Applied Clay Science 57 (2012) 3948

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Applied Clay Science

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Research paper

Mineralogical and geochemical characteristics of Roman pottery from an

archaeological site near Monje (Slovenia)
Sabina Kramar a,, Judita Lux b, Ana Mladenovi c, Helmut Pristacz d, Breda Mirti e,
Milan Sagadin f, Nastja Rogan-muc e
a
Institute for the Protection of Cultural Heritage of Slovenia, Conservation Centre, Restoration Centre, Poljanska 40, 1000 Ljubljana, Slovenia
b
Institute for the Protection of Cultural Heritage of Slovenia, Conservation Centre, Preventive Archaeology Centre, Tomieva 7, 4000 Kranj, Slovenia
c
Slovenian National Civil Engineering Institute, Dimieva 12, 1000 Ljubljana, Slovenia
d
University of Vienna, Institute of Crystallography and Mineralogy, Althanstrasse 14, 1090 Vienna, Austria
e
University of Ljubljana, Faculty of Natural Sciences and Engineering, Department of Geology, Akereva 12, 1000 Ljubljana, Slovenia
f
Institute for the Protection of Cultural Heritage of Slovenia, Cultural Heritage Service, Regional Ofce Kranj, Tomieva 7, 4000 Kranj, Slovenia

a r t i c l e i n f o a b s t r a c t

Article history: Roman pottery excavated from the remains of a villa rustica near Monje (Slovenia) was analyzed in terms of
Received 28 April 2011 its mineralogical and basic geochemical characteristics, to elucidate the technologies of manufacture. Select-
Received in revised form 8 December 2011 ed samples were examined with optical microscopy, X-ray powder diffraction, SEMEDS and ICP-OES. Results
Accepted 24 December 2011
show that the studied pottery samples can be divided into two main groups based on the nature and size of
Available online 23 January 2012
grains; calcite-tempered pottery and pottery containing predominant ne quartz grains. This mineralogical
Keywords:
distinction also reects differences in production technology.
Roman pottery 2011 Elsevier B.V. All rights reserved.
Mineralogical composition
Petrography
Geochemistry
Technology
Monje (Slovenia)

1. Introduction
Ceramic production is one of the oldest and most widespread of all
human activities. Archaeological artefacts such as pottery, brick and
tile are important sources of information regarding ancient civiliza-
tions, providing clues not only of their technological skills, but also
of cultural and trade links between continents. Mineralogical and
chemical characterization of pottery, beside their documentation
value (Barone et al., 2002; Barrios-Neira et al., 2009; Belore et al.,
2007; Comodi et al., 2006; De Clercq and Degryse, 2008; Iordanidis
et al., 2009; Papachristodoulou et al., 2006) may reveal signicant
information about the provenance of the raw material used (Adan-
Bayewitz and Wieder, 1992; Barone et al., 2005; Sherriff et al., 2002;
Wieder and Adan-Bayewitz, 1999), and potentially the technology in-
volved in the manufacturing process (Belore et al., 2010; Breeze,
1986; Mangone et al., 2009; Rathossi et al., 2004; Schwedt and
Mommsen, 2004; Velraj et al., 2009).
When natural clay is not suitable for direct use in ceramic produc-
tion, treatment takes place in order to produce a workable clay paste
Corresponding author. Tel.: + 386 1 23 43 100; fax: + 386 1 23 43 176.
E-mail address: sabina.kramar@rescen.si (S. Kramar).
with optimum properties in terms of forming, ring and the resultant
physical properties of the nished ceramics (Hoard and O'Brien,
1995; Iordanidis et al., 2009; Tite et al., 2001). Many technological
procedures are currently available to achieve these desired character-
istics of the nal product, including levigation, tempering with
non-plastic materials and/or mixing of clays (Tite, 1999).
The presence or absence of certain mineral phases provides infor-
mation regarding the ring conditions in terms of both temperature
and atmosphere used during pottery production (Iordanidis et al.,
2009). It is known that during ring, clay minerals decompose and
react with temper minerals to form new microcrystalline mineral
phases, with the latter depending mainly on the composition of the
raw clay-rich material, its granulometry, additives, the ring temper-
ature as well as the kiln atmosphere conditions (Cultrone et al., 2001;
Daszkiewicz and Schneider, 1999; Maggetti, 1982).
Nevertheless, as yet relatively few studies have investigated the
abovementioned aspects of Prehistoric (ibrat-Gapari, 2008;
Zupani and Munda, 2006) and/or Roman ceramics (Daszkiewicz and
Schneider 1999; Daszkiewicz and Schneider, 2008a; Daszkiewicz and
Schneider, 2008b; Zupani, 2006; Zupani and Bole, 1997) in
Slovenia. One of the most important newly discovered archaeological
sites in Slovenia is located near the village of Monje, in the north-
west of the country. Architectural remains, together with the familiar

0169-1317/$ see front matter 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.clay.2011.12.008
40 S. Kramar et al. / Applied Clay Science 57 (2012) 3948

Fig. 1. Aerial photograph of the villa rustica site (residential building circled).
analogies of Roman villas and ancient literature sources (Lux, 2008;
Sagadin and Lux, 2010) indicate that the site is that of a Roman country
villa (villa rustica), which may also had been used as a road station
(mansio). Basic archaeological study of the selected pottery, based on
examination of ware shape, style, colour, decoration and overall fabric
was performed, although mineralogical and chemical analyses were
not conducted.
The present study therefore deals with the characterization of this
pottery, in order to determine potential differences in composition or
technology and their correlation with various time periods. The aims
of the study are:
- to determine the mineralogical characteristics of the Roman
pottery
- to assess the geochemical composition of the pottery sherds, and
- to determine the technological processes involved in their
production.
2. Experimental
2.1. Materials
Archaeological excavation conducted in 2007 of a Roman villa
rustica located near Monje, Slovenia, revealed the remains of ve
masonry buildings incorporated within an embankment (Fig. 1;
Kramar et al., 2008). Two of the main structures represent a residence
and a farm building, with the former having seven rooms, including
bath (balneum). Rooms of the bath complex were decorated by red
wall painting and polished white renders, while oor of the hot room
(caldarium) was covered with white and black mosaic (Kramar et al.,
2011). The discovery of small nds such as coins, jewellery, elements
of costume and fragments of pottery within closed stratigraphic layers
suggests that the Roman villa rustica was inhabited during the 1st and
2nd centuries AD, and that by the 3rd or early 4th century was already
in ruins (Sagadin and Lux, 2010). Various other archaeological nds
from mixed layers further indicate that the area has been inhabited
since the early Iron Age.
Information regarding the microlocation, type, surface colour and
probable date of the pottery samples is provided in Table 1.
Fragments of pottery were selected from closed stratigraphic units
exclusively from the area of the residential building of the villa rustica
and mostly dated to four specic time periods (Fig. 2). It is widely
known that coarse ware and also domestic tableware are usually of
local manufacture and usually these forms are not chronologically
very sensitive (Vidrih Perko, 1997). Nevertheless, it was possible to
date the oldest fragment to La Tne period (Late Iron Age) or
Early Roman period, followed by fragments from Early Roman
period, Roman period and the youngest fragments from Late Roman
period.
Only those samples of pottery, which according to archaeological
considerations were recognized as local or perhaps regional products
(i.e. not imported/terra sigillata) were selected for the study. Howev-
er, an amphora sherd was included as most probably representing an
imported sample (Horvat, 1999).
2.2. Methods
In order to characterize pottery texture, type and content of
particular components and technologies of manufacture, optical mi-
croscopy, X-ray powder diffraction, SEMEDS and ICP-OES analyses
were employed.
Polished thin sections of pottery samples were examined with op-
tical microscopy using an Olympus BX-60 microscope equipped with
a digital camera (Olympus JVC3-CCD).
Bulk mineralogical composition was determined via X-Ray Powder
Diffraction (XRD) using a Philips PW3710 X-ray diffractometer
equipped with Cu K radiation and a graphite monochromator. Data
were collected at 40 kV and 30 mA in the range 270 2, with a scan-
ning speed of 3.4/min. All samples were milled in an agate mortar to a
particle size of less than 50 m prior to XRD analysis.
Microtexture and chemical composition of polished thin sections
of the sherds were examined using the back-scattered electron
(BSE) image mode of low vacuum Scanning Electron Microscopy
(SEM) and the Energy Dispersive X-Ray technique (EDS), on a JEOL
5500 LV SEM.

Table 1
Pottery samples from the archaeological site near Monje.

Sample Location Type Surface colour Date

Grid square Stratigraphic unit (Munsell colour chart)

K1 L10 187 Coarse ware 7.5YR5/1 (grey) Late Roman (4th beginning of the 5th c AD)
K2 N8 160 Coarse ware 10YR7/6 (yellow) Late Roman (4th beginning of the 5th c AD)
K3 L10 137 Fine ware 7.5YR6/8 (reddish yellow) Early Roman (end of 1st c BC to beginning of 1st c. AD)
K4 N8 164 Fine ware 5YR6/6 (reddish yellow) Late Roman (4th beginning of the 5th c AD)
K5 N6,N7 127 Amphora 7.5YR7/4 (pink) Roman (1stc.4thc.AD)
K6 N7,O7 162 Coarse ware 7.5YR6/4 (light brown) Early Roman (end of 1st c BC to beginning of 1st c. AD)
K7 L9 196 Fine ware 10YR4/1 (dark grey) Early Roman (Late Iron Age?) (1st c.BC)
K8 L13 529 Coarse ware 10YR3/1 (very dark grey) Early Roman (end of 1st c BC to beginning of 1st c. AD)
K9 N7,O7 162 Fine ware 5YR6/8 (reddish yellow) Roman (1stc.4thc.AD)
K10 M9, N9 198 Coarse ware 10YR4/1 (dark grey) Early Roman (end of 1st c BC to beginning of 1st c. AD)
K11 N10 164 Coarse ware 7.5YR5/4 (brown) Late Roman (4th beginning of the 5th c AD)
K12 N7,O7 162 Fine ware 5YR7/6 (reddish yellow) Roman (1stc.4thc.AD)
K13 O7 162 Fine ware 5YR6/6 (reddish yellow) Roman (1stc.4thc.AD)
K14 L12 329 Coarse ware 7.5YR5/2 (brown) Early Roman (end of 1st c BC to beginning of 1st c. AD)
K16 N8 164 Coarse ware 7.5YR5/2 (brown) Late Roman (4th beginning of the 5th c AD)
 S. Kramar et al. / Applied Clay Science 57 (2012) 3948 41

Fig. 2. Map of the archaeological site, showing the residence and corresponding sampling locations.

All pottery samples were analyzed in terms of their major chemical
composition (SiO2, Al2O3, Fe2O3, MgO, CaO, Na2O, K2O, TiO2 and P2O5)
in an accredited commercial Canadian laboratory (Acme Analytical
Laboratories, Vancouver, B.C., Canada), after fusion with a mixture of
lithium metaborate/tetraborate and dissolution in nitric acid by induc-
tively coupled plasma emission spectroscopy (ICP-OES). Total carbon
content was obtained via combustion in an oxygen current (LECO
method), while CO2 and volatiles were measured by precision scale
weighing after calcination at 1100 C (LOI). The accuracy and precision
of the analysis are estimated to be better than 5% using the reference
material CCRMR SO-18 CSC. This was conrmed by the results of dupli-
cate measurement of 10 pottery samples as well as of the standards.
To identify distinct grouping of investigated pottery samples, hier-
archical cluster analysis was applied using Ward's method and
squared Euclidean distance. The basic statistical parameters for each
element and the calculations mentioned above were computed
using the statistical software programme Statistica VI.
3. Results and discussion
3.1. Optical microscopy analysis
According to optical microscopy, all investigated pottery samples
could be divided into two groups; one dominated by coarse calcite
grains (Group 1) and the other dominated by ne silicate grains
(Group 2).
The coarse grained sherds belonging to Group 1 (samples K1, K2,
K6, K8, K10, K11, K14 and K16), are characterized by the presence
of poorly sorted coarse calcitic grains, 4050% of the total mass,
which are randomly distributed throughout the sherds (Fig. 3). In

Fig. 3. Photomicrographs (Transmission light, crossed polars) of the pottery samples in Group 1. (a) Poorly-sorted coarse calcite grains with a high proportion of smaller grains, sam-
ple K2. (b) Coarse-grained monocrystalline calcite and elongated pores, sample K6. (c) Larger calcite grains with reduced content of ner fractions, sample K10. (d) Slightly rounded
calcite grains, sample K16.
42 S. Kramar et al. / Applied Clay Science 57 (2012) 3948
terms of their grain size (according to the UddenWentworth grain
size scale), pottery samples can be classied into those consisting of
a coarse sand fraction of up to 1 mm in diameter (samples K11 and
K16), a very coarse sand fraction (samples K1, K6, K8 and K14), and
those composed of very coarse gravel (sample K10).
With the exception of samples K11 and K16, which contain round-
ed calcite grains, in the remaining samples grains are angular and
probably derived from intentionally crushed rock, most probably
marble, which was added to the clay as temper. In the matrix,
minor amounts of small quartz and muscovite grains were also ob-
served. Rounded single-crystal quartz grains ca. 0.07 mm in size
occur in all samples within the group, although in samples K10 and
K16 rounded quartz also occurs in the form of slightly larger polycrys-
talline grains (up to 0.66 mm) and in sample K11 as microcrystalline
grains (up to 0.13 mm).
The most important difference between samples within this group
lies in the abundance of non-plastic inclusions (quartz and illite/
muscovite), as well as the smaller size and shape of calcite grains.
Dated to the late Roman period and containing only small amounts
of quartz, samples K1 and K2 are similar to those dated to the early
Roman period. It seems therefore that during the very late Roman pe-
riod (K11, K16) the source of the clay mass used in pottery produc-
tion had changed. In addition, the rounded calcite grains in samples
K11 and K16 could also represent the original clay mass, which con-
tains coarse carbonate grains.
The ne-grained sherds of Group 2 (samples K3, K4, K5, K7, K9,
K12, and K13) are primarily characterized by abundant quartz and
by lesser amounts of illite/muscovite (Fig. 4). Due to the large vari-
ability within the group, the sherds can be subdivided only according
to their grain size into those largely composed of a ne silt fraction
(samples K3, K5, K9, and K13), a ne very ne sand fraction
(sample K12), and those characterized by a medium sand fraction
Fig. 4. Photomicrographs (Transmission light, crossed polars) of the pottery samples in Group 2. (a) Fine grained pottery, sample K5. (b) Coarse sand fraction, sample K7. (c) Iron
nodules, sample K9. (d) Carbonate grains, fossils and well-orientated red clay streaks, sample K13.
(samples K4 and K7). Samples K4 and K13 in places also contain rem-
nants of well-oriented red clay illuviation a characteristic of the pri-
mary clay mass (clay accumulation). Samples in Group 2 are
differentiated in terms of their grain size, with samples K5, K3 and
K9 consisting of grains up to 0.15 mm, and samples K4, K7 and K12
being composed of middle-sized sand grains up to 0.6 mm.
Quartz grains in Group 2 sherds are mainly monocrystalline,
although polycrystalline forms were observed in places. Sample K12
also contained individual microcrystalline grains (chert). In sample
K9 grains of sericitized K-feldspar (0.140.37 mm) were identied,
while carbonate grains are present in sample K13, the latter consid-
ered to originate from the primary clay mass. These carbonate grains
are represented by rounded micritic limestone, ca. 0.200.64 mm in
diameter, as well as fossil fragments (foraminifera, 0.130.26 mm).
These microfossils are not present in the local geological formations
(Cimerman, 1967; Grad and Ferjani, 1976), suggesting a non-local
source for the raw material used for this sherd. However, fossils are
commonly quite common in archaeological ceramics, with marls
frequently being used as raw materials for pottery; Egyptian light
pottery is especially rich in microfossils (Riederer, 1992, 2004).
The sherds of Group 2 contain also numerous iron nodules, includ-
ing silt-size quartz grains, that are abundant in samples K9, K5 and
K13. This could suggest another clay source, as their occasional
streak-like appearance (as in sample K4) is similar to that occurring
in a heterogenous mixture of two clays with different iron content.
The mixture observed here is likely that of two varieties of a local
clay, probably from a natural source, rather than a mixture deliberate-
ly made by the potters (Daszkiewicz and Schneider, 1999). Wieder
and Adan-Bayewitz (1999) have reported that such soil nodules
were also added as temper in cases where the initial soil material
was rich in carbonates, apparently in order to improve the properties
of the raw material used in pottery production. However, iron
 S. Kramar et al. / Applied Clay Science 57 (2012) 3948 43

nodules are common constituents of clay in Slovenian soils and are
therefore also fairly abundant in archaeological pottery from the re-
gion (ibrat-Gapari, 2008).
The presented composition results indicate that it is possible to as-
sign the neware sherds to groups based on the various types of raw
materials used, i.e. clay containing carbonate grains, soil nodules, and
the occurrence of monocrystalline and/or polycrystalline quartz.
The mineralogicalpetrographic analysis results provide evidence
of two technological aspects involved in the production of the inves-
tigated pottery: samples containing coarse-calcite grains, were added
to reduce the plasticity (Group 1), and those with ne grains that are
part of the primary clay mass (Group 2).
With the exception of sherd K13 (Group 1), in which the carbonate
grains are probably constituents of the primary clay, in all other sherds
the coarse calcite grains were probably added as temper. Thus Group 1
may represent a collection of calcite-tempered pottery, well known for
being widely used in cooking vessels since the prehistoric period in the
midwestern United States and Europe (Hoard and O'Brien, 1995; Rye,
1976). This includes Neolithic and Roman Slovenia (Daszkiewicz and
Schneider, 1999, 2008b; ibrat-Gapari, 2008), with several examples
of shell-, limestone- and marble-tempered vessels. Calcite was often
also preferred as a temper over quartz, especially when manufacturing
tableware due to the exibility provided to create smaller vessels of
various shapes and wall thicknesses (Papachristodoulou et al., 2006).
A similar recipe might be expected for cooking pots, as calcite temper
generally ensures a high thermal shock resistance necessary for articles
exposed to repeated heating and cooling cycles during use (Tite et al.,
2001). Highly plastic clays, cannot be used alone for pottery making.
By adding the non-plastic calcareous material these changes swelling
and shrinkage are diminished, resulting in a more suitable raw material
(Adan-Bayewitz and Wieder, 1992). Also, calcite decreases the refrac-
tory nature of clay, allowing pottery to be red at lower temperatures
(Greene, 1986; Lawrence, 1972). The higher proportion of temper ob-
served in coarseware results in a tougher vessel, with the higher ther-
mal shock resistance required for cooking pots (Sherriff et al., 2002;
Tite et al., 2001). Moreover the thermal expansion rate of calcite is
very similar to that of the raw clay minerals used, thus preventing
the development of microcracks upon ring of the clay paste (Rye,
1976). The results presented here suggest that the vessels in Group 1,
given their temper content, were tough cooking vessels with high ther-
mal shock resistance, which were probably red at lower tempera-
tures. However, the use of a high temper concentration and low
ring temperature is the associated high porosity and permeability of
the vessel wall, which reduces the heating effectiveness of the resulting
cooking pot.
In general, to produce pottery with high strength requires a low
temper concentration and a high ring temperature. The lower con-
centration of temper in amphora, as observed also in our case,
would produce a material with high strength required for transporta-
tion (Sherriff et al., 2002).
3.2. X-ray powder diffraction
Results of X-ray powder diffraction (Table 2 and Fig. 5) are in gen-
eral agreement with mineralogicalpetrographic observations. Feld-
spar, hematite, magnetite, diopside and montmorillonite were
identied only using X-ray powder diffraction.
The two pottery groups dened according to optical microscopy
results also have distinct mineralogical composition. Group 1 contains
abundant calcite, followed by lesser amounts of quartz and in some
sherds also feldspar (Fig. 6a). With the exception of calcite, other car-
bonate minerals identied included ankerite in sample K11, suggest-
ing a different source of fabric for sherds of this type. Clay minerals
include illite in all Group 1 sherds, and traces of montmorillonite in
sherds K1, K10, K14 and K16. All these samples contain smaller
amounts of illite/muscovite compared to sherds in Group 2. Group 2
itself is characterized by the absence of calcite (with the exception
of sherd K13) and montmorillonite, and the presence of a signicant
amounts of quartz, followed by illite/muscovite and feldspar
(Fig. 6b). The presence of calcite in K13 indicates a parent carbonate
clay. Traces of hematite were recorded in some samples, while mag-
netite was observed in sherds K3 and K5. Diopside, typical of high
temperature ring, was identied in K5.
The mineralogical composition of the sherds depends on the com-
position of the raw material and on the ring conditions. Quartz
(Table 2) is often considered an indigenous phase found in clay de-
posits and thus its use as an intentionally-added temper is not easy
to conrm (Papachristodoulou et al., 2006). Quartz temper is more
likely to initiate cracking upon ring of the clay paste, owing to the
higher expansion rate of the quartz crystal (Hoard and O'Brien,
1995; Tite et al., 2001). As a result, quartz-tempered pottery is less re-
sistant to mechanical and thermal stresses arising during use, when
compared with calcite-tempered pottery (Tite et al., 2001). The pres-
ence of calcite in certain samples suggests that these sherds were
subjected to ring temperatures below 800 C (Iordanidis et al.,
2009; Musthafa et al., 2010). At temperatures higher than 700 C, cal-
cite will start to decompose to lime which rapidly hydrates on cool-
ing. This hydration is accompanied by expansion, which causes
spalling and cracking of the pottery (Feathers, 1989).
Feldspars, which are constituents of the original clay, are present
in all sherds in Group 2 and in most sherds of Group 1. The
feldspar-free sherds represent calcite-tempered pottery, suggesting
another type of clay used.
Although some XRD peaks may be masked, clay minerals tend to be
found only in sherds red at low temperatures (Daszkiewicz and
Schneider, 1999). Clay mineral structure collapses after dehydroxylation

Table 2
Results of X-ray powder diffraction. Number of (*) relates to mineralogical phase abundance. (/) mineralogical phase not detected, (?) possible presence.

Sample Quartz Calcite Ankerite Feldspar Illite/muscovite Montmorillonite Hematite Magnetite Diopside

K1 * ****** / / * ? / / /
K2 * ****** / / * / / / /
K3 ****** / / *** ** / * / /
K4 ****** / / * ** / * / /
K5 **** / / ** ** / * * **
K5 ** ***** / * ** / / / /
K7 ***** / / * *** / / / /
K8 ** ****** / * * / / / /
K9 ****** / / ** ** / * / /
K10 ** ****** / / / ? / / /
K11 ** **** / * * ? / / /
K12 ****** / / ** * / * * /
K13 **** ** / ** ** / * / /
K14 ** ****** / / ** ? / / /
K16 *** *** / ** ** ? / / /
44 S. Kramar et al. / Applied Clay Science 57 (2012) 3948

Fig. 5. X-ray powder diffraction patterns of pottery samples: (a) Coarseware (Group 1), (b) Fineware (Group 2).

to resemble an illite-like structure when a temperature of between 450
and 550 C is reached (Evans and White, 1958). A dehydroxylated phyl-
losilicate phase, structurally different to the hydrated version
(Guggenheim et al., 1987) exists at temperatures of up to 950 C when
complete breakdown of dehydroxylated illite occurs (Peters and Iberg,
1978). The greater illite/muscovite content in Group 2 sherds suggests
that they were decomposed at 7001000 C (Rathossi et al., 2004).
Depending on the composition of the ceramic body, complete
destruction of illite-muscovite at 9501000 C normally yields diopside
and gehlenite along with iron oxides such as hematite (Molera et al.,
1998).
Traces of hematite were identied in almost all Group 2 sherds,
causing the vivid orange colour of the sherds, which implies an oxi-
dising ring atmosphere. Sherd K7 on the other hand does not con-
tain hematite, which together with its grey colour suggests a low
ring temperature. The presence of magnetite in samples is related
 S. Kramar et al. / Applied Clay Science 57 (2012) 3948 45

Fig. 6. SEM photomicrographs of pottery samples. (a) Preserved laminar habit of phyllosilicates, sample K1. (b) Vitried matrix, sample K5. (c) Abundant phyllosilicates in the ma-
trix of sample K12. (d) Elongated pores, sample K16. (e) Illitemuscovite micromass, sample K7. (f) Limestone grain, sample K13.

to the occurrence of iron nodules (recognized under the optical mi- Si/Al ratio results (Table 3) reveal the use of a diversity of clays in
croscope), where the oxygen fugacity was not sufcient for hematite the production of the investigated pottery. Sherds of the calcite-
formation. tempered pottery (Group 1) in general contain greater Si/Al ratios,
Diopside was found only in sherd K5, associated by other high suggesting the use of montmorilloniteillite clay an argument
temperature minerals such as hematite. This suggests that K5 was
subjected to a higher ring temperature (>850 C) with respect to
the other sherds. Released by the decomposition of clays and temper Table 3
(quartz and plagioclase), SiO2 and Al2O3 react with free CaO to form Results of SEMEDX analysis of pottery matrixes, employing an average value of 15
spot analyses per sample.
Ca-silicates such as diopside and wollastonite, as well as CaAl sili-
cates such as anorthite and gehlenite (Rathossi et al., 2004). Pottery group Sample Si/Al ratio
In summary the XRD results suggest that the ring temperature Group 1 K1 1.90
did not exceed signicantly 700 C in Group 1 sherds, while in Group 1 K2 1.38
Group 2 sherds ring temperature reached up to 900 C. Group 2 K3 1.35
Group 2 K4 1.70
Group 2 K5 2.40
3.3. SEMEDS Group 1 K6 1.89
Group 2 K7 1.44
Since the type of clay mineral used is difcult to determine using Group 1 K8 2.35
Group 2 K9 1.33
optical microscopy and/or X-ray powder diffraction, a method com-
Group 1 K10 2.05
monly employed is the determination of Si/Al ratios derived from a Group 1 K11 2.00
series of spot microanalyses in sherd matrices. The SiO2 ratios are Group 2 K12 1.72
2.583.47, 1.532.62 and 1 for montmorillonite, illite and kaolinite Group 2 K13 3.88
respectively (Newman, 1987). Signicant textural differences related Group 1 K14 2.22
Group 1 K16 2.37
to pore morphology and pore volume, were also investigated.
46 S. Kramar et al. / Applied Clay Science 57 (2012) 3948

supported by the high abundance of Ca in the matrix of these sam-
ples. Other sherds are characterized by the predominance of illite, po-
tentially mixed with other clay minerals, especially those with very
low Si/Al ratio and enhanced Mg values could indicate chlorite
(Rathossi et al., 2004). In Group 2 sherds, extremely high Si/Al ratios
were identied in K5 and K13.
The matrix of Group 1 sherds is typied by the occurrence of elon-
gated pores or ssures (Fig. 6), with some cracks surrounding carbon-
ate grains. These carbonates do not seem to have been involved in
high-T reactions, suggesting ring temperatures lower than 800 C
(Cultrone et al., 2001). The laminar habit of phyllosilicates (illite/
muscovite) in the samples remains preserved although muscovite
crystals clearly exfoliate along basal planes, most probably due to
dehydroxylation. These samples do not show clear evidence of sinter-
ing or partial melting. The preservation of the laminar habit of phyllo-
silicates may indicate a ring temperature between 700 and 800 C
(Cultrone et al., 2001).
The sherds of Group 2 are characterized by a relatively compact
micromass, with the exception of K9, the elongated pores of which,
suggest another more plastic type of clay. In K7 an illite micromass
was identied, with the unaltered grains of illite indicating a lower
ring temperature (Fig. 6e). The laminar habit of some illite grains
was also preserved in K13, which together with the unchanged car-
bonate grains (Fig. 6f) indicates a low ring temperature. In contrast,
the matrices of other sherds from Group 2 have undergone change
characteristic of higher ring temperatures. For instance, the laminar
habit of illite was not observed in other sherds of this group. In K4, K5,
and K13 sherds pores were observed within the micromass. In K5 a
large amount of small pores was observed, probably due to extended
vitrication. The presence of many small pores is indicative of a
higher ring temperature, in accordance with the XRD results.
3.4. Chemical analysis
Major element analyses of the studied sherds, along with their
means and standard deviations, are listed in Table 4.
The high Loss On Ignition (LOI) values of sherds K1, K2, K6, K8,
K10, K11, K14 and K16 are attributed to the abundant calcite and
CaO present. Abundant levels of SiO2 were detected in samples K3,
K4, K5, K6, K7, K8, K9, K12, K13, and K16. These values are related
to the high quartz and also to the feldspar and illite/muscovite con-
tent in the samples. Fe2O3 and Al2O3 abundances range from 2.12%
to 7.99% and from 7.52% to 22.21%, respectively. The highest Fe2O3
Table 4
Major chemical composition of pottery samples (in %), including means, standard devi-
ations, minimum and maximum values.
concentrations were observed in sherds K3, K4, K5, K7, K9, K12 and
K13. Such values likely reect the presence of hematite/magnetite
and clay minerals in the abovementioned samples, which is in accor-
dance with the absence of coarse-grained calcite. Reecting their
higher clay mineral and feldspar content, sherds K4, K7, K9 and K12
contain the highest amount of Al2O3. Moderate concentrations of al-
kalis were observed in all sherds (0.07%0.75% for Na2O and 0.68%
3.02% for K2O). The highest potassium levels were observed in K4,
K5, K7, K9 and K13, reecting their greater K-feldspar and illite/mus-
covite content. MgO concentrations range between 0.76% and 2.64%,
with the highest values detected in K3, K5, K11 and K13 possibly re-
lated to the presence of montmorillonite, and additionally in K11 to
the presence of ankerite. Furthermore, the MnO content varies be-
tween 0.01% and 0.12%, and the TiO2 and P2O5 concentrations range
from 0.21% to 1.68% and from 0.17% to 1.68% respectively, without
signicant variations among the analyzed sherds. The major element
results generally reect the mineralogical composition of the sherds.
Multivariate analysis showed that the 15 sherds are clustered into
two major distinct groups, according to the prevailing mineralogical
component: carbonate or silicate (Fig. 7). This reects the results of
optical microscopy, in which samples are also distinguished in two
major groups. The only exception is sherd K16, which due to its
high SiO2 content plots as an outlier to the second group.
The rst group consists of 7 sherds (K1, K2, K6, K8, K14, K10 and
K11), characterized by high CaO content and respective stratigraphic
positions. Sherds K1, K2 and K6 form a rst small subgroup with com-
parable SiO2-contents. Sherds K8 + K11 and K10 + K14 also form two
subgroups, because of their very similar CaO and SiO2 contents. The
second group includes 8 sherds (K3, K4, K5, K7, K9, K12, K13 and
K16) characterized by high SiO2 contents. K4 and K9 have similar
mineralogical composition, whereas the other sherds of this group
have slightly different mineralogical composition. Sherds K3 and K5
are considered outliers at the beginning of the second cluster. K5,
the amphora sherd, was added as an imported sample for compara-
tive purposes and thus its position is not unexpected. Consequently,
it is possible that sherd K3 is also part of an imported ceramic vessel.
4. Conclusions
This study dealt with the characterization of pottery sherds from
an archaeological site near Monje in northwestern Slovenia. The
sherd samples differed in their mineralogical and chemical composi-
tion, reecting variation in the manufacture technology and the
type of clay material used. Differences in texture, and the size and
distribution of grains were also observed. The sherds were classied

Sample SiO2 Al2O3 Fe2O3 MgO CaO Na2O K2O TiO2 P2O5 MnO LOI

K1 17.90 7.52 2.28 1.07 35.48 0.12 0.68 0.31 0.39 0.03 34.1
K2 14.30 9.04 2.64 0.76 34.66 0.07 0.83 0.21 0.92 0.02 36.1
K3 51.83 16.86 7.99 2.57 1.57 0.74 1.81 0.97 1.68 0.11 13.6
K4 58.08 22.21 4.71 0.54 0.73 0.25 2.25 1.26 0.66 0.01 9.1
K5 53.24 16.25 7.30 2.22 5.31 0.60 2.04 0.93 0.63 0.16 11.1
K6 18.87 9.39 3.22 1.24 32.71 0.09 1.27 0.39 1.09 0.04 31.6
K7 63.75 19.90 4.83 0.80 0.61 0.32 2.36 1.21 0.26 0.01 5.7
K8 25.55 10.12 3.27 1.35 28.72 0.15 1.64 0.43 0.35 0.02 28.3
K9 57.32 21.62 5.66 1.29 0.76 0.69 3.02 1.03 0.32 0.07 8.0
K10 23.28 9.36 3.07 1.15 31.65 0.11 0.90 0.41 0.19 0.03 29.7
K11 25.63 8.98 2.12 2.58 28.20 0.52 1.09 0.35 0.44 0.03 29.9
K12 58.27 19.70 6.08 1.01 1.32 0.70 1.65 0.93 0.94 0.05 9.2
K13 47.48 14.31 6.03 2.64 10.32 0.75 2.30 0.68 0.83 0.12 14.3
K14 24.01 9.29 2.82 1.09 31.40 0.12 0.88 0.40 0.17 0.03 29.7
K16 38.31 12.95 2.71 1.74 18.52 0.59 1.94 0.46 0.38 0.03 22.2
Min 14.30 7.52 2.12 0.76 0.73 0.07 0.68 0.21 0.17 0.01 5.7
Max 63.75 22.21 7.99 2.58 35.48 0.74 3.55 1.26 1.68 0.16 36.1
Mean 39.95 14.34 4.44 1.49 16.43 0.41 1.77 0.69 0.59 0.05 20.2
Fig. 7. Pottery sample dendrogram based on Ward's method and squared Euclidean
SD 18.08 5.41 1.91 0.69 14.84 0.27 0.82 0.35 0.41 0.04 10.9
distance.
 S. Kramar et al. / Applied Clay Science 57 (2012) 3948
into two distinct groups: (i) Group 1 sherds made from clay with
high plasticity (calcite-tempered ware) contain abundant calcite
and lesser amounts of quartz and in some cases also feldspar and
montmorillonite. (ii) Group 2 sherds with a predominantly ne sil-
icate fabric, part of the original clay, are calcite-free (with the excep-
tion of sherd K13) and montmorillonite, and contain abundant quartz
and illite/muscovite, followed by feldspar.
The Si/Al ratios of clay minerals, revealed the use of various clays
in the production of the pottery. The high Si/Al ratio of Group 1 sherds
is suggestive of montmorilloniteillite clay, as is indicated by the high
amounts of Ca in the matrix of these sherds. In contrast, the sherds of
Group 2 contain mainly illite, probably used with other clay minerals.
Also the major element compositions of the two groups generally re-
ect the mineral composition of the samples. It is suggested that the
sherds of Group 1 were red slightly over 700 C and those of
Group 2 were red at temperatures up to 900 C.
Group 1 sherds are fairly homogenous, indicating that the technol-
ogy of manufacture had changed little with time. The mineralogy and
geochemistry of these sherds are also similar suggesting that they
must have been produced from the same source of raw materials, al-
though the greater quartz amounts observed in two Late Roman
sherds suggest a possible different source of the clay mass at this
time. In contrast, Group 2 samples are highly heterogeneous, indicat-
ing the use of various sources of raw materials.
Knowledge of composition of samples provides information about
the technology of pottery manufacture and indicates the provenance
of the raw materials. The lack of signicant change of the clay mass of
the coarse ware with time, suggests use of local clay deposits, where-
as the heterogeneity of the ne ware indicates various sources of the
raw materials and more possibly patterns of supply and demand of
materials. In order to identify the provenance of the clays, study of
the clay deposits in the vicinity area of the archaeological site will
be carried out in the future.
Acknowledgments
This work was nancially supported by ARRS Programme
group-P1-0195 geochemical and structural processes.
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