal shock resistance in these
ceramics.
From this it is clear that no absolute ordering for materials in terms of their thermal shock
resistance is possible, just as it is not possible to describe a single thermal stress resistance
parameter which is satisfactory for all situations. Theoretical considerations alone, there*
fore, cannot lead to unambiguous results, and experiments are required to assess the influ-
ence of ceramic manufacture on thermal shock resistance.

Thermal Shock Resistance in Archaeological Literature

Thermal shock resistance of archaeological ceramics has only rarely been determined
experimentally and conclusions published in the literature are often based on conjecture.
When focusing on a ceramic's response to thermal stresses, arguments for increased thermal
shock resistance in ceramics have been based on both a higher threshold for crack initiation
(Hoard et al., 1995) and increased resistance for crack propagation (e.g. Feathers and Scott,
1989 ). Investigation into the origin of thermal stresses in the archaeological literature on the
other hand have focused heavily on stresses caused by different expansion coefficients of
ceramic matrix and temper materials, to the apparent neglect of thermal stresses which orig-
inate from differing thermal expansion within an object owing to a temperature gradient. It
has been frequently argued that the selection of particular temper types is connected to their
thermal expansion factors, with an ideal temper material having a similar expansion coef~
ficient to the surrounding matrix. In fact, the similarity ofthe thermal expansion coefficients
of calcite and "typical low fired day;' pointed out by Rye (1976), is frequently used to explain
 MECHANICAL AND THERMAL PROPERTIES 619

the occurrence of this particular temper when it is found in cooking ware. Quartz, which has
a much greater thermal expansion coefficient than "typical low fired clay;' has, accordingly,
been argued to be less suited for producing vessels that are exposed to heat, since the pres-
ence of quartz inclusions would create internal stresses. It should be noted, however, that as
discussed for toughness, these different thermal expansion coefficients are known to cause
microdamage around temper particles during firing, and it is these zones of microdamage
which effectively increase a ceramics potential to resist crack propagation (Kilikoglou et al.,
1995). It appears reasonable to assume, therefore, that these damaged zones enable the fired
ceramic to accommodate thermal stresses when they recur upon heating the vessel during
use, so that one could argue that, in terms of energy dissipation during crack propagation,
quartz tempering might actually increase thermal shock resistance.
Unfortunately, a multitude of factors influence both the emergence of thermal stresses in
a ceramic and its response to such stresses, sometimes in opposing ways. Discussions should
therefore embrace and integrate these different aspects and, in order to make valid state-
ments, thermal shock resistance must be assessed experimentally in simulated service tests,
that is tests conducted under simulated service (use) conditions, rather than being inferred
only theoretically from material characteristics.

Measurement of Thermal Shock Resistance

Owing to the complex response of a ceramic material to thermal shocking and the dif-
ficulties in assessing heat transfer parameters in specific applications, for modern clay-
based ceramics thermal shock resistance is usually measured by assessing the material's
performance under simulated service conditions. Thermal shock resistance is conveniently
determined as the stability of strength levels upon a ceramic's exposure to thermal sbock. To
do so, the transverse rupture strength of a ceramic is determined before and after exposure
to a series of sudden changes in temperature. For archaeological ceramics these temperature
changes should relate to hypothesized ceramic use. For example, a 1\T of qoo'C is sug-
gested for cooking vessels, wbile a 1\ T of woo'C would be more appropriate for many metal-
lurgical ceramics. For the first assessment of thermal shock resistance it is adequate to assess
the reduction of transverse rupture strength upon exposure to thermal shock. However, for a
more comprehensive assessment of the behavior of a ceramic material, recording of thermal
shock curves, that is plotting the reduction in strength as a function of temperature differ-
ence of thermal shock, is required.

Influence ofManufacturing Parameters on Thermal Shock

Resistance of Archaeological Fabrics
Actual measurements on experimental briquettes to systematically assess the influence of
manufacturing parameters on a ceramic's thermal shock resistance are rare. What appears
to be clear from the few studies tbere are, however, is that the addition of aplastic inclusions
is an effective means of improving thermal shock resistance, at least for utilitarian ware that
is coarse and relatively low fired. The addition of temper introduces zones of microdam-
age within the material, enabling it to better accommodate tensions arising from differential
thermal expansion whether caused by thermal gradients or from different phases within the
 F

620 NOriMI S. MULLER

ceramic material, thereby increasing its thermal shock resistance by preventing catastrophic
crack propagation. These zones of microdamage may also explain that for the same tempera-
ture differences, the strength reduction caused by thermal shocking is normally less severe
in ceramics which exhibit stable crack propagation during fracture than those which do not
provide effective energy dissipation mechanisms.
A larger amount of aplastic inclusions increases the thermal shock resistance of the cor-
responding fabrics with regard to the stability of their strength leveL However, it is not only
stability of strength levels but also residual strength after shocking that is important and
should be examined. It is also worth considering that subcritical thermal shocking induces
microcracking in a material, which can improve the ability of a fabric to respond to subse-
quent thermal shock. Therefore, and since experimental results apply in a strict sense only to
conditions of testing-which are not necessarily equivalent to conditions under actual use-
the interpretation of results and subsequent formulation of statements on the suitability of a
ceramic to withstand thermal stress requires caution.

Thermal Conductivity
Thermal conductivity is a measure of the heat transfer in a material under a particular tem-
perature gradient at steady state. Thermal conductivity plays an important role in heating
rate, and, simultaneously but conversely, governs the ability of a vessel to keep its contents
warm once it is removed from a heat source. Moreover, a high thermal conductivity allows
for a more even temperature distribution throughout a ceramic body, lessening potential
thermal stresses in the material.
This property has been discussed for cooking ware and pyrotechnical ceramics. While
of advantage for fuel efficiency and facilitating even temperature distribution, for cooking
vessels a high thermal conductivity is not a priori beneficial: according to the constraints of
particular cooking methods, it can be argued that a lower thermal conductivity is advanta-
geous for slow, long-term simmering. For pyrotechnical ceramics, low thermal conductivi-
ties are normally expected to be beneficial, except in cases when a crucible is heated from
the outside, where a material with high thermal conductivity can be reasoned to perform
better.

Theoretical Background
Heat conduction describes heat transfer in solid materials. Under steady-state conditions,
the heat flux is proportional to the temperature gradient in a body. The proportionality fac-
tor k is a material constant and is called thermal conductivity (Kingery etai, 1976):

dQ dT
-;-kA- Equation 33.8
dt dx

dQ is the amount of heat flowing perpendicular to the area A in a time dt and -dT/ dx the
temperature gradient. For clay-based ceramics, thermal conductivity typically lies in the
range from 0.1 up to 1.7 W-m-'·K-' (Dinsdale, 1986).
 MECHANICAL AND THERMAL PROPERTIES 621

Heat transfer under non-steady-state conditions can be described by:

dT _ ...,, ,
--av 1 Equation 33·9
dt

where a is the thermal diffusivity and defined as the quotient between the thermal conduc-
tivity k and the heat capacity per unit volume p·cr A material with a high thermal diffusivity,
therefore, is able to rapidly adjust its temperature to that ofits surroundings.
The thermal conductivity of a multiphase material such as archaeological ceramics
depends not only on the amount and the individual conductivities of the constituents, but
also on their size, shape, and orientation (Kingery et al., 1976). Since pores act as heat barri-
ers, porosity has a significant effect on a material's thermal conductivity.

Thermal Conductivity and Heating Efficiency

Although thermal conductivity is not directly linked to the heating rate of a vessel, it is an
important parameter directing the heating (and cooling) rate of a vessel, via its influence
on thermal diffusivity, as outlined above (Equation 33.9). In this context a parameter called
"heating effectiveness" has been defined as the time that is needed to bring a certain amount
of water in replica vessels to the boil (e.g. Skibo et al., 1989; Schiffer, 1990). This parameter is
not a physical quantity but a complex product of thermal conductivity, heat flux, heat capac-
ity, permeability, and shape of the vessels. While potentially providing useful insights into
vessel use, this experimentally determined "heating effectiveness" is difficult to interpret, at
least without stringent definition of constraints and without a thorough examination of the
relevant material properties and their interplay. In order to systematically assess the heating
efficiency of archaeological cooking vessels, finite element analysis can be employed on digi-
tal computer models to simulate cooking processes. In this way specific parameters can be
investigated for their influence on the efficiency and performance of ceramic vessels. Using
this approach for cooking ware, it has been observed that differences in thermal conductiv-
ityvalues, which are expected for different archaeological ceramic materials, can give rise to
potentially observable differences in heating time (Hein et al., 2015).

Measurement of Thermal Conductivity

Thermal conductivity of ceramic materials can be determined with a modified Lees' disk
setup (Hein et al., 2008), where the sample is sandwiched between a heat source and a heat
conductor. Since the thermal conductivity of a material depends upon temperature, ideally
the heat source should allow samples to be measured at different temperatures. The ceramic
surface in contact with the heat source will adopt its temperature T,, while the temperature
of the heat conductor T, indicates the temperature of the samples' opposite surface. For
steady state conditions, integration of Equation 33.8 provides the thermal conductivity k of
the samples as:

k(T)-. (T) d
- q,"" ' A(T, - T,) Equation 33.10
•
622 NO EMI s. MULLER

where (I~ - T 1) is the temperature difference between heat source and the ceramic surface
in contact with the heat conductor, A the contact area, and d the sample thickness. Heat loss
from the rim of the sample disk can be neglected provided that its height is small compared
to its diameter. The heat loss of the heat conductor into the environment at specific tempera-
tures if. toss (T) can be determined from an independent measurement, by letting the conduc-
tor cool down while recording its temperature, as:

. (T) dT
qlo.~< = mcP dt Equation 33.11

where dT!dt is the slope of the cooling curve, cl' the heat capacity of the brass disk, and m
its mass.

Influence of Manufacturing Parameters

An increase in firing temperature typically results in an increase in the thermal conductivity
of clay-based ceramics. This increase can be correlated with changes in microstructure-
that is the emergence of an extended glassy phase, with a decrease in porosity and increased
bonding within the matrix-and with changes in mineralogical phases, in particular the
emergence of high temperature phases, with comparatively high thermal conductivities.
In many cases, the addition of relatively large amounts of coarse temper appears to decrease
thermal conductivity. This is because a large amount of temper particles induce additional
porosity: owing to the restricted shrinkage of the ceramic body, elongated pores develop
which are oriented parallel to vessel surfaces and hence in virtually all applications perpen-
dicular to the heat flow. This manufacture-induced porosity accounts for the relatively smaller
conductivities of the related samples. But the thermal conductivity of the temper material also
plays a role. For granite temper, which has a higher thermal conductivity than the surround-
ing ceramic matrix, an increase in thermal conductivity compared to untempered material
has been observed when the inclusions adhere to the matrix and can contribute to the overall
thermal conductivity, for example at low firing temperatures and low amounts of temper. On
the other hand, the addition of phyllitic temper particles, which have significantly lower ther-
mal conductivity perpendicular to their sheet layers, results in decreased thermal conductiv-
ity for heat transfer perpendicular to vessel walls when particles are aligned with vessel walls.
The influence of different types of porosity on thermal conductivity has also been studied,
in view of pyrotechnical ceramics, which are frequently found to be organic tempered (Hein
et al., 2013). Organic temper burns out during firing or use and leaves distinctive pores in a
fabric. An increasing amount of organic temper was thus found to decrease thermal con~
ductivities, as overall porosity was increased, while notable differences were found between
spherical on the one side and elongated or platy pores on the other, with the former being
less effective in reducing thermal conductivity than the latter.

SUMMARY REMARKS

Research into mechanical and thermal properties of archaeological ceramics should aim at

'
identifying choices involved in pottery manufacture and at examining how these affect the

J
..
.
 :\1ECHANICAL AND THERMAL PROPERTIES 623

physical properties of archaeological pottery and their affordances. Considering that the dif·
ferent activities ceramic objects and installations have been used for place different mechan-
ical and thermal demands on the material, such studies may ultimately contribute to our
understanding of various aspects of craft practice and technological change. An integrated
approach, taking into account the multitude of factors affecting potters' choices, is, how-
ever, crucial. Only when placed in the wider context of production and consumption, the
study of material properties will aid appreciation of the complex dynamics behind potters'
technological choices, and ultimately elucidate cultural, political, and socioeconomic factors
which favor perpetuation and diffusion of technological traditions, or facilitate innovation
and transmission of new technologies, for a material which held an integral role in many
parts of everyday life in the past.

REFERENCES

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Hammers and Theories (New York: Academic Press), 107-134.
Bronitsky, G. (1986). "The Use of Materials Science Techniques in the Study of Pottery
Construction and Use:' In: Schiffer, M. (ed), Advances in Archaeological Method and Theory,
vol. 9 (New York: Academic Press), 209-273.
Bronitsky, G. and Hamer, R. (1986). "Experiments in Ceramic Technology: The Effects
of Various Tempering Materials on Impact and Thermal Shock Resistance:' American
Antiquity 51(1): 89-101.
Davidge, R. W. (1979). Mechanical Behaviour of Ceramics (Cambridge: Cambridge University
Press).
Dinsdale, A. (1986). Pottery Science (Chichester: Ellis Horwood Limited).
Feathers,). K. and Scott, W. D. (1989). "Prehistoric Ceramic Composite from the Mississippi
ValleY:' Ceramic Bulletin 68(3): 554-557·
Hasselman, D. P. H. (1969). "Unified Theory of Thermal Shock Fracture Initiation and
Crack Propagation in Brittle Ceramics." Journal of the American Ceramic Society
52(11): 600-604.
Hasselman, D. P. H. (1970). "Thermal Stress Resistance Parameters for Brittle Refractory
Ceramics: A Compendium:' American Ceramic Society Bulletin 49(12): 1933-1937.
Hein, A., Miiller, N. S., and Kilikoglou, V. (2015). "Heating Efficiency of Archaeological
Cooking Vessels: Computer Models and Simulations of Heat Transfer:' In: Spataro, M. and
Villing A. (eds), Ceramics, Cuisine and Culture: The Archaeology and Science of Kitchen
Pottery in the Ancient Mediterranean World (Oxford: Oxbow Books), 49-54.
Hein, A., Muller, N. S., Kilikoglou, V., and Day, P. M. (2008). "Thermal Conductivity of
Archaeological Ceramics: The Effect of Inclusions, Porosity and Firing Temperature:'
Thermochimica Acta 480: 35-42.
Hein, A., Karatasios, 1., Muller, N. S., and Kilikoglou, V. (2013). "Heat Transfer Properties of
Pyrotechnical Ceramics Used in Ancient Metallurgy:' Thermochimica Acta 573: 87-94-
Hoard, R. j., O'Brien, M. j., Khorasgany, M.G., and Gopalaratnam, V. S. (1995). "A Materials·
Science Approach to Understanding Limestone-Tempered Pottery from the Midwestern
United States:' Journal ofArchaeological Science 22( 6): 823-832.
Kilikoglou, V. and Vekinis, G. (2002). "Failure prediction and Function Determination of
Archaeological Pottery by Finite Element Analysis:' Journal of Archaeological Science
29(11): 1317-1325.
624 NOEMI s. MULLER

Kilikoglou, V., Vekinis, G., and Maniatis, Y. (1995). "Toughening of Ceramic Earthenwares
by Quartz Inclusion: An Ancient Art Revisited:' Acta me.tallurgica et materialia
43(8): 2959-2965.
Kilikoglou, V., Vekinis, G., Maniatis, Y., and Day, P. M. (1998). "Mechanical Performance of
Quartz-Tempered Ceramics: Part I, Strength and Toughness:' Archaeometry 40(2): 261-279.
Kingery, W. D., Bowen, H. K., and Uhlmann, D. R. (1976). Introduction to Ceramics. Second
Edition (New York: john Wiley & Sons).
Martin6n-Torres, M., Rehren, T., and Freestone, I. C. (2oo6). "Mullite and the Mystery of
Hessian Wares:' Nature 444(23): 437-438.
Muller, N. S., Kilikoglou, V., Day, P.M., and Vekinis, G. (2010 ). '"!he Influence ofTemper Shape
on the Mechanical Properties of Archaeological CeramicS:' Journal of the European Ceramic
Society 30: 2457-2465.
Muller, N. S., Kilikoglou, V., Day,P. M., and Vekinis, G. (2015). "The InfluenceofMicrostructure
and Texture on the Mechanical Performance of Rock-Tempered Archaeological Ceramics:'
Journal of the European Ceramic SocietY35: 831-843.
Rye, 0. S. (1976). "Keeping Your Temper under Control: Materials and the Manufacture of
Papuan Pottery:' Archaeology and Physical Anthropology in Oceania n(z): 106-137.
Shepard, A. 0. (1956). Ceramics for the Archaeologist. Publication 609 (Washington
D.C.: Carnegie Institution ofWashington).
Skibo,). M. (2013). Understanding Pottery Function, Manuals in Archaeological Method, Theory
and Practice (New York: Springer).
Skibo, ). M., Schiffer, M. B., and Reid, K C. (1989). "Organic-Tempered Pottery: An
Experimental Study:' American Antiquity 54(1): 122-146.
Schiffer, M. B. (1990). "The InfluenceofSurface Treatment on Heating Effectiveness of Ceramic
Vessels:' Journal ofArchaeological Science 17(4): 373-381.
Sillar, B. and Tite, M. S. (2ooo). "The Challenge of '1echnological Choices' for Materials
Science Approaches in Archaeology:' Archaeometry 42(1): 2-20.
Tite, M. S., Kilikoglou, V., and Vekinis, G. (2001). "Strength, Toughness and Thermal
Shock Resistance of Ancient Ceramics, and Their Influence on Technological Choice:'
Archaeometry 43(3): 301-324.
 CHAPTER 34

ASSESSING VESSEL
FUNCTION BY ORGANIC
RESIDUE ANALYSIS

HANS BARNARD AND JELMER W. EERKENS

INTRODUCTION

ORGANIC residues can be defined as the carbon-based remains of plants, animals, or humans,
either in their original or a decomposed state. Biornolecules that can indicate the source of
such residues include lipids (such as fatty acids, sterols, mono-, di-, and triglycerides, di-
and triterpenoids), alkaloids (such as caffeine, capsaicin, cocaine, ephedrine, nicotine, theo-
bromine), carbohydrates (such as polysaccharides and starches), proteins (such as albumin,
casein, collagen, gliadin, hemaglobin, hordein, myoglobin), and DNA. Archaeological
organic residues have been identified in stains on teeth (Stermer et al., 1996; Oxenham
et al., 2002), deposits on stone tools (Craig and Collins, 2002; Li et al., 2013), stains in soil
(Macphail et al., 2010; Butler and Dawson, 2013), smoking pipes (Rafferty, 2006; Eerkens
et al., 2012; Tushingham et al., 2013), and material adhering to potsherds (discussed here).
A comprehensive overview of such an overwhelming number of compounds and range of
methods is beyond the scope of this chapter. Instead, we present an overview for identifying
and interpreting organic residues in ceramic vessels (Figure 34.1, Table 34.1), followed by a
brief discussion of issues related to archaeological organic residue analysis in general.
It should never be expected that organic residue analysis alone can provide irrefutable
answers to archaeological questions (Barnard et al., 2007a; Evershed, 2008), nor to research
questions that are too generically formulated. For epistemological reasons residue analysis
needs to be embedded in an archaeological or anthropological research project (McGovern
et al., 1995; Barnard et al., 2007a; Pollard and Bray, 2007; Evershed, 2008), guided by ques-
tions drawn from archaeological theory, and serve as one among several research avenues
addressing a dear and specific research question. After it has been established that residue
analysis should be part of a research project, the decision how to proceed depends not only
on the research question and the type and preservation of the archaeological material, but
also on the available instruments, funding, and scientific suppOrt. Methods for organic resi-
due analysis can be divided into two large categories, here identified as "microscopic" and
626 HANS BARNARD AND JELMER W. EERKENS

-.-..., Higher densities

near the liquid-air
interface

Lower densities
near a source of
heat

Invisible, absorbed residue Invisible, surface residue

Potential methods of analysis: Potential methods of analysis:
• GC/MS o Raman spectroscopy
o Compound specific stable isotope analysis o Starch grain and phytolith microscopy
o Raman spectroscopy o Bulk sample stable isotope analysis
~ LC-MS/MS o ELISA
o and other techniques o and other techniques

FIGURE 34.1 Schematic overview of different organic residues in archaeological ceramics, and
techniques frequently employed to investigate these (Table 34.1).

"molecular" (Figure 34.2), so named not after the nature of the residue, but rather after the
technique of their analysis.

MICROSCOPIC METHODS

The search for smaller and smaller amounts of organic residue present in ceramic artifacts is
the logical continuation of archaeological practices aided by constantly developing technology.
A microscope is now standard equipment for zooarchaeologists and paleoethnobotanists, and
many researchers successfully use polarized light or electron microscopy to study inorganic
as well as organic materials. Studies of pollen (a field pioneered by Sears, 1937; Deebey, 1944;
Sears, 1953; Dimbleby, 1955; Martin and Schoenwetter, 1960) and opal phytoliths (pioneered by
Matsulani, 1972; Armitage, 1975; Bryant and Williams-Dean, 1975; Rovner, 1975; Pearsall, 1978;
Ford, 1979) are significant in the field of archaeological residue analysis; although phytoliths are
not organic, but rather microscopic silica-based impressions of plant structures.
Spectroscopy represents a suite of techniques that developed out of the study of light, and is
often used in combination with microscopy. The surfaces of all objects absorb and reflect spe-
cific parts of white light, producing the effect that we perceive as color. This can provide impor-
tant information, such as the difference between ripe (red) and unripe (green) tomatoes, which
reflects changes in their biomolecular composition. Objects can also be investigated with other
sources of radiation energy, such as X-rays, sound, or particles (electrons, neutrons, protons).
Comparable to the color of an object in visible light, different materials interact differently with
r

1
!

Table 34.1 Schematic overview of the characteristics of selected techniques to investigate organic residues in archaeological ceramics
(Figure 34.1) i
Starch, grain, Raman Stable isotope ELISA GC/MS LC-MS/MS LC-MS/MS MRM
& phytolith spectroscopy analysis Fragmentation
microscopy scan
·"···-
Class of analytes starch most organic stable isotopes most organic lipids, alkaloids, peptides most organic:
grains and molecules of C, N, 0, Sr, and molecules terpene ids molecules
phytoliths other elements
Based on the search for a yes yes no yes no no yes
predetermined compound
Instrument output imagery Raman spectra 613(0/oo, 615NOJoo, visualized antigen- chromatogram chromatogram ion transition
& other stable antibody complex & reproducible 8 complex mass trace(s)
isotope ratios mass spectra spectra
Method of interpretation library search comparison with comparison with negative (<LOD) library search library search negative (<LOD)
standards natural ratios or positive (often or from first or positive [often
quantifiable) principles quantifiable)
Amount of expert knowledge required substantial limited limited limited limited substantial substantial
Cost of instrument (x $1000) 1-10 10-50 150-300 0-100 50-100 150-500 150-500
Duration of sample preparation (bench hours minutes hours minutes hours minutes minutes
time)
Cost of sample preparation (in $per 10-50 10-50 10-100 50-1000 10-100 10-100 10-100
sample, excluding labor)
Duration of analysis (instrument time) hours minutes minutes minutes hours hours hours
Cost of analysis of multiple samples (in $ <1 <1 1-5 1-5 5-15 5-15 5-15
per sample)
Possible ln a field laboratory yes yes no yes no no no
Destructive to the artifact no no usually no usually usually usually
Total cost for analyzing a single sample medium low medium high low medium medium
Overall value for archaeological research medium low high medium high medium high
628 HANS BARNARD AND JELMER W. EERKENS

Anth ro po!og ic<JI fArch aeol og ica I

research question

Other research avenues Organic residue analysis

Microscopic Molecular

Bulk sampling Complex mix of Predetermined

l~ound

Archaeo logica 1/Anthropo log ica!

interpretation

FIGURE 34.2 Schematic flow diagram showing the position of organic residue analysis in
anthropological and archaeological studies.

each of these incident energy beams. In addition to reflection and absorption, materials can
also transmit, scatter, or translate energy (Figure 34.3a). Of the wide range of techniques based
on these principles ~-ray backscatter, infrared (IR) spectroscopy, neutron activation, nuclear
magnetic resonance (NMR) spectroscopy, optical spectroscopy, Raman spectroscopy, X-ray
diffraction, and X-ray fluorescence have all been used successfully in archaeological studies.
Early applications focused on the study of inorganic molecules; more recently this research
technique has also allowed the analysis of organic residues (starting with Buss-Ashmore et al.,
1982; Hillman et al., 1983; Meacham et al., 1983; Edward et al., 1984; Bass, 1986; Derrick, 1989).
As with all analytical techniques, microscopy and spectroscopy have advantages and dis-
advantages. Some methods can be used non-destructively on solid materials, while other
instruments and applications require the molecules of interest to be isolated by a variety of
sample preparation treatments. Observations about the sample typically have to be com-
pared with those on reference materials or known standards. 1bis makes the choice of such
materials and standards, and the goodness of the fit between unknown and known, criti-
cal components of the analysis. In residue analysis, modern standards often interfere with
the identification of ancient materials, especially when the archaeological samples contain
biomolecules that are not anticipated or have decomposed over time. Materials with a het-
erogeneous composition, either because of ancient production processes or the decomposi~
lion of the original material into a range of degradation products, can be difficult. Related to
this is the influence of the size of the area investigated and the number of readings taken. If
small areas are investigated, heterogeneous materials Will produce different results in differ-
ent places. Large areas, on the other hand, may return a signal that is a mix of two or more
distinct residues. Sampling ancient materials, therefore, always requires choices to be made
that directly affect the outcome of the analysis.
a~
i

ASSESSING VESSEL FUNCTION BY ORGANIC RESIDUE ANALYSIS 629

(a) Incidental beam Reflection

""""~
SAMPLE
(solid)
~ Absorption

Transmission

(b) Analysis

Precursor ronl!Product rons

....•"
II
B

A' Ill
SeparatiOn
--'--~

SAMPLE
(liquid/gas)
Lost lost lost

FIGURE 34.3 The general principles of "microscopic (a)" and "molecular (b)" methods
for organic residue analysis. Microscopic methods are based on the response of materials
to a specific incidental beam of energy. Molecular methods identify individual molecules by
measuring their mass and that of their fragments (product ions).

MOLECULAR METHODS

The analysis of an organic residue by molecular methods usually starts with isolating the
organic residue from the inorganic material in which it was preserved. Often, this involves
dissolving the residue into an extraction solution. The choice of solution determines which
biomolecules are extracted and which are bypassed or even destroyed. As a result, choices
about which types ofbiomolecules will be analyzed are made early in the process; consider-
ations that should be part of the overall research design. If only a limited amount of material
is available for analysis, it may not be possible to explore aU possible avenues of research.
Once extracted, the residue can be studied as a bulk sample, for example by establishing its
total organic carbon (TO C) abundance. This is done by combusting the sample and measur-
ing the resulting flow of carbon dioxide which provides a measure of the amount of organic
material preserved. The interpretative value of the TOC, however, usually contributes little
to our understanding of ancient human behavior.
A more informative approach is the determination of isotopic ratios for selected elements.
The best known application of this is radiocarbon ("C) analysis for dating organic materials
(Libby et al., 1949; johnson et aL, 1951; Stott et al., 2003). The ratio of unstable "C against the sta-
ble 12 C and 13C isotopes provides information about the age of an organic artifact because 14 C is
630 HANS BARNARD AND ]ELMER W. EERKENS

lost at a fixed rate-so% every 5,730 years-after organic metabolism has stopped. The ratios of
the stable carbon ("C and ' 3C) and nitrogen (' 4N and "N) isotopes provide information of great
interest to archaeologists (a field pioneered by Vogel and Vander Merwe, 1977; Chisholm et al.,
1982; Schoeninger et al., 1983; Vander Merwe and Vogel, 1983; Hobson and Collier, 1984; Dorn
and DeNiro, 1985; Farnsworth et al., 1985). Organic carbon and nitrogen are the building blocks
of life and their lighter isotopes are slightly easier to manipulate by the enzymes that assemble
and modify organic molecules. This results in a different ratio of lighter and heavier isotopes
in organic matter (0 13C%o and 0 15No/oo) compared to the inorganic environment. Establishing
these ratios for archaeological organic materials can provide information about their biologi-
cal origin and trophic level. The ratios of stable hydrogen ('Hand 'H), oxygen ('6 0 and ' 80),
sulfur ("Sand ''S), calcium (''Ca and 44 Ca), and strontium (86 Sr and 87Sr) isotopes-which are
naturally present in many organic materials-can provide information about the geographical
origin of archaeological materials, because the distribution of these isotopes is not uniform
throughout the environment (Shackleton, 1973; Ericson, 1985; Sealy and Sillen, 1988).

CHEMICAL ANALYSIS

Study of intact ancient organic molecules began in the 1960s (Clancy, 1961; Miller and
Wickoff, 1968; Briuer, 1976; Condamin et al., 1976; Kuksis et al., 1978; Lin et al., 1978), but
the field only started to receive significant attention in archaeology during the 1980s (Passi
et al., 1981; Knights et al., 1983; Loy, 1983; Rottlander and Schlichtherle, 1983; Morgan et al.,
1984; Evershed et al., 1985; Hill et al., 1985; Paabo, 1985a, 1985b; Patrick et al., 1985; Robinson
et al., 1987; Evershed and Connolly, 1988; Gurfinkel and Franklin, 1988; Rullkotter and
Nissenbaum, 1988; Giila~ar et al., 1989; Hurst et al., 1989; Mills and White, 1989; Newman
and julig, 1989). The number of publications on the subject has grown ever since (Eerkens
and Barnard, 2007). In general, there are two approaches for the analysis of intact organic
residues. Archaeologists, who often have no idea which compounds an ancient organic resi-
due is composed of, are usually limited to a rather general research question: "What is the
composition of this complex mix of unknown compounds?" A theoretically and practically
superior approach begins with a more specific research question: "Is compound X present in
the sample?" The latter requires the identiflcation of one or more marker molecules, as spe-
cific as possible for compound X, after which a specific method can be developed to establish
the presence or absence of these in the sample. In order to identify compounds within a
complex mixture, it is necessary to separate the sample into its components (Figure 34-3b).
This can be done by electrophoresis, using a gel, or by chromatography, where the sample is
passed through a column with an affinity for the molecules of interest either in solution (liq-
uid chromatography) or in a gaseous state (gas chromatography). As the ambient conditions
in the gel or column change, different molecules in the sample will pass into the attached
analytical instrument at different times (Figure 34-4).
In archaeology, gas chromatography combined with mass spectrometry (GC-MS) is often
used to identify a range of compounds present in complex organic residues (Barnard et al.,
2007a, 2007b). A GC-MS instrument first separates the sample into its components by gas
chromatography. After being evaporated, the sample flows onto a long, narrow, glass column
coated on the inside with a polymer to which some of the molecules in the sample will attach
 ASSESSING VESSEL FUNCTION BY ORGANIC RESIDUE ANALYSIS 631

SAMPLE
~ Chromatograpy array
1--------+ --~ ---)> Chromatogram

Chromatograph Detector

Mass spectrometry array

SAMPLE 1------: 1-----,-------> .~ ____________. Mass spectrum

Ion source Mass analyzer Detector
SAMPLE

t Chromatography-mass spectrometry instrument

1-.-----------+ 1------+ 1-------------~ ~ ---->- c~~s~~~~~~;;

Chromatograph Ion source Mass analyzer Detector
SAMPLE
! Chromatography-tandem mass spectrometry instrument

. -------~ 1-------~ 1-----------> 1------+ 1----------~ ~

Chromatogram
,_. ~ Mass spectra
lon transition trace(s)
Chromatograph ion source Mass Collision Mass Detector
analyzer 1 cell analyzer 2

FIGURE 34-4 Mass spectrometry instruments are usually combined with a chromatogra-
phy array which separates the sample into its components and converts these into a form fit
to enter the ion source (top). In the ion source molecules are made into gas-phase ions after
which these are separated according to their mass-to-charge ratio (m/z) in the mass ana-
lyzer. The output of the detector and attached data processing unit consists of a three-dimen-
sional dataset (time-m/z-abundance) which can be visualized as a chromatogram and one
or more mass spectra (bottom).

(the "stationary phase"). When the temperature in this column is raised different molecules
will become mobile at different times and pass through the column in which a steady stream
of a carrier gas is maintained (the "mobile phase"). As they elute from the column, com-
pounds are ionized by electron impact (El+) ionization. This results in positive ions that will
fragment in a reproducible way, both with respect to the mass of the fragment ions and their
relative ratios. The masses of all ions are measured and the resulting mass spectrum is com-
pared to those in one of several large digital libraries.
The advantages of GC-MS instruments are the high resolving power of gas chromatog-
raphy and the fact that the fragment ions formed during EJ+ ionization produce a "finger-
print" which allows molecules to be identified with a high degree of certainty. Disadvantages
include the requirement for thermal stability of the analytes, which necessitates their chemi-
cal treatment into more stable forms (derivatization), and the relatively small portion of the
sample (typically 1-10 ~L) that can be investigated. After derivitization, most small organic
632 HANS BARNARD AND JFLMER W. EERKENS

molecules ( <6oo Da) can be analyzed by GC~MS. Only molecules that are successfully
extracted from the residue and survive evaporation as well as ionization will be available for
identification. In ceramic artifacts, these are mostly acylglycerols and fatty acids-stable and
well-studied compounds, but very common in nature and seldom unambiguous concern-
ing their source-as well as alkaloids, sterols, and terpenoids, which can be more specific
in terms of origin (Hayek et al., 1990; Charters et al., 1993; Fox et al., 199S; Mottram et al.,
1999; Stott et al., 1999; Eerkens, zooz; Rafferty, zoo6; jacob et al., 2008; Eerkens et al., zorz;
Tushingham et al., 2013).
Because lipids survive well in the archaeological record and during GC~ MS analysis,
they have received much attention from archaeologists. Methods to increase the speci~
ficity of lipid analysis, particularly to identify the origin of organic residues, include the
search for "biomarkers;' compounds that are considered unique to a class of plants or ani-
mals (Evershed, 1993, 2008). The level of specificity of a biomarker varies, but often corre~
lates with a l.innaean taxonomic category (species, genus, family). This stems mainly from
evolutionary processes, where specific biomolecules rarely evolve more than once and are
seldom the result of convergent evolution (Hochachka and Somero, zoo2). Once evolved,
biomolecules can remain virtually unaltered for millions of years and may occur in many
related species. Lipid biomarkers are uncommon, and often decompose into even less diag-
nostic molecules.
To mitigate this problem, archaeologists have identified lipid "fingerprints" of particular
organic sources. Such fingerprints are the relative proportions of two or more individually
non~diagnostic lipids. This approach is similar to the one used for geochemical sourcing of
lithic materials; ratios of particular elements or their isotopes provide fingerprints of differ~
ent quarries or lithic sources. Databases with ratios of fatty acids ofknown products and arti~
ficially aged products are available in several publications (Skibo, 1992; Malaineyet al., 1999a,
1999b; Eerkens, zoos). Fingerprints for lipids recovered from archaeological materials can
be compared to those in these databases in order to establish their origin. The level of speci~
ficity of this method is less than when molecules can be identified that are specific for their
source (biomarkers). One reason for this is that organic compounds degrade, and different
compounds degrade at different rates. Therefore, while ratios of particular compounds may
be indicative of specific organic sources in fresh and unmodified samples (Malainey et al.,
1999a), the ratios of these compounds can change dramatically over time (Evershed, 1993;
Malainey et al., 1999a, 1999b; Middleton, zoo4; Reber and Evershed, 2004; Eerkens, zoo7).
As a result, the extraction and comparison of fatty acids from ancient pottery may only be
able to discriminate between general classes of food, such as meat, fish, vegetable, and so on
(Eerkens, zoos).
The second approach-starting with the research question "Is compound X present in
the sample?" -involves identifying a predetermined biomolecule, specific for compound
X, in a sample. This allows for a specific analytical method to be chosen or tailor~ made
and fine~ tuned to detect very small amounts of the chosen molecule or molecules. This is
the preferable approach because it derives from a research question that can be answered
through a deductive process. At the same time it is more in line with the methods
developed by analytical biochemists. One way to determine the presence of a predeter~
mined molecule is by using an immunological method in which the sample is brought
into contact with, preferably monoclonal, antibodies known to bind with the molecule
of interest (the antigen). When these antibodies are chemically or radioactively labeled,
 ASSESSING VESSEL FUNCTION BY ORGANIC RESIDUE ANALYSIS 633

ANTIGEN

• r
Antibody~antlgen reaction
Epltope

ANTIBODIES

/
Monoclonal ant1body
J yL ~Enzyme or
rad1o-act1ve
(immunoglobulin) marker

POSITIVE: NEGATIVE:

• •
Sample Sample

t t f
--er
y
Surplus (monoclonal) antibodies Surplus (monoclonal) antibodies

FIGURE 34·5 Schematic representation of the antibody-antigen reaction. Antigens com-

prise many different epitopes, each of which will bind with a specific (monoclonal) antibody
(top). 'The resulting antibody-antigen complexes can be detected when marked antibodies
are used (bottom).

the resulting antibody-antigen complexes can be detected (Figure 34-S). Immunological

techniques used in archaeology, mostly to identify proteinaceous residues, include vari-
ants of counter immuno-electrophoresis (CIEP), enzyme-linked immuno-sorbent assay
(ELISA), radio-immuno-assay (RIA) and Western blot (Briuer, 1976; Loy, 1983; Ascenzi
et al., 198s; Newman and julig, 1989; Hyland et al., 1990; Yohe et al., 1991; Cattaneo et al.,
1993; Loy, 1993; Petraglia et al., 1996; Loy and Dixon, 1998; Shanks et al., 1999; Billman
et al., 2000; Craig and Collins, 2ooo; Craig et al., 2ooo; Marlar et al., 2000; Reuther
et al., 2006).
634 HANS BARNARD AND JELMER W. EERKENS

Another method used to identify a predetermined biomolecule is liquid chromatogra-

phy combined with tandem mass spectrometry (Guasch-jane et al., 2004; McGovern eta!.,
2009; Barnard et aL, 2011). This combination instrument separates a complex sample into
its components by liquid chromatography, and subsequently allows only ions with a prede-
termined mass into a collision chamber filled with an inert gas. The masses of the resulting
fragments are measured and compared with the spectrum of masses produced in previous
studies of the authentic molecule of interest. A positive identification is made if the sample
returns a significant signal for the selected ion transitions at the retention time of the authen-
tic compound. The disadvantage of this approach is that it requires significant background
knowledge in order to select the molecule of interest; in other words, the archaeologist must
phrase the research question so that it can be addressed by showing the presence or absence
of a predetermined molecule. The advantage is that the method is able to detect the selected
molecule in an unambiguous way. This approach is valuable for identifying biomarkers and
degradation products that indicate the former presence of an archaeological biomarker. It
has been argued, for example, that the presence of coprostanol in soil samples is a byprod-
uct of bacterial decomposition of cholesterol in the human gut and, thus, indicative for the
remains of fecal material in ancient latrines (Bethell et al., 1994). Similarly, the presence of
syringic acid in ancient pottery samples treated with potassium hydroxide (KOH) can be
an indicator of malvidin, the anthocyanidin that gives wine its red color (Guasch-)ane et al.,
2004; Barnard et al., 2011). These derivative compounds can be indicative of biomarkers,
albeit with a lower degree of confidence. The limit of detection (LOD) for most biomolecules
is currently as low as a few picomoles (10-12 mole) for selected methods. Absence of evi-
dence can thus not serve as evidence of absence; the molecule of interest may be present at
levels below the LOD.
DNA is theoretically the most informative biomolecule, but its abundance is very
low in most archaeological residues. Proteins are more abundant in natural substances
and theoretically provide specific information about their origin because they are the
result of DNA transcription and translation, albeit usually followed by significant post-
translational modifications. One of the best studied ancient proteins is collagen (Child,
1995; Collins eta!., 2002; Hedges, 2002), but other proteinaceous molecules have also been
described in paleontological (Miller and Wickoff,1968; jun, 1974; Schweitzer et al., 1997;
Nielsen-Marsh et al., 2002; Asara et al., 2007; Schweitzer et al., 2009) and archaeological
materials (Brooks eta!., 1990; Evershed and Tuross, 1996; Barnard et al., zoo7c; Solazzo
eta!., 2008; Cappellini eta!., 2010). Predetermined, more or less intact, proteins can be
identified with immunological techniques, as described above. The unraveling of a com-
plex mix of unknown proteins and their decomposition products (peptides and amino
acids) poses an even greater challenge than that of alkaloids, lipids, or terpenoids-owing
to denaturation, hydrolysis, decarboxylation, deaminiation, browning, and racemation
of the molecules (Brooks eta!., 1990; Bada, 1991; Child, 1995; Evershed and Tuross, 1996;
Collins et a!., 2002; Hedges, 2002; Barnard et a!., 2007c; Buckley et a!., 2008; Pevzner
eta!., zooS; Solazzo et al., 2oo8)-but at the same time promises a greater reward. One
approach, developed to investigate the remains of proteins in ancient paints, is based on
a statistical analysis of the relative abundance of amino acids, the building blocks of pro-
teins, identified by GC-MS (a field pioneered by Keck and Peters, 1969; Halpine, 1992;
Casoli eta!., 1995; Colombini et a!., 1998; Aruga eta!., 1999). Only a few proteins can
reasonably be expected in paint media, which until recently were made of egg white, fish
 ASSESSING VESSEL FUJ\"CTION BY ORGANIC RESIDUE ANALYSIS 635

bones, milk casein, or rabbit skins. It is therefore feasible to generate amino acid "finger~
prints" of these proteins in fresh specimen and compare these to the results from histori-
cal materials.
Two other approaches for analyzing proteins are peptide mapping, also referred to as
peptide-mass fingerprinting, and peptide sequencing. Peptide mapping is based on the
accurate measurement of the mass of an unknown peptide and comparing this with the
masses of known pep tides generated in silico from a genomic database. Peptide mapping is
generally done by matrix-assisted laser desorption and ionization time-of-flight (MALDI-
TOF) mass spectrometry. Peptide sequencing involves the identification of the amino acids
that form part of a peptide and establishing their sequence. This information can be com-
pared to the sequence of amino acids in known proteins, present in several large online
databases, potentially providing an identification at genus or even species level. Peptide
sequencing is usually done by tandem mass spectrometry (MS/MS), often preceded by liq-
uid chromatography (Aebersold and Mann, 2003; Canas et al., 2oo6; Whitelegge, 2009).
MS/MS involves precisely measuring the molecular weight of a precursor peptide, induc-
ing fragmentation of the peptide by collision with an inert gas, followed by measuring the
masses of the resulting fragments. As this yields both the mass of the parent peptide as
well as amino acid sequence information, relatively confident identifications of the pep-
tides in the sample can usually be made using this technique (Yates, 1998; johnson eta!.,
2005; Whitelegge, 2009 ). The identification of proteinaceous residues may well become the
most important technique in the field of archaeological organic residue analysis in the near
future.

THEORETICAL CoNSIDERATIONs

Archaeology typically borrows its tools and methods from other disciplines (Seaberg, 1964;
Rainey and Ralph, 1966; McGovern et al., 1995; Brothwell and Pollard, 2001; Pollard and
Bray, 2007; Malainey, 2012). Archaeological theory is mostly anthropological theory, but
also includes elements of (evolutionary) biology, (art) history, and physics (Schiffer, 1988;
johnson et al., 2oo6). Archaeology seems ideally situated to be a place where the "soft" and
the "hard" sciences meet and where scholars and scientists from different disciplines can
cooperate to tease as much information as possible out of the material remains of the human
past (Seaberg, 1964; Rainey and Ralph, 1966; McGovern et al., 1995; Pollard and Bray, 2007).
In order for the powerful and ever-improving methods and technologies briefly described
above to reach their full potential, several issues need to be addressed within the archaeo-
logical community. Among these are the archaeological and anthropological significance
of molecular residues, the disconnect between analytical chemists and archaeologists, and
recognition of the field of residue analysis by colleagues. Although we are unable to provide
definitive solutions for any of them, we introduce these issues here hoping that their recogni-
tion will lead to their being addressed in practice.
Firing a vessel destroys all organic matter in the paste, ensuring that organic residues
found in a ceramic artifact are deposited there as or after the item was used. It has been con-
firmed by radiocarbon analysis that lipid compounds extracted from a potsherd can indeed
be ancient (Stott et al., 2003). This has little bearing, however, on the question of whether
636 HANS BARNARD AND ]ELMER W. EERKENS

these molecules represent: the first food to come into contact with the pot, after which the
available binding sites within the fabric are saturated; the last, if older residues are continu-
ally replaced by new ones; or are a combination of all the foods that had contact with the
inside of the vessel, if the molecules that make up the residue compete for available binding
sites. In addition, vessels may have been used to prepare organic dyes or glues, as censers
or coffins, or to store a multitude of organic items. It is also possible that compounds in the
residue were absorbed from its depositional environment long after the pot was discarded,
or even introduced by the archaeologist. There is an overwhelming variety of compounds
that can be targeted for extraction from archaeological ceramics. More often than not, the
available sample material is insufficient for analysis by several analytical methods, which
would obviously be preferable (Regert et al., 2oo6; Ribechini et al., 2007). This, in combi-
nation with limited funding and instrument time, means that archaeologists must make
choices about which group of compounds to investigate. This choice not only determines
the methods and instruments used, but to a large degree also the outcome; a point insuffi-
ciently acknowledged in archaeological organic residue studies.
Heron et al. (1991) found that lipids from the surrounding soil do not easily penetrate into
the fabric of ceramic artifacts, suggesting that once lipids are in place within the ceramic
matrix they are difficult to displace and thus have the potential to inform on ancient activi-
ties. This study has not, however, been repeated under a range of depositional contexts and
ceramic fabrics. Likewise, adjacent soils are too rarely analyzed and compared to the residues
collected from artifacts. Other studies have shown that organic molecules in visible encrus-
tations on the surfaces of potsherds are generally less well preserved compared to those
invisibly attached to the ceramic matrix within the walls of vessels (Oudemans and Boon,
1991, 2007; Oudemans et al., 2007). Stern et al. (2ooo) demonstrated that the lipid densities
vary across the profile of a cooking pot, being low near the base, where the pot was exposed
to fire and lipids have degraded, and highest near the "boil line;' an observation confirmed
by stable carbon and nitrogen isotope analysis (Barnard et al., 2007a). Methodological stud-
ies, such as these, can help archaeologists target certain types of sherds to maximize the like-
lihood of recovering organic residues.
Owing to selective leaching and decay by microbiological attack and chemical decom-
position, organic residues in an archaeological context will change at the molecular level as
well as with respect to their composition (Malainey et al., 1999a, 1999b; Middleton, 2004;
Reber and Evershed, 2004; Eerkens, 2005). Paleontologists and food scientists have stud-
ied the effects of decomposition (Hudlicky, 1990; Collins et al., 2002; Hedges, 2002; Frankel,
2005), but their tirnescales are different from those relevant to archaeologists. In addition,
the effects of different food preparation methods on residue preservation have not been
extensively studied, and it is unclear how pots used for storage, serving, or transporting food
absorb and preserve organic remains. 1hese issues could be resolved through a series of rela-
tively simple experiments, for example extracting the residues of known organic materials
that have decomposed for known amounts of time and evaluating how the compounds have
decomposed. Archaeologists occasionally recover material residues that were labeled by
ancient scribes or whose composition could be inferred (Guasch- jane et al., 2004; Ribechini
et al., 2009; Barnard et al., 2on; Zagorevski and Loughmiller- Newman, 2012). By controlling
for the environment under which these compounds decomposed, it is possible to examine
their long-term degradation. A drawback to this approach is that such finds are rare and
 1
ASSESSING VESSEL FUN'CTION BY ORGANIC RESIDUE ANALYSIS

destructive analysis of vessels to obtain residues for which the source material is already
known in not always possible.
Archaeological research projects with a biochemical analytical component usually
require the cooperation of scholars and scientists with widely varying expertise and
research interests. On one end of this spectrum are anthropological archaeologists, on
the other analytical biochemists, with a large range of different experts in between. Given
the differences in background and research interests, there exists an enormous potential
for misunderstandings among members of these diverse research teams. Archaeological
publications about organic residue analysis are mostly concentrated in Archaeometry and
the Journal of Archaeological Science (Eerkens and Barnard, 2007 ). When published else-
where, they often appear in specialized biochemical journals, making them difficult for
archaeologists to find (Kuksis eta!., 1978; Lin eta!., 1978; Passi eta!., 1981; Robinson eta!.,
1987; Giila<;ar eta!., 1989; Hurst eta!., 1989; Hayek eta!., 1990; Casoli eta!., 1995; Aruga
eta!., 1999; Craig and Collins, 2ooo; Stott eta!., 2003; Guasch- jane et a!., 2004; Hansel
eta!., 2004; Solazzo eta!., zooS). Indeed, biochemists sometimes use archaeological sam-
ples to address biochemical rather than archaeological research questions (Stankiewicz
et a!., 1997; Van Bergen et a!., 1999). Archaeologists do not regularly read Analytical
Chemistry, nor biochemists Archaeometry, which hampers the two groups from connect-
ing, although online search engines increasingly remove this obstacle. More difficult to
mitigate is the fact that journals are reluctant to publish the analytical (in the case of
archaeology journals) or anthropological (in the case of biochemistry journals) research
backgrounds, because they are outside the scope of the journal or considered common
knowledge of their readership. As a result, valuable information fails to make its full
impact, leading to misunderstandings and sometimes heated debates, such as those on
blood residues on ancient stone tools (Kooyman et a!., 1992; Smith and Wilson, 1992;
Cattaneo eta!., 1993; Fiedel, 1996; Newman eta!., 1997) and cannibalism in prehistoric
North America (Diamond, zooo; Dongoske et a!., 2ooo; Lambert et a!., zooo; Marlar
eta!., zooo).
The most important requirement to achieve productive cooperation within an archaeo-
logical research project is open dialogue between all participants. Communication should
be aimed at a critical understanding of the methods, prospects, and limitations of all
research avenues. Archaeologists should be cautious of entering into a biochemical research
project with unrealistic expectations, partly resulting from a literature in which failures are
underreported. Usually there is a fair amount of method development to be undertaken
before ancient specimens can be analyzed. Such groundwork is time-consuming and
potentially costly; archaeologists are typically concerned with producing archaeologi-
cally relevant data rather than developing new analytical methodologies. Analytical bio-
chemists, on the other hand, should understand that the identification of molecules from
an archaeological sample is only part of the research project. Translating the presence of
one or two biomolecules into broader statements about human behavior, without paying
attention to the archaeological context and issues of sample selection and post-depositional
processes, is unrealistic. The results of organic residue analysis should not be severed from
their archaeological origins, but rather made another property of the artifact, alongside its
weight, age, color, shape, context, and so on. Only when firmly embedded in archaeologi-
cal practice and anthropological theory, facilitated by an intimate cooperation between
 ~
I
638 HANS BARNARD AND JELMER W. EERKENS

archaeologists and analytical biochemists, can the field of residue analysis reach its full
potential.
A final challenge in archaeological residue analysis is creating more consistency in the
generation and interpretation of data across laboratories (Kooyman et al., 1992; Clarkson,
2002; Wadley et al., 2004; Barnard et al., 2007a; Lyman and Van Pool, 2009). There seems
to be too little effort among those working in the field of archaeological residue analysis to
standardize methodologies or cross-check results, practices well established in the natu-
ral sciences. This is opening the field to more severe challenges than otherwise warranted
(Kooyman et al., 1992; Smith and Wilson, 1992; Downs and Lowenstein, 1996; Evershed
and Tuross, 1996; Fiedel, 1996; Newman et al., 1997; Diamond, 2000; Dongoske et al., 2ooo;
Lambert et al., 2000; Marlar et al., 2000; Collins et al., 2002; Reber and Evershed, 2004;
Barnard et al., 2007a; Buckley et al., 2008; Pevzner et al., 2008). Archaeologists and analyti-
cal chemists working on ancient organic residues need to spend more time and energy on
establishing the accuracy and robustness of individual approaches to archaeological residue
analysis and continually evaluate the efficacy of the field as a whole. For this it will prove
essential that a consistently maintained online database specific to archaeological residue
research is established, similar to those widely used for fresh lipids and proteins (Eerkens
and Barnard, 2007).

ACKNOWLEDGMENT§

The authors wish to thank Alek Dooley for his valuable assistance in compiling this
chapter.

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 PART VII

DATING CERAMIC
ASSEMBLAGES

L_
 CHAPTER 35

TYPOLOGY AND
CLASSIFICATION

EUGENIO BORTOLINI

INTRODUCTION

IMAGINE that an archaeologist was abruptly brought to a table covered with the most dispa~
rate objects: a mug, a cookie jar, a spoon, a miniature car, a bicycle bell, a light bulb, a shoe,
a glass, a stapler, a nail, a book, a sponge, a note pad, pens, a fork, a pair of keys, a pipe, and
many others.
Imagine now the same archaeologist being asked to sort all the items covering the table in
an ordered and logically sound way; a way that possibly represented the flow of time or the
basic mechanisms of interaction between the individuals that made and/or deposited these
items. The sorting should be flexible, replicable, and yet designed for the case at hand. How
would our archaeologist divide them? Would she or he look at their shape, color, and overall
appearance? Would it be preferable to think of their constituent materials? Or, rather, would
it be better to start from their function? Should she or he look at the entire object or should
she or he focus on some specific elements?
This fictive example is not dissimilar to the actual challenge archaeologists face when they
uncover a context for the first time, or when they want to analyze an already known or famil-
iar set of materials from a completely new perspective. Archaeological materials provide
information about their producers and/or consumers, and their respective social, cultural,
and economic contexts. However, this vast and fluid data needs to be ordered and divided in
more manageable units, so that inferences about causal processes and/or relationships are
possible.
Ordination techniques in archaeology have been developed for precisely this reason, to
"put order into disordered evidence" (Renfrew and Bahn, 2004: n8). Variability in mate-
rial culture derives from the cumulative effect of individual choices, copying errors, social
preference, interaction, taphonomic processes, and multiple loss-of-knowledge events. If
researchers want to identify directions in this sea of variation Without sinking or getting lost,
they need to produce a map in which landmarks are clearly indicated. A systematic arrange-
ment of material culture is the archaeologist's map towards understanding and explanation.
Nevertheless, there is no definitive classificatory structure that can encompass all possible
652 EUGENIO BORTOLINJ

datasets and answer all possible questions. In fact, many different approaches have devel-
oped over time, and scholars have often proposed antithetic explicit definitions or implicit
uses for the terms type, class, group, and assemblage. Most of the archaeological approaches
to typology and classification draw on the different directions that emerged from the archae-
ological debates of the 1940s and 1950s.
Studies on typology, classification, and ordination techniques have always involved
a number of cultural expressions, from early lithic industries to complex pyrotechnical
products. Among the latter, ceramics acquired a particularly relevant status partly owing
to their abundance in later prehistoric and historic archaeological contexts, which can be
in turn ascribed to the durability of pottery compared to more perishable materials, but
mostly because they were increasingly used to measure time in terms of relative chronol-
ogy where absolute dating was unavailable (O'Brien and Lyman, 2006). Observation of
change in the formal and, potentially, functional attributes of pottery has been the key
to building models of diachronic variability (ibid.). Therefore, the theory and practice of
archaeological typology and classification is strongly interwoven with the study of ceramic
materials.

TYPOLOGY OR CLASSIFICATION?
SOME PRELIMINARY DEFINITIONS

The terms typology and classification are often thought of as synonymous and interchange-
able (Adams, 2008). However, a thorough examination of these terms and their definition
suggests that this is not the case.
Archaeologists, and researchers involved in many other disciplines, developed methods
for systematizing and ordering the archaeological record in order to analyze the emerg-
ing picture of past human activities. Analyze literally means to divide something into
manageable and interpretable units, and to infer the dynamic relationship between them.
Classification refers to a series of methods that can be used for the deductive categorization
of observable phenomena. Approaches that rely on different or sometimes antithetical prin-
ciples should not be confused with classification but instead be identified as inductive or
grouping methods (after Dunnell, 1971; see the section "Classes and Groups" for a detailed
explanation).
Typology is a technique developed by archaeologists in which artifacts are arranged
according to perceived or measurable similarity between observed data and specific ana-
lytical units. These units, called types, are aggregates of diagnostic attributes recorded at a
particular sampling site at a particular moment. Similarity is therefore based on the quality
or the quantity of diagnostic attributes that types and data appear to share. Types can either
be conceived as abstract models-theoretical units with no actual counterpart in the real
world-or as real, empirical entities (see Hill and Evans, 1972, for discussion). While a typol-
ogy can be a particular form of classification, the opposite is not always true (Adams and
Adams, 1991; Adams, 2008). It follows, therefore, that the terms typology and classification
cannot be used interchangeably because each term has a precise meaning and background in
archaeological ordination.
 TYPOLOGY AND CLASSIFICATION 653
, __ ,,

DEVELOPMENT OF THE CoNCEPTS OF TYPOLOGY

AND CLASSIFICATION

The Beginning
Systematization in archaeology dates back to the nineteenth century, when the large amount
of evidence uncovered by antiquarians started to be rigorously compared, European prehis-
tory offered the first framework for the identification of diagnostic artifacts and assemblages.
The main objective of this early systematization was to determine a suitable chronological
ordering for dividing collections in museums and other public and private institutions.
Scandinavian scholars are renowned for having formulated the famous "three-age sys-
tem" based on the ordered succession of three main cultural stages, that is Stone Age, Bronze
Age, and Iron Age. The system drew on the direct observation of materials repeatedly used
in different assemblages over a period of time, and ordering relied upon the idea of a pro-
gressive and unidirectional technological development The system, already known from
Classical authors and endorsed by many Danish collectors, was first used in 1819 by Christian
Jurgensen Thomsen to arrange temporally the prehistoric collections of the Danish National
Museum (the method was published in 1836 in Danish and later translated into English; see
Ellesmere, 1848).
Further archaeological investigations across Europe made it immediately clear that
this simple and effective scheme could be adopted for the entire continent This moment
represented a shift towards the identification of novel types. A type-as intended at
this early stage-can be generally defined as a single artifact which embodies a specific
stage of cultural development with defined temporal and spatial coordinates. At the same
time, John Lubbock formalized the "Palaeolithic-Neolithic" sequence (Lubbock, 1865),
and the idea of a sequential, linear development of humanity was further cemented by
the acceptance of geological stratigraphy (Lyell, 1863). In this context, Oscar Montelius
developed the three-stage idea of European Later Prehistory into a series of local or
regional chronologies that could be directly compared and refined into a succession of
subperiods. His relative dating was based on the presence of artifact types or "good finds"
(Montelius, 1899: 308), which helped to seriate phases in different contexts through
cross-site comparison. Montelius coined the terms "typological evolution'' and "typo-
logical series" (ibid.), and his approach inspired directional trends on a continental scale
over more than two millennia.
Refinement of the concept of type proceeded with the work of William Matthew Flinders
Petrie (1899 ), who developed five methods to arrange artifacts from funerary contexts accord-
ing to their plausible original chronological order. Among these methods, Petrie proposed the
analysis of "development or degradation of form" (Petrie, 1899: 297) to be performed through
the "grouping of similar types" based on stylistic resemblance (ibid., emphasis added). By
sorting pottery according to these principles, Petrie was able to chronologically seriate vessel
types over the whole study period, and to arrange them in a single-rooted genealogy with just
one main branch based on formal resemblance (Figure 35.1). Although the model of shape
evolution he proposed was simplistic and relied upon the concept of unilinear development,
654 EUGFN1(1 BORTOLINI

FIGURE 35.1 Two graphical representations of Petrie's chronological ordination of archae~

ological types. On the left there is a summary of diachronic trends articulated in seven suc-
cessive stages. Some diagnostic vessel shapes exhibit continuity between adjacent stages. The
graphs on the right consists instead of an attempt of genealogical sorting. Petrie's assumption
,,vas that of unilinear and unidirectional change over time. (Reprinted with permission from
Petrie, 1899, plates XXXI fig. 1 and XXXII fig. 3 respectively.)

Petrie succeeded in creating types that had a chronological value and alto wed him to explore
issues of"functional versus stylistic" variability over time.

Culture History
111e early t'\ventieth century represented a moment of divergent trends in the use of archae~
ological typology and classification, especially in Europe and the New World. On the one
hand, scholars involved in the study of European and Asian prehistory built upon typologies
that functioned as the basic observational unit for the different archaeological cultures doc-
umented by researchers. These "cultural markers" facilitated the systematization of the con-
spicuous amount of data continually emerging from new excavations on the Continent and
in the Mediterranean. This work developed from the seminal contribution ofVere Gordon
Chi! de (1925, 1929, 1930, 1932), and many specialized trends across Europe originated from it.
For example, just to mention two cases for their abundance of programmatic and method~
ologicalliterature on the topic, French prehistorians focused on production techniques (the
concept of chafne opCratoire is an example) and on the formal as well as functional attributes
of artifacts (Laplace 1966, 1968; Bordes, 1988, among others). Italian prehistorians focused
instead on the highly articulated and hierarchical arrangement of pottery and other artifacts,
 TYPOLOGY AND CLASSIJ7ICATION 655

based upon the occurrence of specific formal attributes (Peroni, 1967, 1998, among others).
These complex and rigidly defined ordination systems were empirically determined by
grouping together observed materials in order to identify basic types. Their normative char-
acter favored the emergence and spread of an essentialist approach towards archaeological
types. This meant that many archaeologists advocated the existence of types in the real world;
that is, the existence of material expressions of mental templates which are immanent and
invariable, models whose essence can be reconstructed by archaeologists or directly grasped
by ethnographers (Hull, 1965a, 1965b; Sabloff and Smith, 1972). 1be term typology, therefore,
began to indicate a systematization based on formal resemblance between observed data and
empirical types. This similarity was measured either on a number of diagnostic attributes or
on the object as a whole.
New World archaeology proceeded slightly differently. Although it adopted the same
approach as in Europe, archaeologists started looking at typology and classification as a
means to address specific questions of relative chronology and human interaction (Adams
and Adams, 1991; Adams, 2008). Alfred Kroeber refined and used types in order to pro-
duce effective relative chronologies by observing increase, peak and decrease in their
relative frequency at different sampling sites (the method is known as frequency seria-
tion; Kroeber, 1904, 1916a, 1916b, 1919, 1948, 1952). Chronologies obtained by frequency
seriation have been used to investigate the genealogy of cultural types, going beyond the
strict unilinear model proposed by Petrie (Kroeber 1948). Although Kroeber was explic-
itly referring to his types as artificial units imposed by the archaeologist over the continu-
ous variability of human material culture, he also revealed an essentialist approach (1916a,
1916b; see Sabloff and Smith, 1972 and Lyman and O'Brien, 2006: 27--70 for a more detailed
discussion).

A Brief Digression: Frequency Seriation

The method of frequency seriation assumes that a portion of total variation expressed by
formal attributes is a function oftime (see Figure 35.2). In other words, if time and human
interaction are considered the main factors governing change in formal attributes (or some
aggregate of the same attributes, i.e. types), time can be represented as a gradient along which
sites or assemblages are sorted. 'The chronological scaling of sampling sites follows the rel-
ative abundance of chosen attributes or types at each location. More specifically, sites are
arranged so that each attribute/type shows the longest possible historical continuity and its
frequency distribution through time is unimodal. Graphic representations of such ordina-
tions are often symmetric curves traditionally labeled battleship-shaped curves (Petrie, 1899;
Phillips eta!., 1951; Dunnell, 1970; Neiman, 1995; Lipo eta!., 1997; O'Brien and Lyman, 1999;
Lyman and O'Brien, 2006; Smith and Neiman, 2007).
The imposition of a unimodal or roughly normal distribution represents a strong anal-
ogywith ecological and biological phenomena. Species follow a unimodal distribution along
environmental gradients, with the highest frequency around optimal values (mean) and
decreasing abundance towards the tails (Hutchinson, 1957; Hill, 1973). The same principle
can be applied to the ideas embedded in material culture. Ctiltural elements are first intro-
duced into a population and its cultural background, then gradually spread until they reach
a peak in popularity (i.e. they become the modal class at a specific location in time), and
 ..,..
656 EUClENIO BORTOLIN!

A B c D

1. 97 I]
2. 95 ffil
3. 90 [jQ]
86 [ill Iii
4.
80 0[]
5.
6.
70 I 28 I IZI
60 I 35 I [§]
7.
§§353§1 1:'::'30'8:1 !§;] ~ ~

E
B.
I 35 I 50 m:J ;.::
9. [jQ] 55 30 liD
10. 50 II 45 rn
11. l2l 43 I 45 [jQ]
12. 0[] I 35 I 45
13. [j]] OI:J 65
15. m:J 85
16. I] [] 92

FIGURE 35.2 An example of frequency seriation. The relative abundance in sixteen sam-
pling sites of four variants (A-D, expressed in percentage) is arranged so that their overall
frequency/probability presents a unimodal distribution. These battleship-shaped curves
effectively represent the flow of time due to the apparent trends in popularity of the observed
types or classes. The graph shows that the space occupied by the earliest variant (A) is pro·
gressively invaded by two, low-frequency traits (B, C). These are in turn are replaced by a
later innovation (D) that progressively leads to the extinction of all other variants. As sug·
gested by the double time-arrow on the right, frequency seriation gives no preliminary
indication of time directionality. This has to be archaeologically inferred. (Reprinted with
I
permission from Dunnell, 1970:312, fig. 3.)
l
eventually decrease to extinction as they are replaced by other, newer ideas (Phillips et al.,
I
1951: 220; Dunnell1970: 309). t
This working assumption has been further developed by observing (Dunnell, 1978, 1980,
1986; Teltser, 1995) and demonstrating (Neiman, 1995) that the frequency distribution of II
specific formal traits (e.g. decorative attributes) predicted by frequency seriation resembles
that of non-selective alleles studied in biology and genetics. This parallel suggests that when
cultural elements, not subject to any functional preference or social bias, are free to vary
1
,,
,.
over time according to the exchange of information between humans (i.e. in the presence
of cultural drift), they produce a unimodal distribution analogue to that of non-selective
genetic variants (determined by genetic drift; see Cavalli-Sforza and Feldman, 1981, and
Boyd and Richerson, 1985, for a detailed discussion of parallels between genetic and cultural
tranSmission).
Ordinations generated through seriation are merely formal and their chronological value
must be inferred. For this inference to be robust, frequency seriation must meet three condi-
tions: (i) all sampling groups or sites must have the same or comparable duration in time, so
that frequency distribution is not affected beyond sample-size effects; (ii) all groups in a seri·
ation must be homologous; in other words, deriving from a shared ancestor and presenting
 TYPOLOGY AND CLASSJFICATION 657
················--·--·······

heritable continuity aside from historical continuity (Cochrane, 2009); and (iii) seriation
has to be conducted to an appropriate spatial scale, so that attribute or type frequency distri-
bution can be considered as determined by chronology rather than geographical distance,
information transfer, and migration (Dunnell, 1970: 316; Lipo et aL, 1997 ).

Early Debates over the Notion Type

The first epistemological discussion on typological ordination appeared within the frame-
work of Americanist arcbaeologyby!rving Rouse (1939) and Alex Krieger (1944). The mean-
ing that Rouse assigned to the term type was radically different from that established by early
nineteenth-century archaeologists. In his words, the concept type indicates a theoretical
unit, a class to which empirical objects can be assigned if they present a set of necessary and
sufficient modes or attributes (Rouse, 1939:9). Rouse's type was intended to be immutable,
and its origin, diffusion, persistence, decreasing popularity, and replacement could be used
to investigate change in a given culture (Rouse, 1939: 14; see Dunnell, 1986: 169-176, for fur-
ther discussion). Rouse's units were based on stylistic and formal attributes and-Similarly
to Kroeber's-could be used to generate relative chronologies (Rouse, 1939: 18).
Krieger expanded upon Rouse's work from both a theoretical and practical perspective.
In his words, an archaeological type "should represent a unit of cultural practice;' that is, the
fossil of an ethnographically observable cultural trait (Krieger, 1944: 272). The function of
types was to identify patterns in material culture that would facilitate inferences about the
mechanisms of information transfer, human interaction, and culture change. Types were,
therefore, "organizational tools" that enabled researchers to divide artifacts into groups with
"demonstrable historical meaning" (Krieger, 1944) (see Figure 35.3).
Krieger refused the use of hierarchical arrangements of artifacts or assemblages (i.e. taxo-
nomic classifications) and envisaged a six-stage process named "the typological method"
(Krieger, 1944: 279-281). The process started by grouping together artifacts that could be
the product of similar design or mental templates. Groups were progressively refined, and
clusters with comparable distributions were merged into higher-level types. Consistency and
robustness of the obtained types were iteratively tested through comparison with indepen-
dent information and other collections. Types were then formally described and finally used
for cross-cultural comparisons.
In Krieger's work, ,types emerged as artificial entities which defined particular instances
of association between a determined number of variables. These units were distinct from
the empirical objects that may or may not have belonged to a given type (Dunnell, 1986: 171;
O'Brien and Lyman, 2002: 39-40). At the same time, when Krieger proceeded toward
interpretation and archaeological inference, types were implicitly considered as phenom-
ena of the real world, a conflation of analytical units with observed patterns (Krieger, 1944;
Cochrane, 2001; O'Brien and Lyman, 2002). Therefore, his seminal paper reiterated the idea
of types having a chiefly chronological relevance, as well as the incongruence between "types
as mere tools" and "types as existing entities or mental templates:'
The post-war discussion on typology is exemplified by the so-called Ford-Spaulding
debate. james Ford's contribution to the notion of type consisted of a long sequence of prob-
lem-oriented works, aimed primarily at systematizing ceramic materials of the American
southeast (Ford, 1938, 1952; see also Dunnell, 1986, for a more detailed discussion),
658 EUGENIO BORTOLINJ
···················· ....................

STEP .QliS: sorting into working

patterns of distinct structural plan.

STEP TWO: sorting into detailed

working groups each consistently
combining features in but one way.

SlffTHREE: recombining
working groups into tentative
types on basis of comparative
distribution and associations of
working groups. (x) transferred from
working grpup of
another pattern
STEP FOUR: consolidation of types through further testing for consistency in form and variation.
STEP FIVE: description and illustration of types with full range of vQriations.
~$!!\:(a) determination of series of linked types; (b) determination of material-culture complexes;
(c) determination of type relationships in related cultures.

FIGURE 35·3 The original diagram by which Krieger explained in detail the procedure for
a correct application of his typological method. (Reprinted \Vith permission from Krieger,
1944:279, fig.2s.J

and of a single, programmatic paper on the concept of type (1954a). Ford's work effectively
shifted the focus of typology from lithic industries and other classes of material culture to
pottery (Ford, 1938, 1952; Dunnell, 1986). Ford used types as instruments, abstract concepts
that were arbitrarily formed by selecting specific attributes. In his view space, time, chance,
and the derivative mechanism of cultural drift strongly affected the formation of archaeo-
logical records (Ford, 1954: 52). Therefore, archaeological types encompassed these processes
in addition to actual individual choices (ibid.).
In the same years, Albert Spaulding published a paper (1953) in which he strongly
opposed the notion of types as artificial instruments created ad hoc by archaeologists.
If, as culture historians claimed, types represented mental templates equivalent to
ethnographic cultural behaviors, they had to be considered as real entities belonging
to the past. 1he only way for archaeologists to avoid discretion in type description was
to make types emerge as non-random patterns from raw data. This could be achieved
through the application of rigorous and explicit statistical techniques based on attribute
association. Spaulding's approach, predating the requirements of Processualism and
New Archaeology, aimed at replacing the iterative testing of the Krieger-Ford approach,
and directly addressed the issue of types' cultural-behavioral value. Spaulding explicitly
relied on an essentialist view of types, that is, he considered types as real entities (Hull,
1965a, 1965b; Sabloff and Smith, 1972), and his method was purely inductive. This created
a problem of an overlap between the definition of types and their empirical test (Dunnell,
1982, 1986; Cochrane 2001), and did still not eliminate subjectivity from the critical step
of attribute choice.
 TYPOLOGY AND CLASSIFICATION 659

Spaulding's paper was followed by a heated debate (Ford 1954a, 1954b, 1954c; Spaulding
1954a, 1954b) in which two fundamentally opposed views--that of types as theoretical, arti-
ficial constructs functional to specific enquiries and that of types as existing entities that
could naturally emerge from the noise of empirical data-confronted each other. Ultimately,
Spaulding won the debate and had a greater influence on the research of the following
decades, as it was more in line with the changing attitude of archaeologists toward function
and behavior.

CLA§§E§ AND GROUP§

Over the last thirty years, archaeological sorting methods have been refined, elaborated on,
and perfected. Nevertheless, all typologies and classificatory arrangements in the literature,
no matter how sophisticated, are rooted in one of the models proposed by Rouse-Krieger-
Ford on the one hand and Spaulding on the other. All systematic arrangements may be
conveniently divided into deductive (top-down) classifications and inductive (bottom-up)
grouping methods (after Dunnell, 1971).
Deductive classification consists of generating theoretically derived units (classes). In
other words, a number of diagnostic attributes and a particular observational scale are
selected depending upon the initial research question. Membership in each class, by any
of the observed objects, is defined by the exhibition of these attributes (Dunnell, 1971: 15).
Deductive classificatory processes constantly test and update theoretical units based upon
the available evidence (as suggested by Krieger). Classes, therefore, are tools produced to
verify expectations about the relationship between categories (Dunnell, 1971: 24).
In a deductive classification, a class can be structured according to two different princi-
ples: monothetic classes, which assume diagnostic attributes that are mutually exclusive and
represent the necessary and sufficient condition for an object to be included in a given class;
and polythetic classes, in which classes are defined by the collocation of a number of diag-
nostic attributes, none of which alone can ever be considered as necessary or sufficient. In a
polythetic system attributes are never mutually exclusive.
An example of monothetic approach is paradigmatic classification (Dunnell, 1971;
O'Brien et al., 2001, 2002; O'Brien and Lyman, 2002a, 2002b). This system produces a non~
hierarchical arrangement of classes defined by the necessary and sufficient exhibition of
equally weighted, mutually exclusive attributes. The high level of redundancy offered by this
method has proven to be particularly useful in tracking change over time and investigating
cultural phylogenies (O'Brien and Lyman, 2003).
The primary weakness of monothetic arrangements is that, in order to create classes that
are strictly defined by necessary and sufficient conditions, the number of attributes that can
be used is considerably lower than all the possible dimensions of variation observable in the
data. Therefore, this classificatory approach simplifies empirical reality by focusing on only a
limited number of diagnostic variables.
The term polythetic was first coined in biology by Sakal and Sneath (1963), and was
adopted into archaeology by David Clarke in 1978 (Clarke, 1978: 35ff.). Clarke claimed that,
unlike natural phenomena, cultural entities could not be forced into strictly monothetic
parameters. Artifacts and products of human culture could be systematically described, but
660 FUGENIO BORTOLINJ

not severely defined by necessary and sufficient attributes. A polythetic approach to classifi-
cation enables the archaeologist to preserve most of the available infOrmation about artifact
variability and respects the idea of continuous variation in the real world, although these
features make it more challenging for the analytical and inferential stages of research.
A theory-driven or deductive classification, whether monothetic or polythetic, conceives of
classes and types as heuristic tools, in other words theoretical units with no necessary coun-
terpart in the real world, and uses these tools to answer specific research questions about a
specific dataset (Klejn, 1982). Deductive classes are abstract models distinct from the groups
of objects they create, and function as an ideational meter of comparison for empirical
observations.
In inductive grouping archaeological materials are observed and divided according to
shared attributes, and types emerge from the analysis itself. Therefore, groups are not prede-
termined theoretical units; they are purely empirical units overlapping with their own defi-
nition, with no distinction being made between actual assemblages and the conditions for
membership in each group. This approach derives from Spaulding's definition of type and
has benefited from the increasingly efficient development of clustering and distance-based
phylogenetic algorithms (Whallon, 1972, 1982; Read, 1982; Whallon and Brown, 1982).
The inductive method is both viable and indicated for the initial exploration of archae-
ological datasets through pattern-recognition techniques (Christenson and Read, 1977;
Aldenderfer and Blashfield, 1978; Hodson, 1982; Legendre and Legendre, 1998; Smith and
Neiman, 2007). Among its objectives are explicit methodological explanation and a ten-
dency towards quantification. However, as in the case of theoretical classes, inductive
grouping methods have some important limitations (Dunnell, 1971, 1986). For example, the
approach is not designed to test hypotheses or to infer processes assumed a priori (Read,
1987). In addition, this approach supports an essentialist view, in which "natural" types
emerge from data and represent mental templates existing in the real world (Hull, 1965a,
1965b; Read, 1987; although see Hill and Evans, 1972, for a critical review of this epistemo-
logical problem).
To conclude, groups and types obtained by inductive ordination may result from gen-
eralizations based only on observed phenomena (Willer and Willer, 1973; Dunnell, 1982;
Cochrane, 2001 ). The potential issue is that units obtained through empirical gener-
alizations are easily falsifiable; they are unable to change or adapt. Rather, these units are
stretched to cover an increasing diversity in the available evidence, and eventually succumb
to continuously emerging exceptions.

How MANY TYPOLOGIES AND CLA§§UICATWNS?

The systematic arrangement of materials, particularly ceramics, is one of the most common
and critical activities in archaeology. Researchers can adopt different theoretical perspec-
tives, a number of possible methods, and almost infinite attributes to describe variation in
equally valid and useful ways (Sinopoli, 1991: 44). Specialist, applied, and generalist litera-
ture on the topic is considerable, and every author explicitly or implicitly emphasizes the
approaches and perspectives that she or he considers more applicable.
F
TYPOLOGY AND CLASSIFICATION 661

But '\.vhich is the right ordination method?" The quick answer is that there is no right or
wrong arrangement of artifacts or ordination method (Hull, 1970; Sinopoli, 1991). There are
simply techniques that can be designed and adapted for individual datasets or to answer spe-
cific questions. Some arrangements may not be appropriate for some contexts, but this does
not make them invalid in other contexts or for other questions. Every systematic approach
has its problems and limitations. It is important to be aware of these issues, and to be explicit
in detailing the chosen method and its pitfalls (Krieger, 1944; Dunnell, 1971).
The first choice that researchers have to make when designing a classificatory strategy is
between structuring their types, classes, or groups in qualitative or quantitative terms. The
former refers to the identification of nominal or categorical variables as diagnostic attributes
(color, shape, formal aspects, decorative motifs) in order to observe their presence or relative
frequency within a context. The latter refers to higher-level variables that can be quantified
at ordinal, interval, or ratio scale (Shennan, 1998: 8-12) and usually focus on aspects of aves-
sel that are directly measurable, such as height, width, diameter, angles, percentages of ware
components, and so on.
Describing the distribution of attributes in a quantitative fashion is the most appropri-
ate way to provide explicit, sharable, replicable, and testable units or types. However, it is
worth remembering that any ordination process is based on the subjective discrimination
of specific qualities over others. In other words, archaeologists choose what to observe and
measure, depending on their questions and objectives. This choice is arbitrary by defini ¥

tion. Therefore, any systematic description consists first of a qualitative process drawing
on discrete variables or attributes, followed by the quantification of attribute distributions
(Dunnell, 1971: 54-55).
It follows, therefore, that the mandatory first step in any classification is attribute selection
(Rice, 1987: 285). Ceramics possess a seemingly infinite number of measurable attributes,
characteristics, and dimensions. Therefore, the choice of diagnostic attributes should be ori-
ented toward answering specific questions on specific sets of data. Attributes might consti-
lute the best scale of analysis, in which case they should be consistently observed through
time and space. Alternatively, spatially and/or temporally bounded aggregates of chosen
attributes can be selected. In the latter case, observational units consist of the product of
an ordination process, whether these are types, classes, or groups.
As far as the systematic description of ceramics is concerned, dimensions of pottery
variability may be roughly divided into formal dimensions and technological dimensions
(Sinopoli, 1991: 56-65: Orton et al., 1993: 152-165). The former refer to observations concern-
ing the shape of the entire vessel, the shape of any specific components of the vessel, or any
type of surface treatment (Rice, 1987: 287). Entire vessel shapes can be described by using
established typological categories or developing new ones. Some formalized descriptions of
individual vessel parts have been published (Gardin, 1976, 1978, among others), and can be
used to achieve a more standardized and replicable representation of vessel design.
Alternatively, and preferably, description of shapes can be reached through direct mea-
surement and quantification of relevant attributes. The use of complete or almost complete
vessels is preferable, in order to reduce the risk of sample inflation and inference over a
non-representative assemblage, although a number of techniques have been developed to
overcome these limitations (Orton et al., 1993; Orton, zooo). An entire vessel shape might
be directly compared with abstract or primitive geometric forms (truncated or overlapping
662 EUGENIO BORTOLINI

cones, cylinders, spheres, ellipsoids, etc.) or '.vith several composite forms in order to sys-
tematically measure volume (Shepard, 1956: 233; Gandon et aL, 20u).
Measurement of both complete vessels and fragments of shapes is possible by theoretically
slicing the vessel into standardized horizontal sections and 'measuring the absolute radius of
each slice (Wilcock and Shennan, 1975), the relative distance from a tangential imaginary
line, or mathematically describing body curves (see Orton et aL, 1993: 159-163, for a detailed
discussion). These methods have greatly benefited from the increasing use of informatics
(Gilboa et aL, 2004; Kampe! and Sablatnig, 2007; Martinez-Carrillo et al., 2009, to quote
some recent examples). Vessel size is most commonly a measurement of absolute height
and diameter, lip angles, shoulder angles, angles at the base, thickness of rim, neck, body,
and base (see Sinopoli, 1991: 61--62). It is also possible to classify vessels according to ratios
between pairs of the above-mentioned measures, so that individual specimens are more
directly comparable (see Figure 35.4). These procedures can be used to infer differences in
the manufacturing process, the transmission of knowledge, and the skills of individual pot·
ters (Roux, 1990; Gandon et al., 20u).
Surface treatment comprises observations on surface color, level of elaboration,
smoothness, the presence of glazing or slips, and the presence of appliques or comparable

base shape and angle ...----

-?-~--"·
L~~~-. "-~ ~.- . ._-~-·-~_______________

base diameter

FIGURE 35.4 Some quantifiable formal dimensions in pottery. It is possible to use ratios
between pairs of measures so that the effects of marked differences in absolute vessel size can
be controlled. A is a tangential, vertical line that can be used to obtain a numerical rep res en-
tation of vessel shape. Alternatively, standardized horizontal sections can be theoretically
traced and measured for their absolute radius.
!I·
TYPOLOGY AND CLASSIFICATION 663

ornaments. All these elements can be systematically described and useful classifications
can be drawn on such data. Because quantification is often more difficult for surface attri-
butes, archaeologists tend to divide them into categorical units (either presence-absence or
multistate variables) and quantitatively treat their distribution through space and time. The
classification of decorative patterns as categorical attributes has been fruitfully employed
to investigate mechanisms of cultural transmission, adoption, and selection responsible
for the formal evolution of material culture (Neiman, 1995; Shennan and Wilkinson, 2001;
Cochrane, 2009). Interesting correlations between formal attributes and potentially func-
tional characters have also been explored (Steele eta!., 2010) (see Figure 35.5).
In addition, technological dimensions can be chosen for ceramic description. Typologies
based on technological characters are comparatively rarer (Rice, 1987: 286-287). One of the
most explored attributes of ceramic wares is their composition. The chemical and miner-
alogical analysis of ceramic fabrics is often used to infer the potential raw material sources
(Neff, 1995; Mery, 2000). Tempers are used to distinguish different technical traditions, to
make inferences about functional aspects of the finished vessels that influenced individual
and group choices, and/or to generate hypotheses about the temper sources chosen by pot-
ters (Feathers, 2006). Firing techniques can be investigated through the analysis of minerals
and components in different wares, as well as through the color of both surface and core
(for example to distinguish between oxidizing and reducing kiln environments; see Rye,
1981: 114-118).

CONCLUSION

In summary, it is important to remember that:

Ordination methods have been developed to systematically arrange disordered infor-

mation contained in the empirical record.
The systematic description of material culture is at the root of archaeological practice
and significant effort has been invested in the classification of archaeological ceramics
in particular.
1he systematic arrangement of archaeological phenomena originated from the need
for reliable chronological sequences. Initial typological and classificatory efforts led to
normative approaches and involved the classifiCation of cultures supported by a unilin~
ear and progressivist view of human societies.
Later developments focused on typology and classification as tools for generating effec-
tive relative chronologies (frequency seriations), and to investigate the interaction
between individuals and human groups.
The term type, although it generally refers to an aggregate of particular characteristics
in space and time, has been used alternatively to refer to actual objects, abstract units,
mental templates, analytical tools, and groups of real entities.
As emerged in the debates over typology in the l940S and l950S, all systematic arrange-
ments, no matter how sophisticated, can be divided into deductive and inductive
approaches. The first generate abstract or theoretical units starting from a particu~
lar set of research questions. These units (classes) are then used to divide observable
(a) ri'-:---:---- ----.:~-:-----~,----.-~,-:;::~ [b) Incised lines I Lines and Impressions
" I
~i~8
I /1 ~ ~ £~ fzi!hi
'f;/1.1
::
~:
$if: ~z ~~~.
Ill ;;:~'
111
,F 18 ;;;, 30 ~~q;, 23 m38 "'.,
.
.,,,,.,
~·v
t1
l"I~H
10

/11/, I "'
"'
'"
,,:: 13
..
(j]~/s lh~
//f, ffi/ "'
Iff' 12
....
l ll !!H
!!if 19
:::·?;,...:~~\
~·<~;\,:•
',, \ /,
<::·~·::;;!.~' 20

I, ll, I 111. lZ, //,

I ~,,.,

:::,':/
~~

I ~
~
" 14

FIGURE 35·5 An example of categorical classification of pottery surface decoration from a Central European Neolithic context. a)
Two almost complete Bandkeramik vessels from Merzbach valley (reprinted \'>'ith permission from Shennan and Wilkinson, 2o01:581,
fig.2, after Luning and Stehli 1994, plate 6.3 and 29.7 ); b) diagnostic decorative motifs used for classification and to investigate poten·
tial processes of cultural transmission (reprinted with permission from Shennan and Wilkinson, 2001:582, fig.3, after Frirdich, 1994,
fig.lO).
 TYPOLOGY AND CLASSIFICATION 665
,,,,, '

phenornena, and each class may or may not have an actual counterpart in the real
world. 1be second approach allows analytical units to emerge from empirical data as
"natural" groups based on shared attributes,
It is impossible to create a single classificatory structure for general purposes or to
answer questions that are not theory and context specific (Hull, 1970 ), In fact, different
sorting methods need to be developed to meet the requirements of different contexts
and datasets. In addition to the choice of an appropriate observational scale, attribute
selection is the most critical step to build effective units (types, classes, or groups),
The explicit definition of categories and the replicability of their quantitative evalua-
tion make classificatory practices the most amenable to communication and problem-
oriented archaeological enquiry,
Ceramic materials can be arranged according to a vast number of variables. These com-
prise both formal dimensions (shape and size of entire vessels or their portions, surface
treatment), and technological dimerJsions (composition, firing techniques, tempering,
and manufacturing processes).

A famous quote by Box on model building stated that "all models are wrong, but some are
useful" (Box and Draper, 1987: 424), This means that all abstract representations of reality
elaborated by researchers are, by definition, distinct from reality itself (from a linear meter
to increasingly complex simulations, from weight units to mathematical abstractions). By
pointing at selected elements models offer useful and often repeatable comparisons with
observed phenomena. For us to understand and explain the empirical world, models need
to be rejected and hypotheses need to be tested; only then can causal processes be inferred.
In the same way, one could state that all classes and types are wrong, but some are use-
fuL All arrangements of empirical objects conducted by researchers are models of reality,
Types, classes, and ordination systems constitute, for the archaeologist, a door connecting
a theoretical, abstract) or ideational level to an empirical, material, or phenomenological
level (Dunnell, 1971: 26-30). In order to generate knowledge, the archaeologist has to move
between these worlds in both directions, which means she or he must view material culture
both deductively (from theoretical to empirical, or top-down) and inductively (from empiri-
cal to theoretical, or bottom-up; Willer and Willer, 1973), Types and classes, therefore should
offer a controlled, repeatable, and formally testable background against which observed
phenomena can be measured in order to answer specific questions.
As in the case of models, building problem-oriented types and effective classificatory
systems implies the simplification of reality. The large amount of variability expressed by
human actions at an individual level has unpredictably broad consequences at the popula-
tion leveL Artifact variation in a population generally results from the cumulative effect of
change, innovation, and taphonomic processes through space and time. If an ordination sys-
tem is limited by the investigator's criteria and purposes) it cannot encapsulate this immense
range of variability. Rather) it must consistently represent a smaller number of dimensions
in order to account for at least some of their causative processes, and to avoid drowning the
investigator in the flood of data generated by the richness of individual creativity (Filippucci,
20ll:l90).
It has been pointed out that there is no fixed or optimal number of attributes that an
archaeologist should include in her or his descriptive system. On the one hand, the more
attributes or characteristics analyzed the more accurate the description. However, if a
666 F.U<lFNTO BORTOT INl

cautious researcher considered all the possible attributes of an object in her or his descrip-
lI
tion, she or he would end up with an exact replica of the object itself which would dearly not
be very helpful in exploring variation, its possible causes, or its patterning and directionality.
This archaeologist would find herself or himself in a sea of variability with only a 1:1 map of
it, unable to focus on information of immediate importance; and, ultimately, she or he would
be forced to abandon the search altogether.

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 CHAPTER 36

DIRECT DATING METHODS

SOPHIE BLAIN AND CHRISTOPHER HALL

INTRODUCTION

DATING an artifact or an archaeological site is a critical component of any archaeological

investigation, providing not only chronological weight and facilitating determination of the
duration of its use or occupation, but also situating the object or site within a (pre-/proto-)
historic context 1hese questions, and those contingents upon them, can only be answered
by a thorough dating of the object or site.
In the case of ceramics, regardless of whether they have an aesthetic, domestic, or archi-
tectural function, their primary chronological attribution is typically achieved typologically.
The difficulty with relying upon typological dating, established by analogy and comparison
of shapes and styles, is that it is often based upon circular reasoning: if a type, considered
to be a chronological marker, is dated incorrectly, then the house of cards collapses since
all the other ceramics which have been dated by comparison will also be incorrectly dated.
Therefore, it is necessary, if not fundamental, for these typologies to be built upon a robust
foundation, that is, on indubitably dated objects. Furthermore, typochronologies are usu-
ally only applicable to prestigious or fashionable pottery which goes into and out of vogue,
and not to ubiquitous common and utilitarian wares, such as cooking pots and storage ves-
sels. And yet, dating the latter would facilitate the dating of many archaeological contexts for
which stratigraphic and/or radiocarbon dates are not possible or practical.
During the second half of the twentieth century, a number of archaeometric methods
were developed aimed at dating archaeological ceramics directly, using their physico-
chemical properties rather than formal or stylistic attributes. Tbe choice of which direct
dating method to use depends largely upon the material and archaeological question to be
answered. Tbe type and quantity of the former determine the type of analysis (destructive
or not) which can be carried out, and the latter conditions both the selection of the samples
(their representativeness) and the analytical method used. It is also important to consider
the precision of the analytical method and confirm that it fits with the chronological resolu-
tion required to answer the archaeological question. Furthermore, a retlection must be made
on the dated event while applying chronometric methods on a ceramic: is the event dated
the artifact itself or an element associated to it? What is the connection between them? Does
dating a ceramic mean dating the occupation of the site? Furthermore, it must be kept in
672 SOPHIE BLAiN AND CHRISTOPHER HALL

mind that dating a ceramic artifact might only provide a terminus post quem to the archaeo-
logical occupation of the site or the building of the wall; for example, if the manufacture of
the object is not strictly contemporary to the archaeological event. The most suitable dating
method is the one which is best adapted to the nature of the material to be dated, its context,
and the specific research question. Two of these methods, luminescence and rehydroxyl-
ation dating, are discussed in detail below.

LUMINESCENCE DATING

Although the idea of using this progressive phenomenon was suggested by Daniels,
University of Wisconsin (USA), in 1953, it is mainly the Oxford Luminescence Dating
Laboratory (UK) that played the fundamental role in stimulating the worldwide develop-
ment of luminescence dating (Zoller and Wagner, 2015). At the end of the 1960s, the first
reliable thermoluminescence (TL) dates were obtained for archaeological ceramic material
(Mazess and Zimmermann, 1966; Ralph and Ham, 1966), first on pottery and later on archi-
tectural bricks (Kasa et al., 198+ Goedicke C., 1985). The optically stimulated luminescence
(OSL) method, deriving from TL, was developed in the 198os-90s and its first applications
on archaeological ceramic were published in zooo for both pottery (Oke and Yurdatapan)
and brick (Bailiff and Holland). An overwiew of the method applied on pottery and bricks is
given by Bailiff (2015).

Background
Physics of the Phenomenon
TL and OSL are radiogenic dating methods that use the property exhibited by certain crys-
tals of emitting light when stimulated with heat or light following irradiation with ionizing
radiation (Aitken, 1985, 1998; Duller, 2015).
Within ceramic materials, minerals such as quartz, feldspars, and other aluminosilicates
have the capacity to store the cumulative effects of ionizing radiation. Natural sources of
radiation are present within the ceramic and its environment in the form of isotopes of ura-
nium, thorium, potassium, and rubidium. These isotopes undergo radioactive decay and
emit alpha and beta particles, and gamma rays. Cosmic rays also make a minor contribution
as a radiation source. These types of radiation carry energy which is absorbed by the ceramic
(referred to as the absorbed dose), and during this process, atoms within crystals are ionized,
liberating electrons. Some of the electrons are subsequently trapped by crystal defects and
the number of trapped electrons builds up over time.
During firing of the ceramics bodies (above 4oo'C), all previously trapped electrons are
released and, following this resetting process referred to as the zeroing event, the crystal
defects or traps begin to acquire electrons again. Since the radiation dose received is deliv-
ered at a low and steady rate (depending on the concentration in naturally occurring radio-
nuclides in the ceramic and its environment), the total quantity of trapped electrons, which
is related to the cumulative radiation dose, is proportional to the time elapsed since the
 DIRECT DATING METHODS 673

Absorbed dose

r '
/ '
' /
1>:'
AGE
/
:<::,
•••...
Time

sf~
\;1:'#','
dJ:;:W ~
FIGURE 36.1 A zeroing event resets the material by releasing electrons trapped during
since the formation of the crystals. In the case of ceramics this is achieved by heat during
firing, but in the case of unheated sediments this can be achieved by exposure to daylight.
The archaeological clock starts from this event. The radioactive elements within clay of the
pot and within the surrounding environment (e.g., burial medium) deliver a radiation dose
at a steady rate (the annual dose), the cumulative effects of which are stored in the crystals.
By extracting the crystals from the sample in the laboratory and stimulating them all the
trapped electrons are released, producing luminescence which can be detected and mea-
sured. The intensity of the luminescence is related to the time elapsed since the zeroing event.

firing of the pot (Figure 36.1). This time span is calculated as the ratio of the cumulative dose
(termed "paleo dose" and expressed in units of gray, Gy) and the dose rate (mGyper year).
Thus the luminescence age equation can be expressed as follows:

Luminescence Age(years )=Paleodose (Gy )!Dose rate(mGy/year)

When crystals extracted from an archaeological ceramic are stimulated in the laboratory
they release the stored electrons as light or luminescence, the intensity of which is related
to the size of the paleodose. 1bere are two ways in which the crystals can be stimulated-by
heat (thermoluminescence) or by light (optically stimulated luminescence).

Description of the Luminescence Signal

When measuring TL, the minerals are thermally stimulated by heating at a constant rate (e.g.
5°C/s) from room temperature to, typically, soooc. Electrons, trapped in specific energy levels
or traps, are freed only at certain temperatures, reflected as peaks in the TL curve (Figure 36.2),
which is produced by plotting the intensity of luminescence emitted (Y-axis) against tem-
perature (X-axis). The position of each peak indicates the amount of thermal energy required
to release the electric charge from a certain trap type, and consequently the mean lifetime
of electrons stored in the trap at ambient temperatures. Only traps that store charge over an
 SOPHIE BLAIN AND CHRISTOPHER HALL
l
4000 l 325

&='
N
30001
"' c
0
0

""
?
·~
c
20001

l'
.s 1000 .
~
~

Temperature [0 C)

FIGURE 36.2 TL glow curve on quartz grains with the various characteristic peaks and a
total OSL decay curve, made of its different components. The surface under the peaks or sig·
nal is a function of the number of traps occupied before the stimulation.

6ooo T
-===Total

""w - - Medium+ 51
""'"~'=Fast
d

"'
c
0
0
--52+53

""?
-~
c

-~
~
2000
v;
0
1000

10 20 30 40
Time (s)

FIGURE 36.3 TL glow curve on quartz grains with the various characteristic peaks and a
total OSL decay curve, made of its different components. The surface under the peaks or sig·
nal is a function of the number of traps occupied before the stimulation.

archaeological timescale are suitable for dating purposes. In the case of quartz minerals, the
two TL peaks generally used are located at 325"C and 375"C.
When measuring OSL, the crystals are stimulated by light of a particular wavelength (dif·
ferent from that of the luminescence) using a source of constant intensity. The OSL signal
obtained (Figure 36.3) is in the form of a decay curve when the intensity of OSL (Y-axis) is
plotted as a function of the optical stimulation time (X-axis). The OSL signal is a compos·
ite of components of differing rates of decay including an ultrafast, a fast (the main one in
quartz, also used for dating purposes), a medium, and a more slowly decaying component
(Duller, 2015).
 DIRECT DATING METHODS 675

Principle of the Method

The various protocols, techniques, and methods to measure the paleodose compare the
natural luminescence signal (related to the paleodose to be determined) with regenerated
signals deriving from known doses artificially given to the crystals in the laboratory (Murray
and Wintle, 2ooo). The integral of each signal within a given temperature or stimulation
time range is used to plot luminescence intensity versus dose, from which the paleodose
responsible for the natural luminescence signal is deduced.

Applicability of the Method

This method may be applied to any fired mineral material and/or any mineral material suf-
ficiently exposed to light. Containing quartz, feldspars, and other aluminosilicates, pottery
and ceramic building materials thus constitute good sample material for this method.
The chronological range of luminescence dating varies from one sample to the other.
However, the lower chronological limit depends on the detection threshold of the facilities,
in other words the differentiation between the background and the lowest intensity of a dim
luminescence signal from a young sample, for instance. In view of the current technological
progress, even a wo-year-old ceramic can be accurately dated.
In the case of archaeological ceramic dating, the main requirement for the datability of
the sample is related to the full reset of the chronometer, for example a heating above 400°C
or an efficient bleaching. Since the upper dating limits of TL and OSL are respectively con-
sidered to be about one and half a million years, and since the oldest ceramic in the world,
the Venus ofDolni Vestonice (Czech Republic), has an estimated age of z6,ooo years, every
existing ceramic falls within the chronological range of applicability and, theoretically, can
be dated by TLJOSL.

Analytical Protocol of the Dating

All sampling, preparation, and measurement processes are performed in darkened condi-
tions in the laboratory to avoid the resetting of the archaeological material to be analyzed.

Sampling
OSL/TL dating is a destructive method, requiring removal of a portion of the material to be
dated in order to recover the minerals which carry the chronological information; usually
the quartz and/or feldspars. The amount of bulk material needed will depend on the mineral
composition of the ceramic.
In the case of brick dating, a "large'' sample (~wo grams) is required. The sample is
obtained by using a chisel and a hammer or with a core drill ( -4-5 ern diameter) designed for
wet or dry cutting, which is more practical. Aesthetic damage of building walls is minimized
by reducing the size of the samples (using a small diameter core drill bit) and by repairing the
hole with pigmented mortar, as close to the original brick color as possible. The brick sam-
pling location strategy is designed in conjunction with an assessment of the historical and
archaeological questions to be answered. Where possible, multiple samples are taken per
676 SOPHIE BLAIN AND CHRISTOPHER HALL

building phase to check their individual contemporaneity and achieve a more precise date of
the phase, by reducing the uncertainties on the mean. Only one or two samples are required
to verify the presence of reused materiaL
In the case of pottery, 10 or so grams are required, usually by cutting, according to the
number of similar artifacts and/or the authorization obtained for sampling. If the specimen
is rare or constitutes a fine art piece, one discreet microdrilling is performed (usually under
the base of the pottery or the statue) to recover ~100 mg of powder.

Preparation of the Sample

Since the mineral grains to be analyzed must be of a specific mineralogy and size, the ceramic
sample material is subjected to a series of mechanical and chemical treatments. Although
the exact nature of these treatments may differ from one laboratory to another, in general
the bulk material will be gently crushed and sieved (grains with diameter of a few hundreds
of microns, or even less than 20 microns, are selected) and one of several chemical treat-
ments performed on the powder to get rid of any potential pollutant for the luminescence
measurements:

Decarbonation of the material with hydrochloric acid (HCl)

Removal of any organic material with hydrogen peroxide (H, 0,)
in the case of quartz analysis, feldspar removal by hexafluorosilicic acid (H,SiF 6 ) or
hydrofluoric acid (HF) etching and/or heavy liquid separation, based on the difference
of density of quartz and feldspars.

After preparation, the grains recovered are deposited on 10 mm diameter stainless discs
either as a monolayer of powder or inside individual micro holes on these discs for single
grain analysis.

Instrumentation
To determine the paleodose, these discs are mounted on the carousel of a semi-automated
luminescence reader which turns from a calibrated radioactive source (usually Sr9o/Y90,
emitting beta particles) set on top, to a stimulation source and photomultiplier tube (PM)
placed below and above the carousel respectively (Figure 36-4).
The stimulation source consists of a lifting heater and/or a light source (laser or LEDs).
The PM tube detects and amplifies the light emitted from the samples that are being heated/
illuminated. In order to cut out undesired wavelengths and let on only those corresp,ond-
ing to the quartz or other specific minerals, filters of a chosen bandwidth are placed at the
entrance of the PM tube (Thomsen, 2015).
To determine the dose rate) three contributions are calculated.

The first contribution come from the radioactive isotopes within the grains themselves;
Another one from the radionuclides external to the grains in the sample. These first two
contributions can be determined using methods which evaluate radionuclide concen-
trations and apply conversion factors, such as inductively coupled plasma-mass spec-
trometry (ICP-MS), high-resolution gamma spectrometry, and so on.
......-----~
il'

DIRECT DATING METHODS 677

FIGURE 36.4 Luminescence reader: carousel holding the disk with the crystals turning
from under a radiation source to the stimulation source (a lifting oven and/or light source)
and a photomultiplier tube to detect the emitted signal.

The third contribution comes from the immediate environment (e.g. the masonry, the
adjacent ground) of the sample and from cosmic rays.

Assessment of the latter depends upon whether the sample has been moved from its pri-
mary location or not. In the case of a known environment-for example, the masonry from
which the bricks were sampled or the archaeological strata from which the pottery was exca-
vated-either an artificial dosimeter is left in situ for a duration of several months to a year
to record the environmental dose rate or punctual measurements are performed with a por-
table gamma-spectrometer.
If the environmental contribution of the sample is unknown, which is often the case for
artifacts in museum collections, art from a private collection, or a reused archaeological
brick, then either a modeled reconstruction of the environmental will be calculated/esti-
mated based on indication or evidence of the previous original environment and the time
of the removal, or a standard value will be affected to the calculation (between 4 and 6
mGy/yr). Estimating the environmental contribution increases the uncertainty in the dose
rate and, therefore, the calculated age of the ceramic artifact In the latter case, we can there-
fore only qualitatively evaluate if the sample is old or recent (but no numerical data and
therefore age can be provided).
It is also necessary to take into account of the average moisture content of the sample
material when calculating the annual dose rate since water attenuates a, ~. and y radiation
more strongly than the clay fabric and causes the annual dose to be reduced.

Results
Data Reporting
A dating report should present the following information:

The description of the sample to be dated and its position in the stratigraphic/masonry
structure;
Details of paleodose measurement: the method (TL or OSL); the technique (single
grain, multiple grains, which minerals, which grain size); the analytical protocol;
678 SOPHIE BLAIN AND CHRISTOPHER HALL

and the values of the ratios to check the suitability and reliability of the experimental
parameters.
The different steps involved in calculating the annual dose: the choices and arguments
for the moisture content value, the radionuclide contents from the different materials of
the environment, and from the artifact to be dated.
o The age measurement and the analysis of the result according to the choices made dur~
ing the calculation process.

Interpretation of the Results

The calculated date is given as a range: uncertainties are usually at 1 sigma (68.3% oflikeness)
(Wallinga and Cunningham, 2015). '!he error associated with the age is estimated by com-
bining random errors and systematic ones. Overall, the uncertainty associated with the TL
age is typically between ± 5 and ± 10% of the age. In OSL, the experimental process reduces
this uncertainty dramatically to a relative value generally between 3 and 5%. Using either
method, dating several samples representative of the same event signifiCantly reduces the
uncertainties and increases, by statistical analysis, the precision of the final date. In TL!OSL
dating, the dated event, such as the last exposure to light or the last firing, might not be con-
temporaneous with the archaeological event being studied. In the case of bricks, the dated
event therefore will not be the building of the masonry structure, but the material manufac-
ture (Bailiff et al., 2010); although evidence for a subsequent fire in the building should be
taken into consideration. It is important to keep in mind that luminescence dates relate to
the most recent firing event to which the ceramic artifact was subjected when interpreting
the data, notably in the case of reused material. In the case of a cooking ceramic, its submis-
sion to a cooking fire above 400-500°C, temperature sufficient to reset the "clock;' is likely
to be within no more than a few years of its manufacture, gap which falls within the range of
uncertainty on the age.

Limits and Potentials

I
The acquisition of accurate dates for a site or masonry structure requires a thorough meth- j.I
,I
odology and shared effort and communication between the different actors, the archaeolo-
gist or curator and the chronologist, in order to balance the sampling with the archaeological II:,
question before proceeding to the analyses.
In order to ensure the representativeness of the samples, regarding location and
li
material, the presence of both the chronologist and the archaeologist in the field is manda-
tory. The sampling procedure must be the result of an in situ collaboration between the
~I
archaeologist, who will assess the relation of the sample with the archaeological question
and the environment, and the chronologist, who will judge the pertinence of the sam-
pling. Furthermore, this discussion will allow the chronologist to determine the burial!
II
embedding and irradiation conditions of the artifacts as accurately as possible and pro-
vide a refined analysis of the factors of change of the environmental radioactivity in space
and time.
F

DIRECT DATING METHODS 679

Once the data has been analyzed and processed correctly and dates obtained, but before
reaching any conclusion, an open discussion between the two experts must be conducted in
which a close examination of the results is performed in the light of the considered hypoth-
eses from the field and/or pre-existing interpretations.
To conclude, it should be kept in mind that, though the data provided by luminescence
dating for a homogeneous material found in its primary position are reliable, there are lim-
its for accurately dating heterogeneous material or artifacts without known environment,
where the situation is more complex. Despite the fact that TL can be used for authentication
purposes on a small amount of powdered material, for dating purposes, the OSL and TL
methods remain invasive.
A last but crucial requirement is that, since OSLand TL are radiogenic methods, it is abso-
lutely essential that the samples have not been exposed to any artificial irradiation prior to
their analysis and, in the case of OSL dating, have been exposed to as little light as possible.
The potential of the TL/OSL methods are numerous. In the case of ceramic dating, the
chronological range of the method largely exceeds the historical span of ceramic produc-
tion, so any brick or pottery should be able to be analyzed.

CASE STUDY: THE CERAMIC BUILDING MATERIALS

(CBM) OF CHIPPING 0NGAR'S CHURCH (UK)

Chipping Ongar is a little town in southwestern Essex located at the crossroads of several
roads, one of which leads to London (at 40 km), and is situated at the confluence of the River
Roding and Crispey Brook, on London clay.
The church originally consisted of a long and narrow nave (18 x 7 m) and a rectangular
long and narrow chancel (9 x 5.5 rn), to which were added in the fifteenth century a bell
tower and in the nineteenth century a south aisle and a vestry (RCHM, 1921: 51-52). 1be -1
m wide primitive walls are made of well-laid flint rubbles, some fragment of Caen stones
and a single row of CBM. CBM is also present in quoins and the original south doorway,
which has later been blocked. Bricks mainly show a red-orange color on the surface, while
the core seems to be reduced (gray-colored); their fabric is substantially homogeneous with
a number of inclusions and they are sand-tempered. The mean size of the entire bricks into
the building is -380 x 190 x 38 mm, although lots of them have been used broken in half or in
thirds. Another minor group ofbricks shovvs the smaller size of ~230 x 170 x 35 mm.
Remains of the original windows-long round-headed windows, with slight chamfers
dressed with Caen stone-visible in the side walls of the chancel and the north wall of the
nave allow the earliest building to be assigned stylistically to the early Norman period, at
the end of the eleventh century (RCHM, 1921: 51; Powell, 1956: 162; Pevsner and Radcliffe,
1965: 125; Taylor, 1978: 8o).
1bere is no known Anglo-Saxon or Norman written source which explicitly refers to
the church, the latter having been mentioned for the first time in 1210, in the accounts of
Robert Peverel, farmer of Ongar. However, the notion of the manor described in earlier
sources tends to suggest the existence of an associated church, as most parish churches in
680 SOPHIE BLAIN AND CHRISTOPHER HALL

Essex originated as manorial churches and the church is usually close to the site of an ancient
manor house whose lord possessed the advowson. Therefore it can be supposed that a church
existed in Chipping Ongar at least since the Saxo-Norman period. Indeed, the earliest refer-
ence to Ongar goes back to 1043-5, in the will of the thegn Thurston (Sawyer, 1968: n. 1531),
in which it is indicated that the manor of Ongar is held by his wife JEthelgyth (Wareham,
zoos: 68-74), the latter also being mentioned in the Domesday Book (Powell, 1956: 159). The
manor was then passed to Ingelric, a high status priest likely of Germanic origins, impor-
tant in Edward the Confessor's court (Taylor 2002: 223-231), and from 1086 to his successor,
Eustace II, Count of Boulogne, an important Essex landowner. It then passed to the hands
of his daughter Matilda as a dowry for her wedding to Stephen, Count of Blois, future King
of England (Morant, 1768; RCHM, 1921), It was Matilda who also granted Coggeshall Abbey
land to the Savignac order in 1140.
The opinions regarding the origin of the bricks are mixed. The CBM has often been
described as reused Roman bricks. This assumption is based on the Roman archaeologi-
cal remains discovered in the eighteenth century in the graveyard of the parish (Muilman,
1770, 316-317; Gough, 1789: 51; Wright, 1836: 330 ), suggesting that Roman building materials
would have been available for the building of the church. However, based on typological
criteria (size and fabric), Rodwell (1998), Drury (zooo), and Ryan (1996) do not consent with
the Roman identification, and assign them to a medieval period. The former even designates
them as "great bricks:' a type which was first identified at the twelfth-century Cistercian
abbey at Coggeshall, located 45 km from Chipping Ongar. However, and despite both being
linked with Matilda, the bricks from each site are not comparable, since the great bricks' size
is 330 x 160 x 50 mm.
'Iberefore, doubt over the origins of the bricks from Chipping Ongar remained. In order
to elucidate the question, OSL dating was performed on four bricks sampled by wet core-
drilling. Two come from the primitive doorway of the southern nave, another one from the
southeastern quoin of the chancel, and a last one from a rubble at the south angle between
the nave and the chancel, all taken in the primitive masonries of the church,
The samples were analyzed in the Luminescence Dating Laboratory at the University of
Durham. The paleodose values were determined with the OSL method, while the internal
grain contribution to the dose rate was determined by ICP-MS (inductively coupled plasma-
mass spectrometry), the brick matrix one by high-resolution gamma-spectrometry and~­
TLd (~-thermoluminescence dosimetry) and the environment one by in situ dosimetry.
The obtained values providing homogeneous dates for the production of each of the four
bricl~1 (AD 1060 ± 64; 1011 ± 68; 1025 ± 61; 1005 ±58 at 1 o), they can be considered as being
contemporaneous and therefore the calculation of the pooled mean gives an overall date of
AD 1025 ± 56 for the manufacture of the bricks (Bailiff et al., 2010 ). This result is consistent
with the earliest phase of construction of the church.
The results confirm that bricks are neither Roman reused CBM nor Coggeshall-type
ones, but are amongst the earliest post Roman specimen of bricks. Owing to the histori-
cal context of the church (its association with the Count of Boulogne), an importation
of the material from the continent could have been suggested since there is evidence
of early medieval brickmaking in France (Blain, zou). However, chemical analysis
(ICP-AES) (Hughes, 2009) shows the clay supply was likely local rather than imported,
suggesting therefore that these early post-Roman bricks would be a precursor to the
Coggeshall type.
 DIRECT DATING METHODS 681

This example is not unique, since a brick from Bradwell-juxta-Coggeshall (AD 1038 ±
6o) also appears, thanks to OSL dating, to be pre-twelfth-century material (Bailiff et al.,
2010 ). Therefore these results tend to suggest that established brickmakers were already
established in Essex before the arrival of the Cistercians in the twelfth century (Blain et al.,
2014), the latter previously being considered to be the conduit for the (re)introduction and
diffusion of the technical know-how of brickmaking, like the Romans eleven centuries
before them.
~This scientific dating evidence indicates that a reassessment of the role of Cistercians
in the reintroduction of brickmaking through Gothic architecture not only in England
(Ryan, 1996; Rodwell, 1998; Andrews, 2oo8; Blain et al., 2014) but also in northern Europe is
required, along the lines ofPerlich (2007), who suggests a polycentric model for the develop-
ment of post-Roman brickmaking in this area, although she situates it only at the end of the
twelfth century.

REHYDROXYLATION DATING

In 2003, in a paper on moisture expansion in fired-day brick, Wilson et al. noted that their
results suggest a possible new method for archaeological dating of ceramics". The idea
sketched there was described fully in 2009 (Wilson et al.), where it was called rehydroxyl-
ation dating or, later, RHX dating. For archaeological ceramics, a general dating technique
such as RHX would be of the highest value. At present, however, RHX dating is a research
method that has not yet been comprehensively validated and, as a result, is not available for
routine use.
1be concept of RHX dating arises from the fact that fired-clay ceramics undergo pro-
gressive, long-term alteration by chemical reaction with water. Alteration produces a small
but measurable mechanical expansion, and a small associated gain in mass. When Wilson
et al. (2003) demonstrated that the kinetics both of expansion and of mass gain follow a
simple (time)''4 power law, RHX dating became possible in principle by bringing together a
cumulative material process of long duration and an associated clock. In its present imple-
mentation (Wilson et al. 2009, 2010, 2012), the primary measurements for dating a ceramic
specimen are changes in mass, made with a precision microbalance, rather than changes in
expansive strain because mass measurements can be made with much greater accuracy than
strain measurements. It is possible that other methods (such as chemical or spectroscopic
analysis) may be used in the future to determine the extent of alteration by rehydration/
rehydroxylation.

The RHX Process

The irreversible moisture expansion of fired-day brick has been known for many years, at
least since the work ofSchurecht in 1928.lt was also known that ceramic bricks fresh from the
kiln had, in the words of Washburn and Foottit in 1921, "a great avidity for moisture:' showing
mass gains as large as 1% over 120 hat room temperature. To these authors it seemed to have
been established beyond question that "burned" clay slowly rehydrates in contact with water;
682 SQPHTF Bf AIN AND CHRISTOPHER HALL

"the extent of the rehydration being dependent upon lime, temperature, and the condition of
the body" (Washburn and Footitt, 1921). The link between moisture expansion and mass gain
was made in 1962 when Cole demonstrated that, in a kiln-fired kaolinite-mica-quartz clay,
the moisture-expansion strain was proportional to the mass gain, in experiments lasting 90
days. Also in 1962, Heller et al. introduced the term rehydroxylation for the recombination
of water with clays which had been dehydroxylated (that is, had lost chemically combined
hydroxyl ions) during firing. In the context ofRHX dating, the term rehydroxylation serves
to emphasize that the long-term recombination with water is a chemical reaction within the
fired-day mineral assemblage, not a physical adsorption process. There are many studies of
rehydroxylation in individual clay minerals (reviewed by Hamilton and Hall, 2013). Clay min-
erals commonly lose hydroxyl ions at firing temperatures of soo-6oo'C to form dehydroxyl-
ated meta-clays, which rehydroxylate when exposed to water vapor on cooling.
Studies of alteration in archaeological ceramics are few. Kingery (1974) found by ther-
mal analysis that archaeological ceramic specimens originally fired at below 700°C-8oooc
reacquire many of the characteristics of an unfired clay over several millennia:' Shoval et al.
(1991) detected similar rehydrational changes in Bronze and Iron Age pottery by infrared
spectroscopy. Long-term alteration has also been reported in some non-clay minerals found
in fired-day ceramics: for example, goethite forms slowly when iron minerals are present, as
does analcime in pottery made from calcareous clays (see Hamilton and Hall, 2013). These
alteration minerals may contribute to mass changes in RHX dating procedures.
While the mineralogy of rehydroxylation was mapped out minutely by clay scientists,
little attention was paid to long-term RHX kinetics. But for those working on moisture
expansion in bricks, understanding these processes was critical for controlling progressive
damage in structural masonry. Several studies (e.g. Smith, 1993) reported expansion-strain
data over periods as long as 65 years. Re-analysis of published data strongly confirms the
correctness of the (time)' 14 power law for moisture expansion (Hall etal., 2011; Hall and Hoff,
2012), providing proxy justification for using the (time)' 14 power law in RHX dating. Data at
the longest times do not indicate any deviation from the power-law description. Gravimetric
studies confirm that RHX mass gain is also well described by the (time)" power law over the
short times used, with n equal or dose to 0.25 (Hare, 2012; Nachasova and Burakov, 2012;
Wilson et al., 2012; Barrett, 2013).

RHX Rate Equation

The fundamental RHX rate equation based on the power-law model ofRHXkinetics is:

y = a(T)t'1' Equation 36.1

where y is the fractional RHX mass gain at time t, and a the RHX rate constant of the
ceramic. For any material, a varies with temperature T; a varies also from material to mateH
rial, depending on the ceramic mineralogy, and the maximum temperature and duration of
firing.
Values of a for day ceramics are in the range 1-6 x 10-3 yr;c'. Taking a mid-range value, a
specimen of initial mass 1g gains 3 mg in 1 year from the time of firing, 6 mg in 16 years, 9 mg
in 81 years, and so on. The specimen mass after 1296 years is 1.018 g, and at this age the mass
 DIRECT DATING METHODS 683

increases by about 3 f..lg per year. The quantities of water to sustain the RHX reaction are tiny,
and become smaller with increasing age.
The (time) 114 power law is unusual, and does not yet have a satisfactory physical explanation.
It has been noted (by Wilson et al. (2009 ), for example) that the exponent 1/4 in Equation 36.1
suggests a "subdiffusive" process, and therefore may arise from transport of water or hydroxyl
ions along constricted pathways within the ceramic body. However, this qualitative explana-
tion is unsupported by any theoretical analysis directly related to ceramic microstructures.

The RHX Age Equation

"The purpose ofRHX dating is to determine the age ta of a ceramic specimen from laboratory
measurements of the RHX rate constant a and of the fractional lifetime RHX mass gain y,.
The quantity t, is the time between firing (manufacture) and dating. It follows from Equation
36.1 that for an individual ceramic specimen:

Equation 36.2

Humidity Effects
Laboratory experiments (Drelich et al., 2013) confirm that the rate of the RHX process does
not depend on the ambient humidity. However, a ceramic specimen invariably takes up
physically adsorbed water in quantities which do depend on the humidity. This so-called T1
water (Wilson et al., 2012) is adsorbed reversibly, the quantity adjusting to changes in humid-
ity on a short timescale, such as hours or days. T1 water is considered to exist as monolayer
or multilayer molecular films on pore surfaces, and its mass increases roughly in proportion
to the pore surface area. In making RHX gravimetric measurements, it is critical to hold the
amount of T1 water constant by working at precisely controlled relative humidity (Wilson
et al., 2013). The water taken up by the RHX process is designated T2 water. Operational deli-
nitions ofT1 and T2 are given by Wilson et al. (2012).

Temperature Effects
'The RHX process is a chemical reaction, and its rate increases with temperature. This trend
is visible qualitatively in moisture expansion: expansivities are greater in warmer climates
and in summer months (Hall and Hoff, 2013). Laboratory-microbalance data (Wilson et al.,
2009; Barrett, 2013) show that the temperature dependence of the RHX rate constant a fol-
lows the Arrhenius equation, so that:

a= a exp[- 4R
0 E, (..!.-
T T
..!..JJ
0
Equation 36.3

with an activation energy E., that is a material property (Hallet al., 2012). Here a, is the RHX
rate constant at some reference temperature T0 , R the gas constant= 8.314 )/(mol K), and T,
T, absolute (Kelvin) temperatures.
t184 SOPHIE BLAlN AND CHRISTOPHER HALL

To predict the extent of the RHX process under varying temperatures, the activation
energy Ea must be known. It is assumed that Ea varies from specimen to specimen. Data are
sparse, but indicate (Wilson et al., 2012) thatE, lies in the range 40-100 k)lmol. Using a mid-
range value of 70 kjlmol, Equation 36.3 shows that the RHX rate constant a is 23% smaller
at soC than at 15°C, but 28% greater at 25°C than at 15°C, the difference arising from the non-
linearity of Equation 36.3.
An archaeological specimen, whether pottery, brick, ortile, experiences a variety ofambient
temperatures during its lifetime, from firing to dating. This lifetime temperature history T(t)
must be estimated as part of the RHX dating procedure, for example by combining histori-
cal temperature data from meteorological records with ground-temperature models (Hall
et al., 2012).
An important concept in the analysis of thermal effects in RHX is that of the effective life-
time temperature, EI.:f (Hallet al., 2012). The ELT is the single (constant) temperature T,
which gives the same lifetime RHX mass gain as that produced by a variable temperature his-
tory T(t). The ELT depends on the activation energy E, but not on a 0 • The EI.:f T, is always
slightly greater than the simple mean lifetime temperature Tm because of the non-linearity of
the underlying Arrhenius equation.
Hallet al. (2012) show that the effective lifetime RHX rate constant:

Equation 36-4

The quantity a'"' is the fourth power mean of a(t), where a(t) are values of a corresponding
to the lifetime temperature history T(t). Using Equation 36.4, T, is easily calculated.

Dating Methodology
There are no standard protocols for RHX dating, but Wilson et al. (2012) describe a proce-
dure which follows in outline.
A ceramic specimen, typically 0.3-3 g dry mass, is cleaned, washed, and oven-dried.
It is transferred to a temperature-controlled microbalance operating at fixed humid-
ity, for example 30% (as in Wilson et al., 2012, 2013). The temperature is set to a value
close to the ElT of specimen. The mass of the specimen is allowed to reach a constant
equilibrium value, indicating that the adsorbed T1 water content has stabilized. This
mass is recorded as mr Next the specimen is transferred to a furnace at soo°C and
heated for long enough to remove all the RHX water acquired by the specimen during
its lifetime.
The dehydroxylated specimen is cooled and returned to the microbalance at the same
temperature and humidity as used previously, and the mass recorded continuously. The
specimen mass increases as both T1 and RHX water are taken up. After some hours or days,
the T1 water comes to equilibrium, but the RHX water continues to increase according to the
power law. After the mass data become linear in t 114 , the mass m 4 is obtained by extrapola-
tion of the linear data to the time t = o; and the slope am of the linear portion of the data is
calculated to obtain a= a, I m.,. The quantity m4 is the sample mass including 1'1 adsorbed
water but with no RHX water. The fractional lifetime RHX mass y" = ( m2 - m,) I m." that is
to say the fractional mass loss from reheating. Figure 36.5 shows microbalance data obtained
 DIRECT DATING METHODS 68S
,--~--- --~----

2.5220

3
2.5210

2.5200
.,)
E
~ - m,
ro
2 2.5190

"1
2.5180

2.5170
0 0.5 1.5 2 2.5 3
(Timet)''' (hv~)

FIGURE 36.5 Microbalance data obtained on a Werra earthenware specimen excavated at

Enkhuizen (1979) and bearing an inscribed date AD 1605 (Wilson et al., 2012). Mass gain m
against time (time)' 14 at u.o'C and 30% RH following reheating at 500'C. T1 denotes the
Type 1 (adsorbed) water and T2 the Type 2 (RHX) water. The slope of the linear portion of
the plot m(t'14 ) equals m4 a.

on a seventeenth-century earthenware specimen. In this case, the microbalance was set at a

temperature of 11.o'C, close to the estimated ELT of 10.5'C.
It is assumed that the mass ofT1 (adsorbed) water is the same in measuring m, and m4 ,
and therefore cancels in calculating Ya· The activation energy Ea is determined in micro-
balance runs at several different temperatures. Then from the estimated lifetime tempera-
ture history T(t), the ELT is calculated, and hence finally the specimen age t, is calculated
from y, and a( T,) using Equation 36.2. For the Werra pottery specimen, we have from
Figure 36.5 values of m 4 = 2.51931 g and am= 7.124 X w· 4g h-·• 14 • The stabilized mass of the
sample before reheating and measured at n.o'C and 30% relative humidity is the quantity
m2 ; for the Werra specimen, m 2 = 2.55031 g. From m 2 and m 4 , we calculate Ya = 0.01231;
and from m 4 and am we calculate a= 2.828 x w- 4 h·- 114 at the microbalance temperature
of lLO'C. The measured activation energy is 83k)/mol. The corresponding RHX rate
constant at the ELT, 10.5 'C, is a= 2.785 x w· 4 h-' 14 Therefore, the specimen RHX age is
t, =[Y, I a(rJJ'
= 435 yrs.
Uncertainty in the estimated RHX age is discussed by Wilson et aL (2012). A number of
independent uncertainties contribute to this, related to the laboratory gravimetric proce-
dures and reconstructed lifetime temperature history, among others (Hallet al., 2012). For
the Werra specimen, the age uncertainty from these sources is estimated as ±15 years. A
further source of error lies in possible contributions to the furnace reheat mass-loss from
mineralogical changes other than dehydrox:ylation. Where these are understood, appropri-
ate corrections can be made by supplementary measurements (e.g. carbon measurements to
allow for decomposition of organic matter). Alternatively, specimens may be cleaned chemi-
cally to remove selected components.
6t>6 SOPHiE BLA1N A~D CIUUSTOPHER H/\ LT.

Critique and Status

For the moment, RHX dating is a research method under development. The RHX concept
depends on the existence of slow, long-term alteration in fired-clay ceramics in which water
combines irreversibly with the mineral fabric. TI1e RHX reaction apparently continues indef-
initely, although at a diminishing rate with increasing age. The amount ofRHX water varies
with clay mineralogy and firing history, but the change of mass appears to be described gen-
erally by the (time)' 14 power law. Therefore, a single RHX rate equation can be applied, and
for any specimen an RHX rate constant a can be determined. The RHX mass gain is insensi-
tive to the ambient humidity, but increases with temperature. The temperature dependence
of a follows the Arrhenius equation, with an activation energy that varies from specimen to
specimen. The lifetime RHX mass gain of an archaeological ceramic specimen is found from
the mass loss on reheating at soooC, and the RHX rate constant of the specimen from the rate
of mass gain of the reheated specimen. The RHX age is then calculated from the age equa-
tion, using the estimated effective lifetime temperature of the specimen.
RHX dating has been applied so far to only a small number of materials, so that its range
of application is unclear. Published results include modern, medieval, and Roman ceramics,
with instances of fired-clay brick, tile, and pottery. Little is knmvn about high-fired mate-
rials. In brick, moisture expansivity decreases sharply at firing temperatures above about
1,150°C, so that high-fired ceramics may have reduced RHX activity. Reported lifetime RHX
mass gains do not exceed 3SYo, and there is no sign that the RHX capacity reaches a limit on
archaeological timescales. In glazed materials) microscopic cracking may create pathways to
sustain the RHX reaction of the ceramic body (Hamilton and Hall, 2013).
The RHX dating method is conceptually simple but its practical implementation poses
some difficulties. The quantities of water taken up by the ceramic specimen are small, and
precise microgravimetric techniques are needed to determine the component masses. In
the laboratory, adsorbed (T1) water contributes to the specimen mass, and if not stabilized
may obscure the underlying RHX mass changes. Likewise, non-RHX processes, such as
the decomposition of carbonates or organic matter, may contribute to the observed mass
changes. In some cases, it may be difficult to reconstruct the lifetime temperature history.
Measurement protocols for RHX dating are not yet established. A physical explanation of
the (time)' 14 RHX power law would strengthen the theoretical basis of the method.

CoNCLUSIONS

Besides the two methods presented in this chapter, archaeomagnetism (AM) on ceramic
structures or bricks and radiocarbon on the organic material found within a domestic pot-
tery can also be applied.
The former aims to compare the direction of magnetization characteristic of the Earth
magnetic field (EMF) at the time of the firing, recorded by the iron oxides within the ceramic,
with a reference curve of the variations of the EMF through time. This method allows dat-
ing the last firing of the ceramic, as does TL!OSL. Therefore the two methods complement
each other. Although AM might appear to be more accurate than TL/OSL, it requires more

I
F''
DIRECT DATING METHODS 687

samples to be taken, and it is not applicable to chronological periods for -which the reference
curve has not yet been established. However, combining the two methods can also improve
the reference curve for AM.
TL!OSL methods are sample-dependent and need to be adapted to the material; like
RHX, they are not strictly speaking routine methods. Indeed, RHX, being a rather new
method, is still in a state of development, though its setup should offer a very interesting
uncertainty range.
Amongst all the dating methods which allow direct dating of the ceramic material (TL!OSL,
AM, RHX), TL/OSL proves to be currently the most often applied. The presence of organic
material within domestic pottery can offer an alternative for dating the use of the ceramic, since
if it proves to be contemporary to the organic material inside, it can be dated by the radio car~
bon method. By combining the methods, further archaeological information can be obtained.
Owing to the range of these applicable methods, before proceeding to any dating process on an
artifact, a reflection between the archaeologist and the chronologist on the input of scientific
dating methods to the archaeological question is needed to evaluate the limits and potentials
of each of these methods, and finally to determine which is the most convenient and suitable.
Whatever the method used, not only before but also and especially after the analysis in
laboratory, discussions between the chronologist and the archaeologist are required to inter-
pret the data in the most suitable way, particularly the relation between the dated event by
the scientific method and the occupation of the archaeological site, the former proving often
a terminus post quem to the latter, or the meaning of the precision range on the calculated
date (different from the duration of the occupation of the site).
Finally, since the methods described in this chapter allow dating of any type of ceramic
material, they can provide a chronological attribution not only to prestigious and fashion-
able ceramics, but also and especially to the most ubiquitous archaeological artifacts: com-
mon potteries, which are not datable by typology, and bricks often used as a common
substitute to building stone. Therefore these methods are of great interest and contribute
greatly to archaeological studies.

NOTE

For this chapter, the introduction, conclusion, and the section on luminescence dating were
written by Sophie Blain, and Christopher Hall wrote the section on rehydroxylation dating.
The chapter was completed in August 2014, and, apart from minor additions at proof stage,
cites only literature published before that date.

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 INDEX

Tables and figures are indicated by t and jfollowing the page number

abandonment 30-1,36,38, 116,191 Africa 473,475-6,570,572

Accelerateur Grand Louvre d'analyse East Africa 409
elementaire (AGLAE) 457 North Africa 158,203,273/
accelerator mass spectrometry Sahelian Africa 569
CAMS) 311,578 South Africa 480
Achar potters 477 southeastern Africa 480
Achuarwomen 191 West Africa 479
acid 128,270,272,291,312-14,337,346,403, African
408, 570, 634, 676 ata 480
amino acids 634-5 case studies 481f
digestion 408, 425 agate 346, 437, 511
dissolution 10, 403, 408-10, 418-19 agency 131,182,191-2,200
extraction 403, 408 agent-based
fatty acids 625, 632 modeling 135
leaching 317 simulation 135
soils 167, 172-4 agriculture 30, 126, 133,190,206,269,
solutions 167, 173-4 277-9,576-8
Acre 156 Agrigento 97f
actants 123-7, 129, 131,133-5, 138 Aguntum 173], 174
actinolite 2451,2511,301 Aharkoy 315
actor-network theory (ANT) 115, 123 Ahrens, L. H. 352
Adan-Bayewitz, D. 172,546 Aiser ware 417
Ada Tepe 277 Ajdanlijsky, G. 277
Advanced Light Source 450 akermanite 300
Advanced Photon Source 450, 460 Akko 65j, 66
Aegean 76 alabastra 561
stirrup jars 546, 559 Aland 278
Aegina 209 albite 241, 2451, 248-91, 292, 297t, 301
aerosols 314,400-4 Alex, B. A. 317
aesthetic algae 269-70,566-7,570
assessments 183 Alhonen, P. 278
changes 58 alkali 9, 13, 51, 155-6, 176,2471,2491,2971,
damage 675 308,338,403,438
features 490 metals 51,347
function 671 alkaline
qualities 379,473,477,479 earths 176
aesthetics 125, 129 elements 171, 174,176
Afghanistan 568 alkaloids 625,6271,632,634
692 INDEX

alluvial Anarta culture 229

clay 94-5 anatase 536
deposits 307, 3!2, 315,416/ ancient
sediments 306 activities 636, 279, 509, 566
alluvium 94, 317 ceramics 8, 88, 162,261,266,279,301-2,
alteration 4, 6, 24, 41, 49, 54-5, 87, 93, 154, 389,425,496,503-4,509,515,519-20,
!58, 162-72, 174-6,2441,2481,2501,254, 523,536,555
261,274,276,301,307,312,317,343-4, chaines operatoires 102
347,365,403,409,496-7,499,605,606, cultures 162,307, 578
613,681-2,686 earthenware 336-7
aluminosilicates 88, 295f, 2971,3341,403,437, environments 566
537,672,675 Europeans 453
aluminum (AI) 87,92-3, 95, 165, 174, 242- firing 272,275,478,488,503,607
Sit, 293, 294f, 295,297-81,332,338,346, glasses 13,305
350,369, 370f, 371,388,392, 393f, 394, heritage 451
404,406,410, 41lt, 4131,4251,426,430- human behavior 629
2,436,453,50lf,502,538,550,555,565 kilns 490
Amazon 54,477,570,572 latrines 634
American markets 267
archaeology 675 materials 628
facilities 450 objects 304
Indian burials 544 organic residues 630, 638
majolica 452 organization 114
researchers 603 paints 634
southeast 657 people 51
southwest 233,318,369,409,451 populations 577
universities 460 potters 441,488,499, 503-4
American Society for Testing and Materials pottery 162, 181, 223, 261, 279, 336, 488,
(ASTM) 346 495,501,503,509,522,632,634
Americas 76, 442 production 114, 234,490,496, 628
America/United States 74, 80, 309, 311, 315f, proteins 634
317,435,450,452,455,544,637 rice cultivation 569
amorphous 299,515,525,566 scribes 636
concentration 208-9 sherds 488, 503
materials 208, 339 societies 185,307
phases 164,166,168,300,339,493,509, stone tools 637
511,515,520,536 symbols 390
selenium 550 technology 88,334,488, 503
silica 275 times 87
solids 327 trade 305
structure 510,515 traditions 107, 110
texture 241 vessels 196,549
amphiboles 93, 239-40, 2421, 2441, 246-71, workshops 96
2501,289,292,301,306,350 Ancylus Formation 278
amphorae 21-2,30,33,60-2, 63f, 66, 171, Andalusia 591
188,211,276,288,372, 513f, 554-5,558 Andean culture 389
analcime 165,171,337f,682,seealso Andes 390
wairakite andesitic rocks 301, 306
..----------------------- INDEX 693

components 299
AndUjar 27
animals 115, 123, 125-6, !35, 266,390,566, compounds 299
570,574,625,632
grains 89
inclusions 19,208,299,459,605,607-8,
bones 544
612-13,615-17,619-20
dung 125-8,130-1,255,487,491,493,
raw materials 20-2
568,572
temper 615
material 570f, 574
apprenticeship !02, 120, 193
products 10
remains 565, 577 aquatic
conditions 277
tempers 568,570-2
environments 269-70,535,576
anisotropic
eukaryotes 266
grains 239
habitats 535-6
matrix 261
microfossils 277
minerals 239-40
optical properties 260 Arabia 135
Arabian Gulf 372
anisotropism 205, 260
Arabian Peninsula 569
annite 242t
anorthite 88, !65, 245t, 248-9t, 260,292, aragonite 241,337, 517f
300-1, 312, 336-7, 511, 516f, 519-20 Aratashen 409
archaeoceramics 288-9, 296
anthropogenic
archaeoethnography 355
inclusions 206
archaeomagnetisrn (AM) 686-7
pyrometamorphism 288
archaeometric
anthropological
analysis 22, 153, !83
archaeologists 637
characterization 27,32-3,35,39-40
assumptions 343
classification 38
context 277
community 550
inquiry 469
data 24, 150, 159,553
interpretation 628, 354
features 159
issues 343
identification 96
link 110
questions 3-4,29,217,342,357,628 images 553
research 471,625,628,638 investigation 457
laboratories 75
rules 102
meetings 162
studies 628f
methods 671
terms 196
post-stratification 39
theory 635,637
problems 25
understanding 103,447
publications 49
views 191
research 19, 21, 23-5, 28, 31-5, 43, 78,
anthropology 102
89, 115
of techniques 101,191
standards 460
antibodies 627t, 632-3
stratification 43
antigens 627t, 632-3
studies 25-6, 30, 32-3, 38-43, 49, 51, 53,
antigorite 92
99,289,363,493
antimony(Sb) 13,412-13t,425t,
archaeometry 8, 22-3,33,43,77-9, 116,
432f, 537
122-3,134,!36-7, 159,353,363
anti-Stokes scattering 532
apatite 95, 249t, 266, 292t, 309-10 Archaeometry 8, 637
archaeothermometric index 280
aplastic
694 INDEX

architecture 125,127,131,233,390,477, empire 132-3

671-2,681 Middle Assyrian carinated bowl 126, 130/
Arezzo 39, 40f 42, 168, 1691, 174 Middle Assyrian period 126, 128
argillaceous vessels 133
inclusions 234 Assyrians 132
minerals 23 5 Atamadai pottery 355
rock fragments 208, 252, 254 Athenian red-figure pottery 13
sediments 50, 92 Athens 60-1
argon (Ar) 356,391,400-2,404,497,534 atomic absorption spectroscopy (AAS) 10,
Argonne National Laboratory 450 162,327
Armenia 409, 450 atomic emission spectroscopy (AES) 401,680
Arnold, D. E. 267,275,399,438,472,475 atomic mass 426, 430, 434
Arretine atomic number 289,291-3,296, 328,344-5,
sigillata 167-8, 172 383,386/
ware 453 atoms 44,289,327-8,330,344-5,383-4,
arsenic (As) 174, 345, 4111, 4131, 4251, 436-7 400-1,427-8,433-4,538,672
art 200,266-7,382,390,544,635,676-7 Atterberg
art-historical period/phase 217f 218 cylinder 334
artifacts 4, 6, 8, 11, 19,21-2,26, 28-3!, 50, limits 98
52,71,80,87-8,96,98-9,115,119-22, Attic 459
133, 148, 149, 172, 181, 184, 189, 192, black 22, 505
233,237,266-7,270-2,275-6,279-80, ceramics 459
302,305-7,311,314,318,373,389,419, pottery 454, 559
425,437-9,443,470,565-9,571,576, red figure ware 455, 505
578,587,590,592,626,6271,629,632, ware 336
635-7, 652 .. 4, 657, 659 .. 61, 665,671-2, Auger electrons 344-5,383
676-9,687 augite 2421,2471,292, 300
artisans 12,87, !15, 121-2,124,184,471,490 Australia 415
artworks 219,221,540 Australian Synchrotron 448f, 460
Artzy, M. 79 Austria 173f 174
Asaro, E 78 autochthonous adaptation 190
Asia 450, 568-9 Ayacucho 414
East Asia 450 Aztec empire 355
Asia Minor 308
Asian backscatter 302, 417f 628, 629f see also
archaeological sites 569 Rutherford backscattering (RBS)
prehistory 654 backscattered electrons (BSE) 289-90, 292-3,
stoneware 371 294f 295f 296, 299-301, 364/
assemblages 4, 10, 13, 21, 25,29-36,38-43, bacteria 21,266,634
50,59-62,66,101-3,107-10,121,123-4, Baetulo 28f 29, 35-6, 38, 42, 44
126, !31, !33, 185-6, 196,202-3,208, Balearic Islands 193
217,227,229,267-8,273-9,301,318, Bali 569
355,374,403,417,450-1,454, 459 .. 60, Balkans 309-10,316
471,510-11,545,549,556,560,589,604, Baltic Sea 278
607-8,652-3,655,657,660-1,682 Ban Chiang 566
Assyrian Bandkeramik vessels 189,664/
administration 133 Bang Pakong Valley 569
 INDEX 695

Baq'ah pottery 546 biotite 90, 92,209-10,212,239-40,242-41,

Baranowski, M. 173f, 501/ 2491, 290f, 293
Barcelo,). A. 6 birefringence 208,239-40,2431, 2451,
barium (Ba) 95, !59, 166,168-70, 174, 176, 247-501,254,259,495
297-81,298,365,367-8,372,409,412- Bishop, G. 590
131, 417, 4251, 436, 501/ bisque 22, 499
Barnard, H. 6 Black Sea !56
Barone, G. 459 blackening 480, 499
basalt !06f, 130,301,306,309,435, 50!f, Blackman, M. ). 442
520,523 Blakely,). A. 545
bases 32,38 Blue Nile 491/
basketry/baskets 130, 132, 186, 195,266, Bohr,N. 328
477,480 bonding 156,204,256,534,612,616,622
Batan Grande 11 bones 167-8,383,442,544,570-1,
Baxter, M. ). 353-4, 356 577,635
Bay ofNaples 42 fragments 577
Bearat, H. 165, 172 temper 570-1
behavioral tissues 305
archaeology 115,119,121-3,135 tools 125
chain 30,43,121-2,130 bonfire 201,478-9,487,489-90
choices 51 boron(B) 296,4111,4131,
complexity 27 Bertolini, E. 6
rules 102 Bouchain, I. 212
value 658 Bourdieu, P. 195
beidellite 92-3 Bowser, B. 190,477
Beirut 154, !58 Box, G. E. P. 665
wares 155-6, 157/ Bragg equation 330, 332-3, 3341, 350
workshops 155-6 Bragg-Brentano configuration 329f, 333
Belgium 570 Bragg's rule 386
Belize 408 Braun, D. 603
Bell Beaker pottery 189 Brazil 54
Berg, I. 6 Brazilian pottery 373
Berthier, S. 457 Brems, D. 310
beryllium (Be) 291,350, 386j; 411t, bremsstrahlung 328-9, 348-9
4131,4251 brewing 127, 131-2
Big Data movement 73 bricks 90, 95, 97f, 130,203,279,407,411,435,
binocular microscope 9-10,12,159 442,490, 49lf, 565,605,6061,672,675,
bioclasts 294f, 299 677-82,684,686-7
biography 126,130-3, 136,237 brickmakers/brickmaking 97,680-1
biology 115,271, 306, 565-6,573,630,635-6, briquettes 99,274-5,492-3, 494f, 495-9,
655-6,659 503-4,603,605,607-8,619
biomarkers 480, 632, 634 Britain/UK 8, 311
BIORAD 312-13 British Museum 9, 77f, 554f 558-9,561
biostratigraphical Broekrnans, T. 458-9
analysis 276-7 bromine (Br) 425t, 437,625
approach 275,277 Bronitsky, G. 604
studies 266 bronze 128, 132f 172, l87f311
Bronze Age 135, 209, 267, 273, 276, 310, 3\5,
511,514,526,549,557-9,653,682
Early Bronze Age 106f, 204,209,276,459
Late Bronze Age 50, 167,277, 294f, 318,
342,355,560
Middle Bronze Age 273, 276, 560-1
Brookhaven National Laboratory 8
Brumfiel, E. M. 116
Brysbaert, A. 135
Buamunding 418
building 127, 129-30, 132, 134, 195,200,
255-6,279,480,490,546,548,555,558
560,589,603,610,665,672,675-6,678-
9,680,687
Bulgaria 277,311, 315f, 316
Bunge,M. 44
burial 51,60, 120,125,131-2,159,162-5,
167-76,233,241,252,276,296,301,312,
317,337,343,399,409,417,459,536,
537f, 544, 605-6, 673f, 678
Burk, C. 590
burnishing/polishing 9, 13, 20,104,108,237,
256,291,293,296,390,477,479,499,505
Burrough Hill 273f, 274f
Buxeda i Garrigos, ). 3, 29, 171, 342-3
Byzantine
period 290,294/
workshops 151/
cadena 121, 126, 131, 136
Caen stone 679
caesium (Cs) 51, 54-5, 166, 171, 174-5,412-
131, 425t, 432f, 436
calcareous
ceramics 163,335,337,510-11, 513f, 519,
52lf, 522,612,615
clay 88, 93, 95, 126-8, 156, 164,254-5,
259-60,336,495,520,525,612,682
illitic clay 333, 3341, 335-6
inclusions 273,417
matrices 502
microfossils 268, 270, 273-4
nannofossils 266,271-3,275,277,279-80
paste 27, 153, 155-7
pottery 164-6,168-71,173-7,336
sands 571
sherds 167, 173
calcite 88, 90, 93, 95, 164--7, 172-3, 176-7,
208,210,239,241,243t,252,255,257,
260,266,270,274-5, 292t, 335-6, 337,
441-2,495,498,504,510-15, 517f, 520,
521f,522-3,525,533,536-7,618
calcium (Ca) 13, 27, 51, 88, 93,95-6, 156,
164-8, 172-6, 242-5t, 247-Slt, 257,290,
292-3, 294f, 295f, 297-8t, 300-1,307-8,
312,317,3341,335-7,344-5,347,364,
366, 369, 370f, 391-2, 394, 411t, 4!3t,
425t, 436, 452f, 495, 501f, 502,504,533,
537-8, 546, 570f, 574, 630
Caltanissetta 97f
Campania 94t
Campanian B sherd 455-6
Canaanite
cooking vessels 523
sherds 318
sites 511,514,526
carbohydrates 625
carbon (C) 104, 164,258-9,291,492,499,
533,536-7,573,578,625,629-30,
636,685
carbonaceous material 258-9
carinated bowl 126, 127f, 128-9, 130f, 131-33
Carter, S. W. 309, 317
Carthage 203, 258/
Casagrande apparatus 98
cassiterite 452f, 537
catalhOyiik 11
Catalonia 28, 30
cathodoluminiscence 288
Cau Ontiveros, M. A 208
Caucasian pottery 409
Caverna dell'Aquila 567
celadon 409
celadonite 92
Center for the Advancement of Natural
Discoveries using Light Emission 450
Central America 267
ceramoclasts 294f, 299
cereals 568-70, 575-7
cerium 50, 95, 159,290, 294f, 410, 412-13t,
4251,432/. 436
Cerrillos Hills 318
certified reference materials (CRM) 52-3, 406
chaff 206,255,568-9,571,575-7
 INDEX 697

chaineoperatoire 4,101-3,105,106/.107, structure 414

109-10, 120-1, 122, 126-9,130/. 131, techniques 234,261
133-4,136,195,200,212,236,374,654 treatment 272,631,676
Chal 316 variabiity 343, 300, 368
Chalcolithic 409,567 variation 414
chamosite 92-3 chemistry 13, 89, 93, 2431, 254, 267, 289, 300-
chamotte, see grog 1,332,342-3,364-5,409,438,480,501
Chan Chan 390 chemometrical analysis 540
charge coupled device (CCD) 534 chert 241,269,273,276,545
chemical Cherwell, Lord 8
alteration 51, 158-9, 162, 166, 168, 1691, Childe, V. G. 654
172,176,259,343,347,365,409 Chimor 390
analysis 4, 10, 25,27-8,48, 50, 52, 67, 69, Chimu culture 389-91
74,99,149-50,152-3,159,163,166-8, China 278,315-6/.317-19,409,442,451,
171,173,175,202-3,327,338,343-4, 569,577
345,400,439,500-1,503-4,546,630, Chinese
663,680-1 porcelains 442
characterization 24, 35, 39, 48, 50, 52, 367, provinces 319
382,389,400,403,405,408,418,425,443 purple 537
composition 7, 9-10, 11, 23, 52, 69,88-9, TangSancai 309-10,317-19
92-3,941,95, 154-5, 163, 165-6, 173, wares 409
175,260,289,292,296,300,327,3341, Chipping Ongar 679-80
339,342-4,349,357,389,403,414,439, chi-square test (X2 test) 29, 69, 71-2
488,494/.495-6,500-1,510,536,539, chlorine ( Cl) 176, 368, 392, 394, 4251
545,566-7 chlorite 92-3,2421,2501,260,335,495
data 24, 49-50, 54, 153, 157-9, 163, 166, chloritoid 2431
176,234,288,342,345,352-6,374,460 chondritic uniform reservoir (CHUR) 309
decomposition 636 Christian period 504
differentiation 417 chromatography 314, 630-1
elements 48,52-3, 154, 166, 168, !75, 353, gas chromatography (GC) 9-10,626,6271,
383-5,391 630-2,634
evidence 277 ion chromatography 312-14
groups 49-55,156,158,343,354-5,369, liquid chromatography 630, 634-5
414,418 chromite 302
heterogeneity 365 chromium (Cr) 54, 95, 153, 159,174,313,
homogeneity 355 328,367,372,391-2,394, 411t, 4131,423,
information 388, 399-400, 408 4251, 436, 440, 50 lf
level 21, 24,43-4 chronocultural
markers 89 approach 182/
matrix effects 367 entities 189
methods 25 markers 103
preparation 312,314 chronological
procedures 312 attribution 671,687
processing 552 context 88, 90, 99
properties 19, 488 data 156, 578
resemblances 88 determination 196
staining 243t evolution 150
698 INDEX

chronological (Cont.) cobalt (Co) 95, 367, 373, 411 t, 4131, 4251,
frameworks 187 432}: 436, 443
indicators 389 coccoliths 268f, 270,274
life-course 130 Coconino Plateau 317
ordering 653 Coggeshall 680-1
ordination 654f Cogswell, ). W. 409
overview 115 coiling 104, 105-6f, 108,201,256,547, 548f,
periods 687 554, 558-9, 560f, 572
purposes 133 Cole, W. F. 682
range 276,675,679 Colomban, P. 538
reference 158, 188 color 9, 11, 19, 20f, 21,27-30, 34-5,58,
relevance 657 99,156,173,203-4,221,223,227,
scaling 655 229,235,237-40,242-81,2501,254,
segments 186 256-9,278,310,335,387f,391,409,
sequences 188,663 474,478,489-90,493,497-501,502,
sedations 217 504-5,537, 551f, 572,589,626,637,
value 654, 656 651,661-3,679
chronology 31,36,152,156,188,233,382-3, Colorado Desert 278
389,477,585-6,591,599,652-3,655, complete vessel 34-8,217,404,549, 555,
657,663,671 557,661-2
chronometric Compton
information 31 effect 531
methods 671 peak 369
chrysotile 92, 2501 scattering 344, 350
Clarke, D. I. 588, 659 Compton and Rayleigh method 367
classes 31-2,36,39, 99,201,206-7,212,236, computers 74-5,333, 552
522,545,585-7,593-4,596,599,632, applications 134
656,658-61,663,665 data storage 78
classification 4, 6, 12,24-5,31, 34, 39, 42, 48, modeling 605,608-9,621
87-8,90,93, 105, 107,116,149, 152, 155, programs/software 211,219,223,349,386,
!59, 181, 182f, 183-9, 192, 195,206-7, 435,511-12,533,546,553
217,219,234,237,241,302,318,453, science 585
477,487,500-3,535-6,539-40,567, simulation 131
575-6,585-9,592-4,596, 5971,651-5, systems 234
657,659-61,663-4 techniques 135
clastic/clasts, 92,209,289,290,299,300, technology 77,592
301,501 vision 590
cleavage 238-40, 242-91, 251 t, 260, 300 computed tomography (CT, CAT) 552
climate 163, 165, 167,174,277-8,577,683 conodonts 266
clinochlore 92-3,2921 consumers/consumption 26-9,38,42-3,60,
clinopyroxene 240, 242-41, 246-81, 101,109-10,115,118,120,131,149-50,
2921,300-2 152,156,184,200,266,278,357,472-4,
clinozoisite 244-5t 569,606,608,623,651
cluster analysis 152-3, 155, 183,353,394,439 contamination 50, 52, 166-7,172, 175-6,271,
clustering/dusters 48, 159,307,353,369, 273,276,346,356,364-5,394,425,437,
371-3,394,539,572,586-90,599, 439,495,568,577
657,660 cooking 125, 127,130-1, 132f, 133, 155,200,
Coarse Orange Ware 415 237,565,606,617
 INDEX 699

pots/vessels/wares 10, 27, 64, 66, 95, 108, crystalloclasts 294(, 299
148, 155-8,189,201,212,253,257, 258f, crystals 90, 92, 96, 164-5, 167,240-1,2421,
269,279,459,472-4, 513f 514,520-3, 245-81, 250-11, 291, 299, 328, 350-1,
604-5,606/,616,619-21,636,671,678 520, 672-5, 677f
Cookson, D. 448/ crystobalite 517/
Copeland, S. R. 313 Cubu 355
copper(Cu) 13,95, 166,172,176,257,310, Cucuteni 294}: 297-81
313,320,328-9,345,369,371,392,394, ceramics 295f
4111, 4131, 4251, 426, 436, 457-8, 540 people 453
Copper Age 294f 295/ Cucuteni-Tripolye culture 451
cordierite 2491, 260, 300, 510 Cui,).F. 314,319
COrdoba 591, 592j Cultrone, G. 88
Corinth 276 cultural
Corinthian ware 211, 336 anthropologists 535
Cornwall 442 aspects 49, 55,192,344
corundum 300, 453-4 behavior 49,354,658
Costin,C. 117-18 change 188,277,498
counter immuno-electrophoresis constraints 4
(CIEP) 633 deposition 121
cracks/cracking 96, 98, 128, 130, 167, 171-3, descent 110
239,253,257,276,499,502,549,571, dimension 101, 189
609-11,613-20 environment 103,115,117
Creswell, R. I 0 I factors 4, 438-9,471,565,578
Cretaceous 941, 156, 268f, 277 frameworks 188
Cretan groups 188,289,589
Bronze Age 558-9 imprint 50
potters 559 interactions 266
stirrup jar 551/ materials 401,545
Crete 94, 165,209,273,276,336,342, 559 patterns 192
cristobalite 260, 338-9, 510 perspective 188,342
crossed polarized light (XPL) 205,209, phenomena 184,191
237-40,257, 258f 495 resource management 80
Crusader technology 119, 120-1,122, 135
period 154, 156 tradition 103
productions 158 transmission 102,656,663,664/
crystalline uncertainty 52, 55
cellulose 346 variance 50
compounds 327 Cumberpatch, C. G. 355
concentration 208,211 cuneiform tablets/writing 129,371
minerals 509 Cupinisque culture 390
orientation 330 Cyprian
phases 28,88,168,300,339,458/ ceramics 373
rocks 87 Bronze Age 267
structure 44, 90, 92,201,205,300,449, import 155
515,540 pottery/vessels 524}: 525, 549,557
crystallization 21, 165,241,252-3,309, 339, Cyprus 267,31!, 315,318
454,493,495,511,525 Czech Republic 674
 -r
700 INDEX

Dacian period 294/ changes 27

Dangstetten 168, 172 evolution 99
Daresbury Synchrotron Radiation Source scope 122
(SRS) 450, 457 study 236,454-5,536,546,591
Daszkiewicz, M. 6, 496, 504-5 trends 654
data Diadovo 316
analysis 3, 53, 70, 75,352,540 diamond 204,291
distribution 63, 76,540 diatomite 570
interpretation 4,48-9, 51, 55, 70,150,152, diatoms 266,268-9,271-2, 273f, 275-9,
176,320,369,373-4,492,607-8,638 565-6,576
recycling 73-4,76-7,80 dickite 92
standardization 74, 77) 367 diffractogram 164, 167, 332-3,
databases 74-6,78-80,99,149,153,159,227, 337f, 452f
234,288,306,311,318,333,345,408, diffractometer 329-30,332-3, 335t, 339
425,438,533,592,594-9,632,635,638 Digby, A. 544
dating 5-6,8,49, 150,152,164,174,176, Digital Archaeological Record
188-9,217,233,279,522,537,569,578, (tDAR) 76,79-80
586,629,652-3,671-2,674,675,677-82, digital
684,686-7,683 cameras 223-4, 553
daub 279 computers 75, 621
Day, P. M. 209 data-storage 75
de Booy, ). 448f formats 553
Debye-Scherrer method 329f, 330-2, 339 imageanalysis 207,211
decarbonation 88,511,676 images/photographs 211,227,553
decoration 3, 7,10-11,13,20-2,24, 34, 58, imaging 550, 552
103-4,120,125,151,154,156,181,183, libraries 631
186-7, 190, 192, 195-6, 20!, 219-21, mapping 293
223-4,227,233-4,237,253,256,271, microprocessor 492
305,308,354,373,389,453,455,477-81, microscope 437-8
524f, 525,537, 545-6,656,661,663, 664{, photographs 224
see also ornamentation radiography 553
Defeyt, C. 540 storage 78
degradation 233, 274f, 275,280,628,634, systems 552
636,653 tools 592
Degryse) P. 5 digitization 79, 81,553,591-2
dehydration 96, 164,252,296 dimensions 661,663
dehydroxylation 164,252-3,296,300,510- dinoflagellates 266, 268-9, 271,274,279
11, 536, 537f, 685 diopside 88, 165,241, 243t, 251t, 260,300,
dendrogram 108,353,394 335-6, 337f, 436, 452f, 495,504,511,
Denmark 278 516f, 519-20
deposition 38, 90, 121, 132-3, 152, 162-3, diorite 241, 301
172-3,211,237,252,255,258-9,267, DNA 625,634
273,301,400,498,504,576 Dobres, M.A. 119
depositional environment 576) 578, 636 dolomite 90, 95,241, 243t, 495
Devon 442 Doran,). E. 588
diachronic Dorset 442
analyses 457 drawing/illustration 151,217, 218f, 219-24,
axis 110 225-6f, 227, 228f, 290,592
 INDEX 701

Duane-Hunt equation 328 energy

Duistermaat, Kim 4 dissipation 6!5-!6,618-20
Dunnell, R. C. 589 distribution 289, 427
Dussubieux, L. 4, 401{, 414 level 347,531-2,535,673
source 7,12,275
Earle, T. 1!6 spectrum 428-9,433
Earth magneticfield 686 state 532, 535
earthenware 9, 12-13, 20!, 336-7,346,437, England 274,442, 443f, 450,459,681
442,618,685 engobes 167,373,390,451
Eastern sigillata A 167, 173 Enkomi 267-8
ecological entanglement 119, 121, 123-9, !31-6
approach 115,116 enzyme-linked immuno-sorbent assay
factors 471 (ELISA) 626f, 627t, 633
origin 576 Eocene 268f, 277
parameters 566 epidote 2441,2471, 250t, 2921,301
phenomena 655 Epi-)omon pottery 355
ecologists 73 equivalent firing temperatures (EFT) 28-9,
ecology 1!,!2,!14-!6,122,!35 260,488
Ecuador 190,279 Ericson, J. E. 590
Eerkens, J. W 6, 355 erosion 87, 310,438,594,595/
effective lifetime temperature (ELT) 684-6 Essouk-Tadmaldca 569
Egypt !58,!88,318-!9,337f,504 estimated vessel-equivalents (EVE) 32
elastic neutron scattering, see electron estimated vessels represented (EVREP) 32
backscatter diffraction ethnic
elastic recoil detection analysis 387 affiliation 188
electromagnetic boundaries 415
field 401 distinctiveness 588
forces 427 groups !02, 188-9, 59!
lenses 290 identity 190
radiation 329,447-8 ethnicity 189-90,474
spectrum 328 ethnoarchaeological research/studies 115,
electron backscatter diffraction 327 343,355,389,478
electron beam 289, 290, 448 ethnoarchaeologists 9
electron microprobe (EMP) 9, 167, 289-90, ethnoarchaeology 12, !01, 116, 122-3,470-l,
292-3,296,300-2,425,454 474,482
electron microprobe analysis (EMPA) 288-9, ethnoarchaeometric studies 23
296,2971,299-300 ethnocultural groups 189
electron probe microanalysis (EPMA) 51, !3, ethnographers 359
260,400,406 ethnographic
electron transitions 329f analogies 189,217
electrophoresis 630, 633 approaches 482
Elemental Analysis Facility (EAF) 410-14 behavior 658
Emporiae 29 contexts 471
energy dispersive spectrometry (EDS) 51, 570, contributions 475
369,373-4,400,406,408,417,571,574 data 107,469-70,480
energy dispersive X-ray fluorescence examples 114
spectrometry (ED-XRF) 5t, 342, models 470
344-52,356,363,365,536,540 observations 415,470-1,474,489
702 INDEX

ethnographic (Cont.) Fatimid

research 359,471 dynasty 457
research 476 period 158
studies 89, 236, 487, 496, 503 wares 150, 157-8
Tumleo ceramics 418 feldspar 87, 90, 93, 95,205,210-12,239,
ethnography 5t, 89, 101, 114, 123,255,469, 248-91,260,289,292-3, 294f, 653,
473,478,480-2 672,675-6
ethnotaxonomies 184 K-feldspar 239, 248t, 252,260,2921, 293, I
Etruria 455 294f, 295f, 297t, 300-1,408,495,518/
Etruscan pottery 186 Felts, W. 233
Euclidean distance 69, !56, 159,594,596 field-portable XRF (FPXRF), see portable
eukaryotes 266 energy-dispersive X-ray fluorescence
Eurasia 460 spectrometry (pXRF)
Europe !89, 277, 305-6,308,319,442,450-3, figurines 3, 200, 569
504,569-70,653-5, 664f, 681 Finale Ligure 567
European Meeting on Ancient Ceramics 496 Finikia Formation 273
European Synchrotron Radiation Facility finishing 103-5, 108, 128,256,390, 545
(ESRF) 450,455,457 finite element analysis (FEA) 30,609,621
europium (Eu) 54, 55, 412t, 4141,4251, Finland 278
432f, 436 firing 7, ll-12,20f,2!-2,24-7,44,51,
Evershed, R. 13 87-90,95-6,98,99,103-5,107,120,
evolutionary 125,127-30,133,154,163-4,167,171,
archaeology 1!0, 354 173,175-7,201,206,208,226,234-6,
biology 635 241,252-3,255-6,258-60,267,269-70,
forces 110 274-5,288-9,295-6,299-30!,334-5,
perspective 109 338,409,437-8,442,454-7,460,472-3,
phenomena !lO 476,478,481,487-8,490-2,494f,
processes 632 495-500,503,505,510-1!,515-!6,
sequence 546 5!9-20.. 522,526,537,566-8,570-1,574,
terms 193 603-5,608,612-!3,619,635,663,665,
excavation 3, 11, 13, 22, 26, 42, 51, 54, 68, 672-3,678,682-4,686
98,126, !54, 158,163, 172,202,2!7, atmosphere 104,254,260,457,489,493,
233,266,268,276,279,307,3!5,337, 495,497
382,390,404,415-!7,438,449-51,487, conditions 21, 35, 89, 176,203,208,236,
585-6,591-2,654,677,685 253,258,280,454,536-7
extended X-ray absorption fine structure
(EXAPS) 13,457,459
experiments 5t, 99,212,488-9,493,503
laboratory controlled 491
I
'i
phases 299-300
fabric/fabrics 4, 6, 12, 21,25-9,35,43-4, stages !20, 128
58, 63, 64f, 99, !05, 107, 128, 131, 137, technology 258,272,274,280,454,478,
149-50,152-3,183,185-6,196,200-13, 487-8,492-3,503,525
233-7,240,252-8,276,296,364,374, temperature 9, 1!, 28, 51, 164-7, 176-7,204,
403,415,449,459,488,496-7,501-2, 209,254,257,260,274-5,278,300,302,
508,5!2,515,545-7,565,577,604-5, 327,336,339,403,438,459,478, 479f, 488,
608,613,617-20,622,636,663,677, 493, 494[,495-7, 504,522-3,525,536-7,
679-80,686 565,578,607,612,615,622,682,686
Faradaycup 314,401 see also post-firing, pre-firing, re-firing
l
------~·-·

INDEX 703

Flavian period 27 photons 432

Fleming, S. ). 546 spectrum 53, 432-4
Florida 372,415, 452f strikes 433
flux 13, 53, 156, 158,257,260,275,318,336, Ganio, M. 313
346,348,425,427-30,433-6,448/,457, Garamantean potsherd 273f
493,495,522,539,620-1 garnet 239,241,243-41, 25!t, 301,404
folk classifications 184-5 garronite 337
foraminifera 266,268,270-3, 274f, 277, Gaul 319,334,453-4
279,566 Gaulish Terra Sigillata (GTS) 29,35-9
Ford,). 657,659 Gaulo- Roman cooking pots 212
Ford-Spaulding debate 657 Gauss, W 209
Forster, N. 365,370 Gazzi-Dickinson method 211
fossil directeur 188-9 gehlenite 88, 164-6, 177,260,2921,300,
fossils 128, 182,188,234,266,269-70, 336-7, 495, 504, 5!1, 514f, 516/,
273,275-6,279,567,586, see also 519-20,526
microfossils, nannofossils Gela 97f
Fouque, F. 148, 233 Gelber!, A. 477
Fourier transform infrared spectroscopy (FT~ geochemical
IR) 51, 6, 288,509-15,516-18/,519-20, analyses 58
521/, 522-4, 524/, 525-6, 607 behaviors 156-7
Fournou Korifi 276 composition 307-8,315
Fourth Nile Cataract 504 context 153
Fowler,K 5 data 3, 54, 73,300,315
Fowles, S. M. 355 discrimination 368-9
fractals/fractality 182, 194,195 features 148, 154
fractionation 307, 311, 314, 404, 407 grouping 373-4
fracture 132, 202, 204-6, 238-9, 2471, 2491, literature 50
409,419,501,570-1,610-18,620 markers 95
energy 613,615 methods 316,320
strength 611-13,618 parameters 154
fragmentation 31-4,37-8,43, 132-3, pastes 364
6271,635 processes 50
France 212,311,450,455,471,570,680 properties 309
Freestone, L C. 167, 172,352 provenance 70,536
Friedrich, W 328 samples 372
fungae 266 signals 373
furnace 97,488,492-3,498,684-5 signature 439
Fustat pottery 319 techniques 305-6
uncertainty 4
gabbro 241,301 variability 441
galena 310 geochemistry 88,202,279,399
Galilee 522 geochronology 276
gallium (Ga) 347, 41!t, 4131, 425t geographical
gamma rays 347,388,427-9,431-3 areas 42,188,261,306,569,576,578
count 78-9 boundaries 399
detection 388, 432 concentrartion 117
emissions 424 distribution 200, 306
 ~··

704 INDEX
I
geographical (Cont.) glass 128, 158, 162-3, 166, 175, 195, 205, 257,
environment 576 261,291,300-1,305,310,338-9,346,
locations 150,441,450,460 351,356,363,371,407,410,505,538,651
origin 439,630 glassy
provenance 42 amorphous texture 241
region 221,589 disk 346
scale 51 matrix 253,261,453,538
sources 127,526 phase 165,172-4,253,338-9,536,538,
space 24-5,27 612,622
trends 150 rims 300
variation 439 silicates 539
geological solids 327
age 273,311,316 glauconite 92
areas 25,42 glaze 9, 11, 13,20-2,90,104,156,163,223,
characteristics 200, 206 234,256-7,305,308,311,314,318-20,
contexts 241 346-7,365,372-3,405-6,408-9,419,
data 105 437, 452f, 457-8,474,499,503,505,511,
environment 372-3 523,534,536-9,686
evidence 277 Gliozzo, E. 455
features 153-4 gloss 13, 20, 22,28-9,35, 167,227,409,451,
formations 148 453-6,489,499,505
maps 149,279 gneiss 92-3,2451,2501
materials 90, 202, 308-9, 313, Gobero 570
343,365 gold (Au) 345,4251,434,573
origin 87 Golitko, M. 4, 401f, 409,416-7/
processes 50, 400 Gongxian 309, 317
properties 200 Gongyi 319
provenance 201 Gosselain,O. 190,471,474-5,477
resources 475 Gothic architecture 681
samples 234 grain 10,87-90,93,95-6,98-9,132,164-5,
sediments 90 167-8,204-5,207,209-13,235,238-42,
sources 208,409 2441,2461,248-91, 251t, 252,254-7,
specimens 79 259-61,270-1,272,276,288,293,
strata 188 296,299-301,306-7,312,315,317,
stratigraphy 653 331-2,335-8,364,366-7,369,371,406,
timescales 307 409-10,415-16,419,459,476,493-5,
geology 10, 89,201-2,206,211,233, 276-7, 502,504,510,519,523,545,567,569,
279,301,332,415,417,475,516 577,608,611-12,616,626,6271,674,
Germanic pottery 170 676-7,680
germanium(Ge) 78,291,349,4251, Granada 591,592/
432-3,450 Grand Canyon 309, 315f, 317
Germany 170f, 311, 333, 334-51 granite 90,92-3,241, 25lt, 301,622
Ghana 473 granodiorite 92,301
Gila River 409 graphite 104,427-8,536
glancing incidence X-ray diffraction 327 Gratuze, B. 406-7
Glanzman, W. D. 546 Greece 50, 66, 94, 151f, 209, 309, 31!, 315-6f,
Glascock, M.D. 355,410,414 551j, 559-60
 INDEX 705

Greek helium (He) 365,400

amphorae 66,276 hematite 90, 165,260,300,335, 452f, 454,
cities 60, 93-4 458, 495, 518f, 524f, 525, 537
communities 193 Henan 319
pottery 601 hedenbergite 2441
vases 489 hercynite 2501, 2921
green body 335,338,489,492-3 Heron, C. 636
Greene,A. 4 hierarchical cluster analysis (HCA)
Griffin, j. B. 74 353,394
Grim, R. E. 98 high-energy ion beam 13
grog 51,206,208,255,299,545,557,565 high-purity germanium (HPGe) detectors 78,
groundmass 25, 93,207-10,235-6,259-61, 349,432-3
273f, 299-300,495,607-8 high-resolution inductively coupled
Guadalquivir River 589, 599 plasma-mass spectrometry
Guatemala 408 (HRICP-MS) 313-14
Guinier, A. 329 high-resolution powder diffraction
Gujarat 229 (HRPD) 454-5
Guthe, C. E. 74 high-resolution wide-angle X-ray scattering
gypsum 130, 132, 165, 167,252, 518f, 537 (WAXS) 339,448/
Hispanic Terra Sigillata (HTS) 27-8,31,
Habicht-Mauche, j. 318 35,37/
hafnium 50,410,4121,4141, 425t, Hodder, I. 11, 190
432f, 436 Hodson, F. R. 588
Haifa 65f, 66 Hoeck, V 5
Hakansson, H. 269, 275 Hoffman, C. R. 119
HalaSultan Tekke 318 Hohokam wares 206, 409
Hall, N. S. 591 holistic
halloysite 92 approach 11,13,119,122-3,135
Hanawalt groups 333 interpretation 183, 194
handheld portable energy-dispersive X-ray perspective 119, 136
fluorescence spectrometry, see portable studies 123
energy-dispersive X-ray fluorescence view 195
spectrometry (pXRF) Holmqvist, E. 4
handheld XRF (HH -XRF), see portable Holocene, 268/
energy-dispersive X-rayfluorescence hornblende 2451,292,301,308
spectrometry (pXRF) Horner, A. E. 471
Harappan civilization 229 Huarmeyvalley 390
Harbottle, G. 49, 75, 77,148 Hull-Debye-Scherrer method 330-1
harmotome 337/ Hulthen, B. 275
Hasselman, D.P. H. 617 human-thing relations 115, 119
hatrurite 300 humidity 163-4,277,683-6
Hawkes,C. 8 Humphreys, A. 472
heat transmission, see thermal conductivity Hungary 569
Hebrew University ofjerusalem 78 Hunt,C.O. 274
hectorite 92-3 Huntley, D. L. 318
Heimann, R. 4-5, 165,337,497 hybridization 193-5
Hein,A. 76 hydrogrossularite 337
706 INDEX
Iberian
Peninsula 28-30
period 591,599
pottery 27, 30,536
settlements 30
vessels 585
Ibida 290f, 294f, 297-8t
Ierapetra 276
ignition 24, !66, !68-9, 17!-2, 176,267
Herda 28f, 29
Ili1ua 294f, 297 -8t
illite 92, !64, 171, 254, 260, 292t, 297t, 300,
335-6,458,495,5!0,518/
illitic
clay !64, 300,333, 334t, 335-6,454,493
groundmass 300
matrix 290f, 293, 295f, 297t
illustration, see drawing/illustration
ilmenite 239, 292t
image analysis 207, 21!-12, 605,607
imaging 235,289,291-3,400,450-1,453,
546,550,552-3,555,575
immunological techniques 632-4
impact resistance 23 7, 257, 289
impermeability 20f, 253,274,523
importation 7, 88-9,99, !48-9, !52, 224,236,
301,315,389,453,498,526,569,607,680
Inca empire 307-8
inclusions 5t, 19-21,25,35,42, 50, 52,63-4,
126,128,156,187,!91,200-!,202,204-12,
233-6, 244t, 248t, 250t, 252-9,269,
271,273,288,299,307,312,317,405-6,
409-10,414,417,454,459,493,495,501,
51!, 544-7, 548f, 549, 552, 565-78, 605,
607-8,611-13,615-17,619-20,622,679
India 190, 217, 229, 273, 409, 567, 577f, 569
Indian Ocean 569
inductively coupled plasma (ICP) 4, 5t, 10,
13,399,4111
inductively coupled plasma mass
spectrometry (ICP-MS) 10, 99, 162,
310-11,313-14,327,342,364,399-400,
418,536,676,680
information entropy 34, 36-40
infrared 447-8,451
microscopy 451, 453
spectroscopy 6, 288,509-10,519,536,628
innovation 110,120,124, !33, 192,442,454,
477,623,656,665
instrumental neutron activation analysis
(INAA, NAA) 4, 5t, 8, 10, 12, 54,77-8,
80,99, 162,166,168,171,174-5,310,
327,342,364,366-7,369-72,399,408,
410-12,4!4-15,4!9,424-31,435-39,
440f, 442-3, 559, 628
instrumentation 74,290,408,424,427,449,
455,534,535,552,676
IntefV!I 337/
interaction 43, 51,109, ll5, 120-1,123-5,
127-8,131,!33,135, 188,192-3,255,
266,305,307,317,320,474-5,481,651,
657,663
International Association of Geoanalysts 435
International Centre for Diffraction
Data 328, 333
International Code for Phytolith
Nomenclature 567
International Standards Organization 346
International Symposium for
Archaeometry 8
intrinsic essential properties 20j, 21,24-5,27,
29-32, 34, 39, 43
ion microprobe 311,313
ionization 291, 3ll-12, 351, 400-l, 405,
631-2,635,672
Iran 319,173
iron (Fe) 54-5,87,90,92-3,95, 155, !57,
166-8, 171-2, 174, 176,208,210, 242-5t,
247-81, 250-!t, 252,257-9,274,288,
293, 294f, 295f, 297-8t, 299-300, 3!0-
11, 313,318,328-9, 334t, 335,365-6,
369, 370f, 371-3,391-2,394,405, 407f,
4llt, 4131, 425t, 426, 432f, 436, 452f,
454-5,459,489,499,501f,505,523,525,
682,686
Iron Age 193,269, 273f, 274,511, 513f, 522,
524f, 525-6, 569, 572, 653, 682
EarlylronAge 316
Late Iron Age 187f, 194f, 277
irradiation 53, 78,347,388,392,424-5,427,
429-37,493,672,678-9
ISIS 450
Islamic
ceramics 11
 INDEX 707
·----- -- ·-----. --····-- ----------
luster decoration 13 Kilikoglou, V. 76,616
Period 457,459 kilns 25, 88, 105, 127, 130, 133, 149, !Slf, !52,
world !56 158-9,!63,!72,20!,236-7,259-60,
isomorphism 92, 182, 186, !87f !89-90, 3!7, 319,336,342-3,354,437, 443f, 454,
193,195 457-8, 479, 487-90, 49lf, 492-3, 494{,
isotope ratio mass spectrometry (IRMS) 311 495-8,565,573,681-2
isotopes 4, 51, 13,306,307-20,347,405-6, atmosphere 88, 95
409,424,426-36,438,626,627~629-30, building 129
632,636,672,676 environment 260, 663
Israel !56, 172,276,373 furniture 148, !51, !55
Israeli ceramics 276 sites 89, 236
Italian structure 26, 487
clays 93-4 technology 128
maiolica 336 wasters 26, 42, 89, !Slf, 236,442,499
Italian Terra Sigillata (ITS) 35-9 Kingery, W D. 9
Italy 9lf, 94t, 3!!, 3!9, 454,567, 57! Kintigh, K. 76
Iznik pottery 537 Kiriatzi, E. 209
Kirilovo 316
jadeite 2461 Knacke-Loy, 0. 309-10,313, 3!5-!6, 318
Jaen 59!, 592/ Knappett, C. 355
Jansma, M. J. 275, 278 kneading !30,252,255,566-7
Janssen, K. 344 Knipping, P. 328
Japan 355 knobbed ware 309-!0, 3!6
jenkins, R. 352 I<nossos 209,273,336,557/
jerusalem 172 knowledge transfer 192-3, !95
Jockgrim 333, 3341, 504 Kolonna 209
Johansson, S. A. E. 383 Kommos 342
jones, M. C. 70 Kouphovouno 209
Jordan !56, 337f 450 Krieger, A. 657-9
joyce, A. A. 355 Krishnan, K. S. 53!
julio-Claudian period 27 Kroeber, A. 655, 657
Kroumovgrad 277
k0 (single comparator) method 434 Kutahya wares 539
kaersutite 246t kyanite 2451, 2501, 299
Kaiep 415, 4!6f, 418
Kaman-Kaleh6ytik 459 La Emerenciana 279
Kamenov,G.D. 410,4!1-!41,4!5 La Graufesenque 29, 39, 40f 42, 168, !69f,
Kandahar 568 454,455
Kanto 355 La Peniche 337/
kaolinite 90, 9!f, 92, !53, 292t, 300, 3!2, 336, Laboratoire de Ceramologie 154
338, 495, 5!0, 512, 514-!5, 5!6f, 5!8f, laboratories 3, 8, 10-ll, 43, 49, 67, 73-8!,
5!9-20, 52!f, 522-3,682 !49,153,158-9,162-3,166,202-3,271,
kernel density estimation (KDE) 69, 72,353 274,313-!4,346,348,356,363,372,
K-feldspar, see feldspar 383,386,401-4,410,425,433,435,437,
K-H analysis 499,500/ 450-1,459,471,488-9,492-3,496-8,
Khartoum 49 !f 502-4,533,535-6,572-5,606,6271,638,
Khok Phanom Di 569 672-3,675-6,680,683,685-7
708 INDEX

Laboratory for Material Analysis with Ion Li,B. 309-10,3!7

Beams (LAMFI) 386 life-cycle 7-9, 11-12, 88, 121, 13!, 133, 185,
Lachish 188 237,389
Ladenburg 170 limestone 63, 93,204-5,209-10,241,257,
Laflin, S. 591 276,308,415-!6,459,495,523
landscape 12,71,133,267,355,450,451,476 limit of detection (LOD) 52,368,6271,634
lanthanides 309,437 limit of quantification (LOQ) 52
lanthanum (La) 50, 54, 95,290,410,412-131, linear discriminant analysis (LDA) 539-40
425t, 436 Linearbandkeramik 189
larnite 300, 495, 511, 519, 520 lipids 10,480,625,6271,632,634-6,638
Larson, D. 0. 414-15 Lippi, M. M. 6
laser ablation (LA) 51, 13, 313-14, 399, liquid sampling 314, 401f, 403,405-6,408
401f; 403-15, 411t, 417, 418f; 419, 425, lithic
439,455 industries 652, 658
laser ablation multicollector inductively materials 356, 632
coupled plasma mass spectrometry (LA- technology !07
MC-ICP-MS) 13, 313-14,403,419 lithium (Li) 93, 251t, 291,305,346,348,350,
Late Hellenistic 308 356, 383, 385, 386f, 411 t, 4131, 425t
Late-Terminal Formative 440/ lithoclasts 90, 294f, 299
Latium-Campania 39,42 Livingstone Smith, A. 471,475,478
Latour, B. 124, 134 lizardite 92
lattice 291-2, 30 !, 329-30, 332, 3341, 335, logistics 447,449,460
510, 538 Lorna Alta 279
lauconite 92 Long, D. A. 531
Laurion 172 loutrophoroi 60
Lausanne 337/ low-fired ceramics 164-5,171,174,253,
LaViolette, A.). 472 336-7,318,520,612,614,616,618
Lawrence Berkeley Laboratory Lubbock,). 653
(LBL) 78-80, 450 luminescence 290,388,574,674-5,677
leaching 51, !66-8, 1691, 17!-5, 177,317, dating 174,672-3,675,678-80,687
409,417,535,636 measurements 676
lead (Pb) 9, 13, 156,166,172, 176,257,305-6, reader 676f, 677
308,310-15,318-20,345,373,405,409, signal 673, 675
411-121,4141,4251,433,457,537-8, Luminescence Dating Laboratory 672, 680
554{, 555 Lund University 504-5
Lebanon 106f, 156 lustre 11, 13, 22,451,457-8
Leiden School 115 lustreware 454, 457
Leilan 442 Lutz, G.). 174
lekythoi 60-1,459 Luzon potters 355
Lemoine C. 172 Lyon 154, 168, 1691, 174
Lemonnier, P. 194
Leon, Y. 454 macroscalarprocesses 186, 195
Leonard, B. L. 559 macroscopic
lepidocrocite 335 analysis 4, 488, 501, 546
Leroi-Gourhan, A. 101 animals/plants 566
Levant 158,276,511,513/ ceramic groups 39
levigation 234, 254-5, 472, 505, 608 characteristics 389
 INDEX 709

criteria 150 process 21-2,24-7,43,469,603

crystal 238 products 22
data 7! techniques 26
examination 255 technology 252, 254, 455, 535-6,
features 390 560,565
level 327 March, B. 217
observations 43, 496, 609 Maritan, L 6
Madrid 29 markets 29, 109, 119, !50, 217,267,
Madrid i Fernandez, M. 3 441,478
Maggetti, M. 164-5,235,289,337 Marks, R. H. 3
maghemite 300,537 marl 273,276-7, 3!5, 372
magma 301,309 Marshall, Sir john 217
activity 310 Martinez-Carillo, A. 6
origin 301 mass production 126,442
processes 309 mass spectrometer 400-2,404-5
rock 241 Massachusetts Institute of Technology 9
magnesiohornblende 2921, 301 materiality 183, 188-90, 192, 47!, 482
magnesium (Mg) 87-8,92-3,95, 137, 159, materials science 332, 342, 369
165, 171-2,242-81, 250-lt, 270,297-81, Matiskainen, H. 278
312,3341,346,348,364, 411t, 4131,4251, matrix 19-2!, 44, 50, 53, 70, 75, 90,207,
430, 452f, 454,495, 50lf 165-7,!73,200-!,206,209,21!,234-6,
magnetic
238,252-61,271-3,289, 290f, 291,293,
field 405
294f, 295f, 2971, 299-301, 312, 3!4, 317,
media 76 345-6,349,353,363-4,367-8,370f,
sector 313,314, 402f, 405 372,386,404,407,410,436,453,496-8,
structures 448 500-4,51!,519,534,538,547,550,596,
tape 74-5,78-9 597-8,605,608,612-13,6!6-18,622,
magnetite 239,2921,300,336, 458f, 495,537 635-6,680
Mahagara 273 matrix groups by re-firing (MGR) 173, 496,
Mahalanobis 498-501,503-4
D 2 statistic 439 matrix-assisted laser desorption
distance 441, 156-8,353 and ionization time-of-flight
filter 50 (MALDITOF) 635
Mahias, M. C. 190 Matson, F. 11-12,115,504
majolica 22, 452 maximum number of individuals
Making of Ancient Eurasia (MAE) (MxNI) 32-9,41
Project 460 Maxwellian !IV law 429
Makishima, A. 313 Mayan ceramics 12,408
malachite 537 meaningful ceramic groups 23-7,29-31,
Mali 569 34-5, 38-43, 49
Mallorca 187f, 194/ mechanical
Manchester Museum 455 properties 51,13, 19, 23, 27, 30, 39, 88, 90,
manganese(Mn) 95,17!,174,176,294f, 200, 47!, 497,523,603,606,622
297-81, 370f, 411 t, 4131, 524f, 525 shock resistance 128
manufacture stresses 472,605-6,610
behaviors 49, 50, 53 medical/medicine 473, 480, 544-6, 550-1,
parameters 608, 622 552f, 553
710 INDEX

medieval 150, 152-3 micropalaeontology 5t, 266-7,270,279-80

brickmaking 680 microstructure 7, 13, 21-2, 35, tl4, 51-2, 205,
ceramics 155,686 207,209,234,259,296,338,374,455,
earthenware 336 458,460,478,488,495,604-12,622,683
lustreware 454 MiddleEast !3!,409,450,457
period 308, 504, 680 Middle Horizon ceramics 414
productions 158 Middle )om on foragers 355
wares 154, !57 Miksa, E. ). 206
Mediterranean 76, 93, 95, !56, !62, 193,209, Miller index 330, 3341
267, 273f, 310-11, 318-19, 453, 559, 654 Milton Keynes 269
Meirer, F. 455 Mimbres Valley 267
Mendeleiev, D. !54 Minc,L. 4
Menek~e <;:atagi 3!6 mineralogy 88-9,202,209,236, 240-l, 254,
mercury (Hg) 299,345,349, 425t, 605,607 259,267,299,301-2,3!7,332,363,365,
mercury intrusion porosimetry 299, 605, 607 367-8,399-400,438,478,501,536,538,
Merzbach valley 664/ 545,676,682,686
Mesa Verde 409 minerals/mineralogical
Mesoamerica 50, 409 alteration 6, 51, 162, 164, 166, 176, 403
Mesolithic 504 analysis 4-5,27-8,39,50-1,99, !59, 312,
Mesopotamia 167,458-9 400,454,509,512,545
Mesopotamian metallic ware 167 assemblage 30!,318,510-!!,682
meta-clay 510-12,515,519-20,522-3, 524f, associations 153,495
525,682 changes 164,166,685
meta-kaolinite 336, 510, 5!2, 5!4-5, 5!6f, characterization 35, 400, 458
519,523 complexity 3
meta-smectite 510,512, 514{, 515, 5!6f, 519, components 302, 566, 568
523,525 composition 7,2!,23,52,89,95, 175,206,
metallic 22, 186,257,306,328,457,538 211,240,259,296,307,309,327,338-9,
ware 167,459 410,453,455,458-9,488,493,494{,
metallurgy 195,307,311,604,608,619 495-6,500,504,509-10,515,522,526,
Mexico 279,309, 3!5f, 317,409,415, 534,536,569,6!~675
432f, 440/ compounds 293
mica 90,92-3,95,206,209-10,212,235,241, data 409, 460
2441,2461,2501,255,261,292-3,300-1, decomposition 260
307-8,355 domains 208
Michel, H. V. 78-80 fabrics 29, 212,663
Michel- Levy interference color chart 240 features 148, 153-4,490,492,495
micrite 208,210,252 fractions 309, 312
microbalance 681,683-5 fragments 208,235,255,261, 3!7
microfauna 93, 267-8, 276 grain 239,240,410,676
microflora 267, 276 hardness 204
microfossils 234, 266-80, 565, 570, see also identification 239, 242-5!t, 258f, 295, 607
fossils, nannofossils inclusions 53, 63, 64f, 206,234-5,253-5,
micromass 207-10,495 258,307,312,409
micromorphology 201,206-8,212,572,575 mixturess 90
Micronesia 571 orientation 239
microcline 245t, 248t particles 98, 364, 546, 549
--
INDEX 711

phases 7, 11,48,260,289,291,293,388, characteristics 88,275,575,577

403,410,493,495,50!,536,565,622 criteria 594
properties 99, 487 curves 593
resemblances 88 dimensions 212
scales 28, 204 elements 189
species 92
evolution 266, 276, 599
structures 44
features 224, 566, 575, 599
temper 63,253,257,439,472,568 filtering 594
transformations 493 groups 107
Minet el-Beida 3!8 identification 607
Mingpottery 451-2 observations 574
minimum detectable concentration properties 207
(MDC) 425, 436 types !07
mining 135, 172, 3!1, 315,319,334-5,363, typology 589, 59!
372,438 variety 566
Minoan
morphology 71,193,20!,206-8,270-1,
amphora 554/
278,293,545,572-3,585,590,594,596,
cup 557/ 603,609
Kamares periods 336
morphometric analysis 51, 58, 183, 185,460,
pottery 12 571,585,591
Miocene 941, 277
morphometries 6, 585
Upper Miocene 9lf morphometry 191
Mission San Luis 452/ morphotypological
Moche culture 390 analyses 187
Moessbauer spectroscopy 504 variability 182f, 186, 192
Mogollon culture 267 Moseley law 384
Mohs' scale of mineral hardness 204 MOss bauer spectroscopy 288
molds/molding 27, 42, 96, 99, 104, 105f, 108, Mount Gibele 91/
20!,237,255-6,277,390,492,546,549 Mozia 275, 277
molecules 92-3,96,427,531-3,535,6271, mudstone 2!1, 317,415
628-32,634,636-7 Miiller, N. S. 6
mollusk shells 495, 568, 571
mullite 164,260, 292t, 300,3341,335,338-9,
molybdenum (Mo) 311,313,328,348, 510,516/
4131, 425t
multicollector inductively coupled
monazite 309-10,410
plasma mass spectrometry
Mont Lozere 3!1
(MC-ICP-MS) 311-14,409
Montana, G. 3, 27
multi~ response permutation procedure
Montans 39, 40f, 42 (MRPP) 69, 72
Montelius, 0. 653
multivariate cluster analyses 439
montmorillonite 92-3,96,312,337, Munsell colors 203, 227
510, 518/
Munsell Soil-Color Chart 58,203,505
morphofunctional
muscovite 90, 92,209-10,241,2431,246/,
criteria 183
250t, 290f, 291,2921,293, 294f,
relationships !89 297t, 302
morphological
Museum of Archaeology and Ethnology
analysis 183, 186,593
of the University of Sao Paulo
attributes 189, 193
(MAE- USP) 389-90
712 INDEX

Mycenaean New Ohio Red Clay (NORC) 407,410,

krater 560f 413-141
period 559-60 New World 504, 654-5
pottery 12, 171,560 Nguni society 480
sherds 171 nickel (Ni) 92, 93, 95, !53, !59, 174,311,313,
vessels 561 329,367, 41lt, 4131,415,429-30, 50lj
Mykene 315 Niger 473,476,569,572
Myrtos 276-7 Nijmegen 168,1691,174
Nile Valley 372
Nabataean sigillata 337f nimite 92
nacrite 92 niobium (Nb) 347,356,367,369,370,371-3,
nannofossils 266,270-3,275,277,279-80, 4111,4131,4251
see also fossils, microfossils nitrogen (N) 348,387,4251,429, 432f, 493,
nannoplankton 274-5, see also plankton 627 I, 630, 636
nanoparticles 13,457 non -calcareous
National Bureau of Standards (NBS) 313 ceramics 163, 173-4,510, 5!3f, 52lf,
National Historical Publications and Records 522,612
Commission 81 clay 93, 164,338,612
National Institute of Standards and matrix 502
1echnology (NIST) 77f, 350,407,410, metallic assemblage 459
411-121,414,435,442 pottery 166,170,175,177
National Research Council 74 resources 260
National Science Foundation 76-7 sherd 167
Near East 306, 504, 546 non-destructive 11,163, 175-6, 33!, 342,
Neff, H. 76, 355, 408-9 344,347,356,363-6,368-9,371-4,394,
Negev Desert 276 404,449
neodymium (Nd) 13,305-7,309-13, 315-18, non-plastic
320, 40lf, 404,4121,4141,4251,436,534 inclusions 10, 25, 50,234-5,252,259,493,
Neogene 941, 268f, 276 495,501,511
Neolithic 87,451,505,569, 572,653 materials 402, 472, 50!, 503, 565
ceramics 233, 278, 570-1 phases 502
communities 189 states 98
Early Neolithic 569 tempers 255, 365
figurines 569 nontronite 92-3
pottery 336, 364f, 373, 453, 504, 569, Norman period 679-80
571, 664f North Furzton 274
sherds 164 nuclear reaction analysis (NRA) 387
sites 273,275,569 nuclear reactions 429, 431
Netherlands 168, 1691,275,278 nuclear reactors 10, 424, 426-7
Neupert, M.A. 355 nuclear research facilities 75
neutron activation analysis (NAA), see nuclides 310,429,433-4
instrumental neutron activation analysis nuclides
(INAA,NAA) quantification 433
neutron diffraction (ND) 447,459 radionuclides 427,672,676, 678
neutron diffraction analysis (NDA) 327
New Archaeology 189, 658 Oaxaca 432f, 440f
New Mexico 267,311,314,318-19,355 obsidian 74,364-5,369,402,409
 INDEX 713

Okhotsk pottery 355 ostracods 266-8,270-2, 273f, 276,279,566

Old World 568 Otterbach 333,334-51
olivine 240, 242t, 2471,261,302,414 Oxford Archaeological Lead Isotope Database
Olsen, B. 122, 124 (OXALID) 306,311
Olympia 172 Oxford Luminescence Dating Laboratory 672
ontology 123, 135 oxygen (0) 13, 87, 90,93-4,274,280, 294f,
opacifiers 9, 11, 13,22 2971,336,338,425~429,489-90,501f,
opal 517f 493, 524f, 533,537-8, 539f, 6271,630
ophiolite 2501, 302 Oztiirk, A. 160
optical emission spectrometry/spectroscopy
(OES) 9-10,12,99,162,327,371,401 Pacific 408,415, 416f, 571
optical microscopy (OM) 9, 35,233,235,237, paddle and anvil 547, 548f, 549, 558
240,288,296,299-300,409,439,536 Padri 229
optically stimulated luminescence painted
(OSL) 672-5,677-81,686-7 amphorae 513f
organic ceramics 537
additives 90 coatings 318
coatings 479-80 decoration 221,223,453
compounds 10,266,565, 568,632 Iberian pottery 27
contents 164, 168, 176,437 jug 513f
dyes 636 motifs 224, 227
fragments 546 pottery 451
impurities 498 Pueblo pot 267
inclusions 51, 545, 565-8, 570, 572-6, 578 sherds 68
material 104,255,259,441,480,498-9, wares 68, 217
535,566,568,571,576,626,629-30,636, painting 104, 156,217,227,256,318-19,383,
676,687 387,537,544
matter 52, 166,207,252-3,259,274,499, paints 234,271,308,347,404-5,409,419,
521f, 567,571,576,630,635,685-6 437,451,453,457-8,474,511,523,524f,
metabolism 630 525,534-5,540,559,634
molecular species 536 Paiutes 355
molecules 6271, 628, 630, 636 Palaeocene 277
origin 299 palaeoenvironmental
phases 168 analysis 277-8
pigment constituents 453 approach 275
remains 636 reconstruction 266
residues 51,6-7, 9, 10, 13,625-6,6271, Palaeolithic-Neolithic sequence 653
628-30,632,635-8 paleodose 673, 675-7, 680
sources 632 paleoethnobotanists 626
temper 125,252,565,568,570,613,622 paleontological
walled microfossils 268-9,272,274 identification 188
waste 167,389 materials 634
organisms 241,293,565-6, 575 paleontologists 73, 636
ornamentation 270-1,354,455,477,663, see Palestine 158, 188,568
also decoration Pallecchi, P. 6, 571
orthoclase 2451, 248-91, 260, 299 palynomorphs 272,274,280, 567
orthopyroxene 2421, 2451, 2481, 302 Pantelleria 91f
. --~

714 INDEX

Papua New Guinea 400,409,415, groups 107-9, 372

416/,417-18 homogeneity 108
Parma University 533 information 353
particle accelerators 447,461 level 21, 24-5, 43
particle induced X-ray emission (PIXE) 4, 51, methods 25,206,315-16
382-8,391-5,458 microscopy 9, 99, 270
paste studies 25,234,237
analysis 365,408-9 petrography 51, 7, 10, 25,88-9,99,202,204,
preparation 20j, 21,24-5,27, 99, 125, 192, 206-7,233-4,236,239,241,254-5,258,
195,272,280,459-60 261,302,317,369,371,374,409,415,
processing 442 439,459,523,526,546,605,607-8
paste compositional reference units petrological
(PCRU) 24-5 level 44
Pastoral 570 microscope 271
Peacock system 204 slides 270
Peacock, D.P. S. 116,204,233 techniques 305-6
pedogenesis 90 thin sections 270-1
pedogenic concretion 294j, 299 petrology 202,206,267,279,545
pegmatite 92 Peverel, R. 679
pelletron tandem electrostatic accelerator 386 Phaistos 336
pennantite 92 phengite 92
people-thing relations 135 phenocrysts 241
peptides 6271, 634-5 phiale 60-1
Pereira, J, 591 phlogopite 2421
performance characteristics 6, 12,26-30,43, phosphorus(P) 166-70,172,174-6,294/,
90,96,121-2,237,253,257,488 301,3341,346-7,367-8,391-2,394,
periclase 290, 495 4111,4131,4251,426, 501j, 571,574
periodic table 154,426 photomicrographs 207, 258j, 499
Perlman,!. 78 photons 328,344,347-8,351,383-5,401,
Perlman-Asaro Standard Pottery 75,78 432,429,433, 448j, 449-50,460
permeability 20j, 27,253,256,258,274, photosynthesis 269
472,621 phyllite 92,205,209-10,241,616,622
Permian 567 phyllosilicates 87, 90,92-3,565
Peru 11,77,390,414 physical properties 4, 7, 9, 12, 19, 21, 96,
Peruvian pot 544, 546 126,189,200-1,357,472-4,487-8,495,
Petra 337j 603-9,623
Petrie, W M. F. 188,653, 654j, 655 physicochemical
petrofacies 105,107,211 changes 497
petrographic characterization 53
analysis 25, 44, 52, 149, 152, 156, 158, parameters 336
233-4,307,410,415,440,501,569,571, properties 104, 471
573,606-7 techniques 75
approaches 153 physicomechanical properties 200-1

I
composition 504 physics 105, 119,329,344,389,394,635,672
data 153, 159,276 phytoliths 266,269,273,278-9,567,569-70,
databases 158-9,241,295,608 626,6271,628
features 153 Picon, M. 28-9, 148, 154, 169, 171, 174

I
J
 INDEX 715
---~

pigments 11, 20f, 21-2,302,308,346,372-3, portlandite 495

382, 387f, 389,425,437,451-3,457,474, post -depositional
479,511,523, 524f, 525,537-8,540,675 alteration 54-5, 154, 163,166-7,171,
Pinter, F. 309-10,316 174-6,343,347,365,368,403,409
Pisa 39, 40f, 42 changes 162
plagioclase 210,239-40, 244t, 248-91,252, conditions 170, 252, 496
260,292, 294f, 2971,301,308,312,335-6, contamination 166,439
495,520 effects 49, 55,166,174
plane polarized light (PPL) 205,237-9, environment 23, 163, 175,576
257,258/ factors 439
plankton 268-70, 273-6, see also phenomena 50, 55
nannoplankton pottery 22
plants 125-7,266,269,277-9,306,566-70, processes 4, 24-5,345,536,637
571f, 574, 576,625,632 time 20
plasma-ion source 401,402/ uncertainty 54-5
Pleistocene 941, 268, 277 variance 51
pleochroism 238, 242-81 post-firing 20f, 22,479-81
Pliocene 941, 273, 277 post-stratification 34-5, 38-9, 43
Plock 504 potassium (K) 51,54-5,92, 95, 171-2, 174-5,
Plumbate ware 408-9 212,242-501,257,291,293, 294f, 295,
polarizing filters 205, 212 297-81, 300-1' 308, 3341, 338, 366, 369,
polarizing light microscope (PLM) 99, 20!-2, 370f, 372,391-2, 393f, 394,410, 4l!t,
205,234, 235f, 237,573,608 4131, 4251, 436, 50lf, 505, 511, 538,
polishing, see burnishing/polishing 634,672
pollen 266, 268f, 269,271,274,276,278-9, potsherds, see sherds/potsherds
565-7, 569, 626 powder
polymer 291,332,630 diffraction 453
polymeri?.ation index 538, 539/ diffractogram 333
polymorphs 92, 249-501, 299, 540 diffractometer 332
polytypes 92 Powder Diffraction File (PDF) 328,
Pompeian red ware 545 333,3341
Pool, C. !!7-18 powdering !63, 174,366,403
Porat, N. !56 Pozzuoli 42
pores 163,165,167,172-3,207-8,235-7, Pradell, T. 13,457,458/
252-4,256,266,269,290,293,299,505, Prague ceramic type 189
565-7,605,607-8,6!1,613,6!6,621-2 praseodymium (Pr) 407f, 4121,
porosity 19, 20f, 21, 30, 127-8, 168, 171, 175, 4141,4251
234-5,237,252-4, 258f, 259,296,343, pre-firing 20f, 22
363,365,367,391,455,472,474,488, pre-Sigillata 453-5
493,495,497,499-500,505,571,605-7, prehistoric
612-13,621-3 ceramic materials 306
portable energy-dispersive X-ray fluorescence ceramic provenance 305
spectrometry (pXRF) 4, 51, 11, 13, 163, contexts 652
175,363-74 firings 259
portable XRF (pXRF), see portable humans 320
energy-dispersive X-ray fluorescence mining 311
spectrometry (pXRF) North America 637
716 INDEX

prehistoric (Cont.) Qala'at a)-Bahrain 569

Old World 568 Quadrate di Torre Spaccata 571
peoples 188, 305 quartz 9-10,90,93, 95,204-5,209-12,239-
plant use 577 41,2441,248-501,252-3,257, 258f, 260,
pottery 74, 196,343,372,571 290f, 291-3, 294f, 295f, 300, 308, 319,
sites 3, 343 3341,335, 337f, 338-9,400,410,415,438,
sociallandscapes 12 441, 453, 458, 495, 512, 513f, 514-15,
Prehistoric Ceramics Research Group 203 517f, 519, 523, 537-8, 545, 613, 615-16,
principal component (PC) 70,353,370, 619,672,674-6
439,540 quartzite 204,206,209,241,294/
principal component analysis (PCA) 69-70, Quaternary 941, 268/
72, 183,353, 370f, 371,394,539 Quechua women 190
producer-consumer relationship 472-3 Quichua potters 477
prompt~gamma activation analysis Quinn, P. 5, 209
(PGNAA) 427
Proto~ Historic Period 278 Racalmuto 97/
proteins 625, 634-5, 638 radioactive
proton beam 387-8,392 decay 308-10,347,427,430,433,672
protozoa 269 elements 174,673/
provenance studies 7, 10, 12, 27, 43,49-50, isotopes 347,424,426-34,436,438,676
80,88,148-50,154-5,158-9,175,273f, waste 425, 438
276-7,305-6,308-9,311,315,318, radiocarbon
354-5,363,373-4,379,399,408,415, analysis 574,629,635
439,501,526,399 dating 578, 671
pseudo-count transformations 32 method 686-7
pseudobrookite 454 radio-frequency (RF) generator 400-2
Pshenitsevo 316 radio-immuno-assay (RIA) 633
Pueblo radiography 548f, 550,552-3,555,
blackpigment 451-2 see also xeroradiography,
pot 267 X-radiography
potters 318 radioisotopes, see radioactive isotopes
Punic radiolaria 266, 268-9, 273f, 276, 566
communities 193 radiolarite 276
wheel-thrown vessels 194/ radionuclides 427,434,672,676,678
workshop 277 Raman
Pyrgos 276 bands 533-5,538
pyrometamorphism 88, 288 data 540
pyrophyllite 92 effect 531,535
pyrotechnical scattering 532
applications 617 shift 533
ceramics 605,620,622 signal 535
installation 21,487,489,605 spectroscopy 51, 6, 11,300,455,531,
processes 603 534-5, 538, 540, 626f, 6271, 628

l
products 652 spectrum 533-4, 536, 538
pyrotechnology 88, 459 wavelength 534
pyroxene 93, 238f, 239-40,242-71,261,289, wavenumber 532
292,300-1,306,312,520 Raman, Sir Chandrasekhara V. 531
pyxides 273 Ramu 418-9/
I
l
 INDEX 717

random numbers 67t, 68 Rishiri Island 355

rare earth elements (REE) 50, 95,309-10, Rizzutto, M. 4, 387f
313,350-1,403,425,440 rocks 87,90,92,95,125,202,206,208-9,235,
raw materials 3, 7, 9,11-13, 19, 20f, 21-27, 241,242-41,245-501,252,276,288,296,
43,48-52,55,59,73,75,87-90,93,95-6, 299,301-2,306,308-10,317-18,415,
98,101,103,105,107,120-2,129,148- 472-3,570
50,152-6,158-9,174,188,195,200-l, Roman
208,212,234-7,252,254-5,259-60, amphorae 21-2,30,62
267-8,276-9,300-2,305-7,309-12, Asia Minor 308
315-18,320,334,343,365,391,399, bricks 680
408-10,418,439,442,452-4,475-6,493, building materials 680
495,500-4,510-11,515,518-20,522-3, ceramics 188,203,686
525-6,536-7,565-6,576,578,603,607, cities 28, 35
608,663 cooking pots 212, 258f
Rayleigh scattering 532, 534 domus 35
re-firing 51,164, 171,173-5,397,487-8,496, empire 318-19
498,501-5 Gaul 454
Read, D. W 184,590 glass manufacture 310
Real Alto 279 Iron Age vessels 569
recarbonatization 165-7, 173, 176 legionarycamp 168
RedSea 569 period 154
Reed Research Reactor 78 potters 335
reference groups (RG) 24-5,27-9,43,51-2, pottery 30, 165, 168,170, 173f, 174,455
90,99,149-50,153,155-9,168-9,176, production centers 30
439,441 Samian Ware 505
refractive index 238-40, 250t, 300 tableware 453
rehydration 164, 166,296,681-2,520 Terra Nigra 170
rehydroxylation (RHX) 164-6, 168-9, 175-6, Terra Sigillata 27, 169, 188,333-4,336
296,504,522,583,672,681-7 towns 30, 38, 42, 44
dating 51,681,683-4,686 Roman-Byzantine period 290f, 294f
Reillon, V. 457 Romania 294f, 319
Renaissance ceramic 572/ Rome 571
Renson, V. 314,318 Romita pottery 409
Research Laboratory for Archaeology and the Rontgen, W 544
History of Art 8 rotative kinetic energy (RKE) 104-5,554,
resin 10, 125,205,237,291,293,312-14,331, 557f, 558-9, 560f
480,573 Rouse,!. 657,659
Rheinzabern 334, 503-5 Roux, V. 4
Rhine 170, 333 rubidium (Rb) 51, 95, 159, 169, 171,174-5,
rhizarians 270 307-8,344-5,360,365-6, 370f, 371-3,
Rhodes 62 407f, 4llt, 4131, 4251, 436, 50lf, 672
Rhodian pots 559 Russia 569, 572
rhyton 561 Rutherford Appleton Laboratory 450, 459
rice 273, 567-8f, 569, 571f, 574j; 577 Rutherford backscattering (RBS) !3, 387-8,
Rice, P.M. 185,477 458, see also backscatter
Rietveld, H. M. 339 rutile 95, 2491, 2921
RioGrande 318,409 Rye, 0. S. 253,544, 546c7, 549,618
718 INDEX

Sabi Abyad 126, 133 secondary electron (SE) 289-90,293,

Sahara 570 299,302
Sahel 569 secondary ion mass spectrometry (SIMS) 313
Sakhalin Island 571 sedimentary
Salinas 319 cycle 90,95
Samian ware 453 deposits 95,206,306-7,317-18
sampling 27, 32-5, 38-40, 42-4, 49-54, 66-9, environment 169, 576
150,152,155,158-9,207,314,330,368, material 206,212,307,309-10,312,320
372-4,400-1,404-6,408, 416f, 419,475, outcrops 277
496,594,628,652,655-6,675-6,678 petrography 204, 206
San Francisco Mountain gray ware 315f 317 rocks 87, 92,206,209,241-3, 245-6!,
sandstone 93,210,252,545 248-50!, 252,306,309, 416f, 570
Sanford, R. E. 352 sources 316
Sanidha 318 sedimentation 200, 255
sanidine 249t, 260, 299, 335 Seemann-Bohlin configuration 329
Santa Fe 318 Segebade, C. 174
Santorin 148 selenium (Se) 411t, 4251,550
saponite 92-3 sensitive high~ resolution ion microprobe
Sardinia 319 (SHRIMP) 311
Sarmizegetusa Regia 294f, 297 -8t Sepikcoast 400,415,416j,417-18
Sawankhalok 338-9 Serbia 319
Saxon-Norman period 679-80 Ser,e Limall! shipwreck 157f, !58
Sayre, E. V. 8, 75 seriation 182,187-8,196,217,655-7,663
Sborianovo 316 serpentine 92, 250!, 302
Scandinavian SerraHills 415,416f,417-8
pottery 364f sgraffitoware 156,158
scholars 653 Shaanxi 319
scandium (Sc) 50, 54t, 41lt,4!3t, 4251, 432{, Shackley, M.S. 75
436,440f shale 309, 317
scanning electron microscopy (SEM) 9, 35, Shannon index 34
39,260,272, 274f, 288,296, 338f, 342, Sheets, P. 409
364f, 369,373-4,400,406,408,417, Shennan, S. 70
452f, 453-4,459,497,536,573-5,605, Shephard, A. 88, 204, 223, 233, 603
607,612 Ceramics for the Archaeologist 8-11
scanning transmission electron microscopy sherds/potsherds 10,32-4,36, 38, 44, 48,
(STEM) 13, 455 50-I, 58,67-9,89, 107, 150·-3, 155,
scheelite 290 162-9,171-6,185,203-4,209,219-20,
Schiffer, M. 121 223-4,227,233-5,237,252-4,256-79,
schist 92,206,209-10,241,245-61, 250t, 409 291,293-4,301-2,305,307,312,314-18,
Schneider, G. 4 320, 331, 346, 364f, 365, 399, 404, 409,
Schokland 275 414-15,417-18,437-8,449-50,452,
Schurecht, H. G. 682 455-6,460,478,488,496,498-504,509,
Sciau, P. 453-4 536,544-6,558,567,570-3,585,589,
Science and Engineering Research Council 8 603,625,635-6
sculptures 200, 566 Shimada, I. 122-3
SeaofMarmara 316 Shirvalkar, P. 4
seawater 96,165, 172, 174 Shoshone 355
 INDEX 719

Shova,S. 6 social construction of technology

Sican culture 390 (SCOT) 119-21, 135
Sicilian workshops 96 social
Sicily 91f, 95, 97f, 275,277,372 actions 191,482
Sierra Madre Occidental 317 activities 191,586
silica 13, 104, 174,210,252-3,257,260,266, agencytheory 191
269,275,293,308,310,313-14,331, anthropology 102
336-9,438,515, 517f, 566,567,570,626 boundaries 102-3
silicates 87-8,90,92-3,95, 165-6, 25!t, 261, complexity 22, 26, 117
306,308,312,337,495,502,504,511-12, constructivist 115, 119-20, 122
5!3-14f, 515, 516f, 519-20,525-6, context 474,482,526
536-7,539 determinants 193
siliceous dimension 101-2
cement 270 dynamics 191
clays 254 existence 469,473
core 290f factors 120,470,474,476
melts 339 groups 12,101-3,109-10,119,121,126,
microfossils 268-9, 272, 273f, 275, 567 132,136, 192,201
spicules 574 identity 12,115,120-1,129,476-7
structure 566 inequality 117, 135
silicoflagellates 266,269,272,566 interactions 193, 475
silicon (Si) 87, 90,92-3, 157, 242-51t, 269, networks 474,481
290-1, 293, 294f, 295f, 2971, 3341, 336-8, relations 1!8-19, 122, 129, 131, 191,471
346,348-9,356,364,369,383,385-7, spheres 109, 194
391-2, 393f, 394,406-7,410, 41lt, 4!31, status 31, 128-9,474
4251,430,450, 501f, 538, 539f, 566,570, structure 114, 1!9, 190-1, 195
571f, 574 systems 19, 355
silicon drift detector (SDD) 348,369 technology 192-3
silicon pin detector (Si· PIN) 348-9, 369, 392 ties 102,415
Sillar, B. 12, 604 Society for American Archaeology 77
sillimanite 250t sociocultural
silver (Ag) 13, 172,310,319,328,345,348, choices 455
4251, 455, 457 complexity 3
skeuomorphism 182, 186, 193 connotations 191
slate 92 constraints 471,480
Slavic ethnicity 189 criteria 535
slips 9, 20f, 90, 104, 156, 163, 176,223-4, environment 22
256-7,269,271, 273f, 318,335,346,365, expectations 29
403-6,408-9,419,437,451,453-5,457, forms !!8
474,489,499,505,511,523,534,662 identities 201
smectite 92-3,95-6,300,337,510,512, 514f, markers 374
515, 516f, 518f, 519-20, 521f, 522-3, 525 patterns 558
Smith, M. F. 188 reasons 7
Smithsonian Archaeometric Research variability 109
Collections and Records socioeconomic
(SARCAR) 75-6 aspects 53
Soba 491/ constraints 4
7/.0 INDEX

socioeconomic (Cont.) standard reference material (SRM) 53,

context 116, 185 435,442
factors 623 Stanford Synchrotron Radiation Lightsource
implications 88 (SSRL) 450,455,460
issues 355 Stanford University 460
perspective 109 staurolite 250t
systems 374 stem and leaf plots 62, 64, 65f, 66, 72
view of a society 190 Sterba,). 4
sociological Stern, E.). !56, 636
complexity 108 Stilborg, 0. 278
composition 108 Stokes scattering 532
groups !08 Stokes' Law 96
interpretation 109 Stoltman,). B. 2!1
structure 110 Stoner, W. D. 410,414
variability 109 stoneware 9, 13,338-9,371
sociopolitical stratification 34-5, 38-9, 4!-3
centralization 118 stratigraphy !88, 266-7,276,653 \
complexity !17, 136 Straumanis configuration 329f, 331-2
organization 117 strontium (Sr) 13, 95, !59, !66-7!, 173-4,
processes 114
sbifts 457
!76,269,305-!3,3!5-17,320,365,367,
369, 370f, 371-3, 4!11, 4131,4251,436, \
sociotechnical 501f 6271,630
approach !15 Sudan 491{, 504
problems 454
sodium (Na) 5!, 54-5,92-3,96, !65-6,
Sukhothai stoneware 338
sulfur (S) 166-7, 176, 4llt, 4251, 630
\
171-2, 174-6, 242-31, 245-91, 251 I, 257, Sultanate of Oman 568, 570-lf 574/
291-2, 294f, 297-81, 300-!, 3341,345-6,
348, 35!, 363, 367, 383, 4llt, 4131, 4251,
Sumhuram 568, 570-lf, 574/
superconducting tunnel junction \
431,436,452,50~ detectors 349
Source optimisee de lumiere d'energie Sweden 569
intermediaire du LURE (SOLEIL) 450
South America 279, 390, 570, 572
Switzerland 165,337/
synchrotron radiation (SR) 4, !3, 23,339,
\
South Sakhalin 570 447-8,450,453,460
Spain 130, !65, 171, !87f, !94f,3ll,3!9, Synchrotron~Light for Experimental Science
343,599 and Applications in the Middle East \
Sparta 60-1 (SESAME) 450
Spaulding, A. 658-60
Speakman,R.). 75,367,369
Speyer 170-1
sphene 310
Syria 126,315,3!8,442,458,49~

Tabacnik, M. 4
talc 92,204,250-11
I
spicules 269,566-7,572,574-5 Tang, C. C. 454-5
spinel 239,2441,2501, 260-l, 300, 335f, 336,
338,510
tanglegram !26, !29, !3! \
Tarawai 4!5, 4!8
spores 266,268-9,274,276,278,567 Tarraco 29f, 30
Spring Hollow ceramics 2!1 TaurusMountains 311,319
St Marcel 2!2 Taylor,). 5 \
Staffordshire 442, 443/ Taylor,M. 2!7
 INDEX 721

properties 13, 20j, 23, 30, 565, 603-5,

technostylistic trees 108
607-9,622
Tel Dor 524f, 525
reactions 511
Tel Haror 276
regime 490
Tell Arbid 173
shock 95,253,257,522,616-20
TellArqa !06f
shock resistance 12, 35, 189,201,237,257,
Tell Beydar 458-9
609-10,616-20
Tell Mishrifeh 49lj
tempering 50, 89, 99, 154,200,255,288, stability 631-2
307,339,415,472,474-5,523,545,555, stress 472, 604-6, 610, 617-20
568-70,576-7,604-5,608,612-13,6!6, Thermal Color Test (TCT) 504
thermal ionization mass spectrometry
619,699
(TIMS) 311-14,405
Teotihuacan Valley 309,317
thermoluminescence (TL) 51,574,672-5,
Terra Helvetica 336
677-80,686-7
Terra Nigra 170
TerraSigillata 21-2,27,29, 34, 39, !67, 188, Thessaloniki 15lj
thin section 4, 7, 10, 35, 99, !07, 165, 167-8,
333,335-6, 337f, 453,503
17!,173-7,20!-9,21!,233-4,236-7,
terracotta 201,373
239-41,2421,246-71,252-61,269-71,
Territory Information System (TIS) 99
273f, 279,288,291,450,453,460,500,
Thailand 338f, 566, 569
504,536,568,573,575,578,607-8
thallium (Tl) 291, 314, 351, 412t, 414t, 425t
Thomsen, C. ). 653
1bebes 337f
thorium ("lb) 50,541,310-11,347,369,370,
Theran pottery 233
371,4121, 414t, 4251, 432f, 436,672
thermal
Thrace 316
affordance 606
three-dimensional mapping 453
alteration 274,499
time-of-flight (TOF) 402f, 405
analysis 682
time-of-flight neutron diffraction
behavior 30!,488,496,500-1,503
(TOFND) 459
breakdown 260
tin (Sn) 320,412-131, 425t, 537
changes 299, 534
Tiryns 315
color 19
conductivity 189, 257, 488, 605-6, 610, titanite 250t
titanium (Ti) !53, !55, 174, 2461, 249-SOt,
617,620-2
294j, 297t, 3341,347,350,369, 370f, 371-
crystallization 525
3, 391-2, 393f, 394, 4111, 4131, 425t, 436,
decomposition 260
440,454,501f
diffusivity 621
Tite, M.S. 9, 12, 88, 93,319,604,612
energy 535, 673
Titterington, P. F. 544
equilibrium 428
Torricelli Mountains 415-16, 418
expansion 235,253,257-8,613,
Tortonian 95
616-19
total organic carbon 629
flux 428
toughness 201,488,608-10,613-19
indicator 278
trace elements 50, 52, 93, 95, !59, 310, 343,
insulation 260
346,350,352,366,373,403,408,410,
loads 606
425, 436,.438, 439,442, 443f
neutrons 428-31,433-4
transition metals 50,437
phases 520, 525
transmission electron microscopy
processes 301
(TEM) 10, l3
profiles 478-9
722 INDEX

transmutation 19, 21, 25, 43, 430 unfired

transverse rupture strength (TRS) 29, clay 682
611-12,619 cuneiform tablets 129
Trias, M. C. 4 objects 492
tridymite 260, 335-6 pottery 20f, 21-5,43
Tripolitanian sigillata 167 waste fragments 129
Tritium 39, 40f unglazed ceramics 12-13, 373,437
Tritium Magallum 27-9,39, 40f, 42 United Kingdom (UK), see Britain/UK
Troy 233,309-!0,315-16,318 United States, see America/United States
Tschegg, C. 267 University of Bradford 8
t-test 69,71-2 University of Bristol 13
Tumbes 390 University of Durham 680
Tumleolsland 415,416f,517-8 UniversityofLyon 160
tungsten (W) 290,346,4121,4141, University of Michigan Ceramic
4251,437 Repository 74,76
Tunisia 258f,3!9 University of Missouri Anthropology
Turkey 11,233,310-11, 3!5-6f, 319, Museum Support Center 79
370,459 University of Missouri Research Reactor
Turpan 278 (MURR) 76-7, 79
Tusayan gray ware 317 University of Sao Paulo 386,389-91
TuxtlaMountains 415 University of Wisconsin 672
typological Unknown Terra Sigillata (UTS) 35-6
analysis 58, !82f, !85, 190-1, !93 Upper Mississippi Valley 211
approaches 114,1!6,118,134-5 uranium (U) 296, 310-11, 4121,4141,4251,
categories 151, 156,66! 427,436,672
characteristics 279 US Atomic Energy Commission 81
classification 88, 99, 181, 184-6, 188, US Department of Energy 81
192, 196 US Energy Research and Development
criteria 680 Administration 81
dating 671 US Geological Survey (USGS) 350, 407
debate 591
differentiation 195 Valdivia period 279
entities 189 Valencian ceramics 373
evolution 653 Vander Leeuw, S. 116
grouping 184, 192 Vander Waals forces 96
-interpretative tools !82f, 186 Van Olphen, H. 96
method 657-8 Van Pevenage, ). 6
ordination 657 vanadium (V) 95,4111,4131,4251, SO!f
phases 217 Vandenabee]e, P. 6, 53!
proposals 18! Vandiver, P. B. 9, 546, 558
series 653 vaterite 5!7/
strategies !87-8, 191-2,194-5 Vel de, B. 212
tasks 587 Velsen 168,1691,172,174
variability 186, 192 Venus ofDolni Vestonice 674
typology 4, St, 6, 118, 137, !52, !58, 183-5, Veracruz 355,415
!88-9!,196,438,585-9,59!,65!-5, Vidy 337f
657-8,663,687 Virgin Branch Anasazi ceramics 414
 INDEX 723

vitreous 43, 299 ·wilkinson, I. 5

coating 257 Williams, M. 5
materials 308 Wilson, L. 209
matrix 21 Wilson, M.A. 681, 685
silica 331 Wolf, S. 319
structures 44 wollastonite 88, 165, 251 t, 257, 260, 292t, 300,
vitrification 163,168,201,204,260-1,288, 336,511,519-20
300,308,455,488,495,497,499,504-5, Worn 416/,417
607-8,612,615 Worral, WE. 96
voids 35,207,209,235,252,255-6,
292-4, 295f, 299, 344, 409, 495, xenotime 309,410
545-7, 548f, 549,552,554,557-8, xeroradiography 546,550, 551f, 552,559,
560,570-1,574 see also radiography, X-radiography
volcanic 315f, 316,416/ Xinjiang 278
ash 312,409,415 X-radiography 544-7,549-50,552,560,
deposits 307 see also radiography, xeroradiography
inclusions 42 X-ray
island 91/ diffractogram 164,333,337/
minerals 95 diffractometer 333, 33St
rock 95,206,233,241, 245t, 248-91,301, emitters 448
306,317 energy 175, 348
temper 95 equipment 546,550-2, 556t
terrain 372 fluorescence 27, 158-9,344,367,450/
von Laue, Max 328 mapping/maps 293, 295f, 299
scanners 553
wairakite 165,337, see also analcime sources 347-9
Waksman, Y. 4 transmission microscope 455
Walis Islands 418 X-ray absorption fine structure (EXAFS) 13,
Wallaert-Petre, H. 478 457,459
Wallis,N.J. 410,411-14t,415 X- ray absorption near-edge spectroscopy
Walton,M. 13,319,456/ (XANES) 13,454-5,457,459
Wand, M.P. 70 X-ray absorption spectroscopy
wavelength dispersive (WD) (XAS) 447,455
spectrometry 5t, 290/ X-ray diffraction (XRD) St, 11, 13,27-8,35,
wavelength dispersive X-ray fluorescence 99, 164-6,458/
spectrometry (WD-XRF) 159, 162-3, X- ray fluorescence imaging (XRFI)
166,168,175,342,344-7,350-2,356, 451,453
500,504 X-ray fluorescence spectrometry (XRF) 4-5,
weathering 21,23-5,35, 43, 50, 87, 90, 95, 10-11,13,23,27-8,35,39,99,158,159,
163,167,169,208,241,278,306,309-10, 163,327,334,342,344-8,352,354-6,
312,317,438 363,383,399,425-6,447,450,453-4,
Werra earthenware 685 458,628
Western blot 633 X-raypowder diffraction (XRPD) 92,327,
wheel throwing 104, 105f, 201,255-6,546, 450,453,457,548/,549,493
548{, 549,554,557,558,560 X-ray scattering (XS) 344,447, 448f, 459
Whitbread, I. 4-5 X-rays 13,288, 290f, 291,328,344-5,347-8,
Wiegand, B. 4 449,460,547-9,552
724 INDEX

Yaane medicine 473 zeolites 165-6,171,337

YanghaiTornbs 278 zinc 92, 95, 159, 166, 172, 176, 310-11, 313,
Yangtze 319,569 349,371,373,392,394,4111,4131, 425t,
Yao, Y.-F. 278 436, 50lf
Yaozhou 309,317 zircon 2421,2441,2481,2921,310,403,
Yap Islands 571 410,536
Yellin, j. 78 zirconium (Zr) !59, 174,347,365,369,
yttrium (Y) 404,4111,4131 370f, 372-3,410, 4llt, 4131,4251,
436, solj
Zacchiroli, G. L 49!f zoisite 247t
Zagros 546 zooarchaeologists 626
Zarrillo, S. 279 Zulus 480