2016 Instrumental Neutron Activation Analysis (INAA) in Thestudy of Archaeological Ceramics

Instrumental Neutron Activation Analysis (INAA) in the Study of
Archaeological Ceramics
Oxford Handbooks Online

Instrumental Neutron Activation Analysis (INAA) in the
Study of Archaeological Ceramics
Leah D. Minc and Johannes Sterba
The Oxford Handbook of Archaeological Ceramic Analysis
Edited by Alice Hunt
Print Publication Date: Dec 2016

Subject: Archaeology, Archaeological Methodology and Techniques, Scientific Archaeology
Online Publication Date: Jan 2017 DOI: 10.1093/oxfordhb/9780199681532.013.24
Abstract and Keywords
Instrumental neutron activation analysis (INAA) is one of the most widely used analytical
methods for bulk chemical characterization of ceramic pastes, owing to its relatively
simple sample preparation procedures, the small sample mass required, and low
detection limits for most elements of interest. At least fifty major, minor, and trace
elements spanning the main geochemical element groups can be readily determined to
the percent, ppm or ppb level, although sensitivity varies by element. In this chapter we
provide an overview of the fundamental principles of activation analysis, and describe the
steps typically followed in sample preparation, irradiation, gamma spectroscopy, and
elemental analysis. In addition, we detail the strengths and weaknesses of INAA for
archaeological ceramic studies, and illustrate a few of the many applications that have
made INAA the mainstay for studies involving ceramic provenance, the organization of
pottery production, and ceramic technology.
Keywords: elemental analysis, INAA, activation analysis, bulk chemical characterization, ceramic provenance
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)
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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 activation 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 instrumental 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,
1995 (p. 425) ). 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 standards 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 characterization of ancient ceramics in the coming decades.
The popularity of INAA is largely the result of its simultaneous multi-element analytical
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 reactor; 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
provide data on 35–40 elements for each pottery sample. Detection limits for many trace
elements are excellent with minimum detectable concentrations (MDCs) in the low ppm
to ppb range, significantly lower than those offered by X-ray techniques such as XRF or
EMPA, and measurement errors are generally less that 5% for routine analyses, an
important consideration 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.
Table 24.1 The sensitivity of INAA in the analysis of ceramics varies by element, from
percent level to parts-per-trillion
Sensitivity Elements detected by INAA
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1 mg/g Si, S, Fe
10 μg/g Ca, Cr, Se, Rb
1 μg/g Mg, K, Sc, Ni, Zr, Nb, Sn, Ta, Os
100 ng/g Cl, Ti, Co, Zn, Ge, Kr, Mo, Ru, Pd, Ag, Cd, Te, Xe, Ba, Ce, Pr, Gd, Tb,
Tm Th
10 ng/g Na, Al, Ar, Cu, Ga, As, Br, Sr, Rh, Sb, I, Cs, Hf, W, Pt, Hg, La, Nd, Sm,
Ho, Yb, U
1 ng/g V, Re, Ir, Au, Er, Lu
1 pg/g Mn, In, Eu, Dy
Not H, He, Li, Be, B, C, N, O, F, Ne, P, Y, Tc, Tl, Bi, Pb, Po, At, Rn, Fr, Ra,
detectable: Pm, Ac, Pa
These advantages come at a cost: per sample fees of c.$30 to > $100 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, INAA provides no information on within-sample
variation or heterogeneity, such as that provided by the electron microprobe or LA-ICP-
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 (p. 426) 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 isotopes 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: 54Fe (5.8%), 56Fe (91.7%), 57Fe
(2.2%), and 58Fe (0.3%), while elemental copper has just two isotopes: 63Cu (69.2%) and
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65Cu (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 practical 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.
This process occurs in several steps. When a sample is exposed to the flow of neutrons
generated 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 excitation 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 (p. 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 10−13 s) to a more
stable configuration, emitting one or more prompt gamma rays (γp) or a charged particle
in the process. The technique of prompt-gamma activation 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
Click to view larger years, emitting beta
Figure 24.1 Schematic overview of neutron radiation and delayed
activation and subsequent decay. gamma rays (γd). 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 keV), 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 activities of the
induced radionuclides are directly proportional to the amounts of the elements present,
the elemental composition of the sample can be quantified precisely based on number 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
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(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 cm2 per second)
produced by a research nuclear reactor, whose primary function is to generate neutrons
for scientific purposes (Figure 24.2). Other neutron generators (including accelerators
and isotropic 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 235U 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.200 MeV
per fission), the reactor core sits within a large pool of water which serves to cool the
system and prevent melt-down. The water provides several other critically important
functions 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 of kinetic energy to water molecules increases the probability that these neutrons
will be absorbed by a 235U nucleus and initiate a fission event. Moderating materials such
as water and graphite (p. 428) 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.
Click to view larger
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Figure 24.2 The core of a research reactor providesAs a result of this
a high-intensity source of neutrons to activate moderation, all research
samples. The 1-MW OSU TRIGA reactor sits within a
tank of water ca. 2 m in diameter by 7 m deep. Fuelreactors produce neutrons
rods are loaded in a circular array and surrounded across a range of energies,
by a graphite reflector (outer gray ring), which helps
known as the neutron
to concentrate neutrons near the core. Between the
energy spectrum. Three
core and the reflector is the rotating rack or “Lazy
Susan” (inner dark ring), where samples are loaded main components are
for long irradiations. The pneumatic tube facility
(largely obscured by the control rods) delivers recognized: (1) the fast
flux consisting of
samples directly into the core for short irradiations.
energetic neutrons (> ~

0.5 MeV) born of the 235 U fission 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 of low-energy neutrons (energies
below ~ 0.5 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−1).
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
materials. Most research reactors have a well-thermalized neutron spectrum, such that
90–95% (p. 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 1/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 neutron 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 1012 n cm−2 s−1, while
larger research reactors of 10–70 MW thermal power provide neutron fluxes up to 1015 n
cm−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 irradiation locations utilized for INAA.
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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:
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 material is placed
within a well-thermalized beam of neutrons is “neutron capture”, also known as the (n,γ)
reaction in which a thermal neutron is gained and a prompt gamma is lost. The
absorption of a thermal neutron (nth) increases the mass of the nucleus (A) by 1 and
creates an unstable compound nucleus which immediately decays through release of a
prompt gamma ray (γp, a high-energy photon):
In some cases, the resulting isotope will be stable. More commonly, the nucleus
(p. 430)
remains 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: also designated as .
Note that the (n,γ) 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 a proton,
denoted the (n,p) reaction: .
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,α), (n,2n), and
(n, t) reactions.
Page 7 of 26

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:
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, can be produced from the thermal neutron (n,γ) reaction on , or a
fast neutron (n, p) reaction on .
Effective Cross-sections
The preceding neutron interactions occur with different frequencies depending on

neutron energy and the nuclear properties of the target isotope. The probability of a
specific reaction occurring is governed by the isotopic cross-section (σ), 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 cm2) 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 (Xi)
generated per unit time is directly proportional to the number of target nuclei (Ni), the
neutron flux (φ) in a specific energy range, and the isotopic cross-section (σi) for the
appropriate reaction: .
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 bombarded with
neutrons, based on the probability that activated nuclei will not decay during irradiation.
Although half-life (t½) is conceptually simple, the use of the decay constant λ is
mathematically much easier. Lambda can be related to half-life by the equation:
Radioactive Decay
Following neutron activation, the excited nuclei will spontaneously 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 (p. 431) the
activated nucleus emits a β particle, the mass equivalent of a high-speed electron. Two
distinct forms of beta decay are possible. In isotopes formed by the (n, γ) reaction which
show a neutron excess, the extra neutron will be transformed into a proton by the
reaction , and an electron (β−) together with an antineutrino (v−) is emitted. In
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contrast, when a fast nuclear reaction has generated an isotope with a proton excess, the
extra proton may be converted into a neutron according to the reaction , and a
+
positron (β ) together with a neutrino (ν) 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
cannot be quantified using INAA; important examples include P32 and S35. 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
working 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
following reaction and decay, and signals the presence of aluminum in the sample:
Similarly, a gamma peak at 1369 keV is characteristic of the following thermal neutron
reaction and decay, and indicates the presence of sodium in the sample:
Since these decays

(p. 432)
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

Click to view larger that most radioisotopes
Figure 24.3 The build-up and decay of radioactivity produce more than one
in an isotope according to its half-life and decay gamma, as they decay to
constant λ.
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 to ground-state occurs in
a single step and thus produces a single gamma. In contrast, the decay of 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 (γ).
Gamma-Ray Detection
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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 peaks in the spectrum. Their
detection and separation 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.
(p. 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 μs), 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
16,000 channels which
taken together represent
the entire energy
spectrum. The
accumulation of pulses or
Figure 24.4 Complex gamma-ray spectrum resulting
from the irradiation of an earthenware vessel from
“counts” in several
Oaxaca, Mexico. Several of the radioisotopes are adjacent channels creates
represented by multiple gamma peaks.
a peak in the spectrum,
representing the
radioactive decay of a specific isotope. The gamma energy of these peaks, reported in
keV, 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

shielding to protect it from miscellaneous radioactivity, such as that produced by
naturally occurring 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.
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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
gammas 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 for m (elemental mass) in the following equation, by
supplying the remaining constants:
where Peak Areai = total counts associated with the i representing the isotope of interest;
m = sample mass of element in grams;
θi = fractional abundance of isotope;
NA = Avogadro’s number (6.02 × 1023 atom/mole);
AW = gram atomic weight (gm/mole) of element;
σth = thermal neutron reaction cross-section;
φth = thermal neutron flux during irradiation;
I = resonance integral (epithermal neutron reaction cross-section);
(p. 434) φepi = epithermal neutron flux during irradiation;
λ = decay constant for the nuclide;
ta = irradiation or activation time;
td = decay time (from end of irradiation to beginning of count);
tc = count time (for collection of gamma spectrum);
γ = gamma branching ratio, i.e., % of total decays with a specific gamma energy;
E = detector efficiency at a given γ energy and geometry.
Page 11 of 26

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 (θi), 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 (φ, the density of available projectiles), the neutron
capture cross-section (σ, the probability of activation by neutrons of a specific energy),
irradiation duration (ta), and half-life or decay constant (λ) 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 (γ) and the detector’s efficiency (E) at the given sample-
detector distance and for the specific gamma energy, over the count interval (tc).
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 of high-purity gold wire) with each batch of samples in order to determine the
flux for a particular irradiation. In this case, the mass of the gold wire is known, allowing
researchers to solve the above equation for flux (φ). 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 k0 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 radionuclides 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 (θ), gamma branching ratio (γ), and the cross-section for
the capture of thermal neutrons (σ). While this ratio could, in principle, be calculated
from known values, it is much more convenient and the accepted approach to use widely
published, measured values (e.g., DeCorte and Simonits, 2003). To use the k0 method at a
given facility, detectors need to be characterized in a series of measurements to
determine their efficiency (E), while the flux (φ) 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
measurement error is about 5%. Thus, the k0 method is mostly applied in routine
measurements where high sample throughput at low total costs is more important than
highest possible (p. 435) precision. To facilitate routine analyses, several suites of
software have been developed that track characterization of the facility and reduce the
Page 12 of 26

time needed to perform an analysis, including the k0 freeware developed by the IAEA
(Rossbach et al., 2007) and the commercial kayzero program (DeCorte et al., 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
composition 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 (including 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 different decay times, the complex parametric
equation above simplifies to:
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 the 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 characterized 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 reference materials (SRMs) commonly used in the analysis of archaeological
ceramics, including 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, 2006). 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. These “check standards” also facilitate interlaboratory
calibration, enabling results obtained by one INAA laboratory to be compared against
those of other labs.
Irradiation and Analysis Procedures
Page 13 of 26

Although analytical procedures differ by INAA laboratory, a full multi-element analysis
necessarily involves two irradiations: a short irradiation for isotopes with short half-lives
(t½ on the (p. 436) order of minutes to hours), and a second, longer one to build up
activity in isotopes with longer half-lives (t½ 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
quickly retrieved and placed on the detector to collect a spectrum of the rapidly decaying
radioisotopes. 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
Na, K, Sc, Cr, Fe, Co, Zn, As, Rb, Sr, Zr, Cs, Ba, La, Ce, Nd, Sm, Eu, Tb, Yb, Lu, Hf, Ta, Th,
U, 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.1-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
interferences 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

The resulting data are distributed to the researcher as a table of concentration values in
percent (%), 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
minimum detectable concentration, or by zeros.
Page 14 of 26

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 1
ppm. The complexity of ceramic pastes, however, provides a worst-case scenario; the
detection limits shown in Table 24.1 are a realistic indication of MDCs attainable for
ceramic materials. 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 1–3% are routine for the (p. 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 combinations of low 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 × 2 cm) 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
surface 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
Page 15 of 26

and affect apparent element concentrations. Small clay tiles roughly 2 × 4 × 0.5 cm fired
in an oxidizing environment for 1 h at 800°C mimic conditions achieved by traditional
potters for earthenware 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 Br and As (Kilikoglou et al., 1988; Cogswell et al., 1996).
In all steps of sample processing, researchers should guard against cross-sample

contamination 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.
Final encapsulation of the powdered material for irradiation is typically done at the INAA
laboratory proper. A sample mass on the order of 200–500 mg is placed in clean vials of
high-purity (p. 438) 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 radioisotopes 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 of location, excavation context), typology (ceramic ware,
vessel form, surface treatment, date, cultural affiliation), and collection (museum, catalog
number), 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 photographically at 50x and 100x 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).
Page 16 of 26

Applications of INAA in Ceramic Analysis

Few analytical approaches highlight the problems of relating human behavior to
its material residues more than the compositional analysis of pottery.
(Arnold et al. 1991: 70)
Ceramic materials, owing to their complexity and plasticity, pose a challenge for
compositional 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
redeposition), 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 subtracts 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, (p. 439) 1988; Cogswell et al., 1996; Sterba et
al., 2009), while specific vessel uses (such as salt manufacture) can strongly modify
elemental signatures through the absorption of contents. Finally, post-depositional
factors may modify the composition of the pottery once it is discarded, through exposure
to ground-water minerals or industrial contamination (Buxeda i Garrigós, 1999).
As a bulk chemical analysis technique, INAA confounds the contributions of these

different factors into a single compositional profile. It is therefore essential to carefully
consider 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 variability 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 technique 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).
Page 17 of 26

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 signature such that artifacts made from that source can be linked to it based
on their compositional 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 dimensions may be needed to accurately characterize and distinguish between
clays or production sources.
Such studies typically begin with the identification of “composition groups” or “reference
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 D² statistic, a measure of the multivariate 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 (p. 440) (p. 441)
of internally consistent and mutually exclusive reference groups are defined. A third and
final step then involves the assignment of less-secure cases to their most likely
composition 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 reference groups.

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)
Page 18 of 26

Provenance as determined through INAA combined When ceramics have been
with petrographic analysis and regional clay survey.
obviously tempered, the
effects of variable amounts
of temper 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
significantly alter the relative chemical fingerprint, they only add mass to the sample,
effectively 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 geographic location.
Where no comparative materials exist, the “principle of local abundance” 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 variability and the areal extent of a “source” (Bishop and Blackman, 2002;
Minc and Sherman, 2011; Minc et al., 2016). For example, it is critical to know whether
the compositional signature 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 communities. 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
concerning 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 characteristics of regional economic systems that can be examined
once the products of a given manufacturer have been identified.
Page 19 of 26

(p. 442)Trace-element data can also be employed to evaluate changes in the intensity of
ceramic production, based on the assumption that, with full-time specialization, concerns
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 standardization
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 of Leilan, 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
differ in their natural degree of homogeneity (Arnold, 2000). 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.
Page 20 of 26

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
materials, 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 modeled 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
earthenwares 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
competition 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, 2008). Further, technical innovations, such as the early formulation of
bone china and the (p. 443) addition of cobalt to lend a whiter hue, are clearly
recognizable from the trace-element composition.

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
Page 21 of 26

one or more paste recipes, with a distinctive trace-
element composition (after Hale, 2008).
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
particularly 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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Leah D. Minc
Oregon State Radiation Cente
Johannes Sterba
Atominstitut, Technische Universität Wien
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Instrumental Neutron Activation Analysis (INAA) in the Study of

Oxford Handbooks Online

Print Publication Date: Dec 2016

Abstract and Keywords

(Muecke, 1980: 43)

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Sensitivity Elements detected by INAA

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10 μg/g Ca, Cr, Se, Rb

1 μg/g Mg, K, Sc, Ni, Zr, Nb, Sn, Ta, Os

1 ng/g V, Re, Ir, Au, Er, Lu

1 pg/g Mn, In, Eu, Dy

Fundamental Principles of INAA

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Following the emission of a

Although relatively simple in concept, the successful application of INAA requires a

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Neutrons and Nuclear Reactors

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energetic neutrons (> ~

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a is the projectile, i.e., a neutron of a specific energy,

The absorption of an epithermal or fast neutron, in contrast, creates a highly unstable

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The preceding neutron interactions occur with different frequencies depending on

Half-life and Decay Constant

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Since these decays

also occur with a

Finally, it should be noted

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Because of the sensitivity of HPGe detecters, the assembly is surrounded by lead

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Nuclide Quantification: Determining Element

m = sample mass of element in grams;

θi = fractional abundance of isotope;

NA = Avogadro’s number (6.02 × 1023 atom/mole);

AW = gram atomic weight (gm/mole) of element;

σth = thermal neutron reaction cross-section;

φth = thermal neutron flux during irradiation;

I = resonance integral (epithermal neutron reaction cross-section);

(p. 434) φepi = epithermal neutron flux during irradiation;

λ = decay constant for the nuclide;

ta = irradiation or activation time;

td = decay time (from end of irradiation to beginning of count);

tc = count time (for collection of gamma spectrum);

E = detector efficiency at a given γ energy and geometry.

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A third approach is known as the standard comparator method or direct comparison

In all of the preceding approaches, it is common practice to include samples of known

Irradiation and Analysis Procedures

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Analysis of each spectrum typically requires an environmental background subtraction

Trace-Element Data via INAA

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