INSTITUTE OF PHYSICS PUBLISHING MEASUREMENT SCIENCE AND TECHNOLOGY

Meas. Sci. Technol. 14 (2003) 15161526 PII: S0957-0233(03)56714-5

Neutron activation analysis and
provenance research in archaeology
Michael D Glascock
1,3
and Hector Neff
2
1
Research Reactor Center, University of Missouri, Columbia, MO 65211, USA
2
Department of Anthropology, California State University, Long Beach, CA 90840, USA
E-mail: glascockm@missouri.edu and hneff@csulb.edu
Received 27 November 2002, accepted for publication 7 April 2003
Published 29 July 2003
Online at stacks.iop.org/MST/14/1516
Abstract
Neutron activation analysis is a powerful quantitative analytical technique
with application in a broad range of disciplines such as agriculture,
archaeology, geochemistry, health and human nutrition, environmental
monitoring and semiconductor technology. Due to its excellent sensitivity,
great accuracy and precision, and versatility, the technique is a suitable
method for analysing many different types of samples. Archaeologists, in
particular, have made extensive use of neutron activation analysis for the
purpose of characterizing archaeological materials and determining their
provenance. This paper presents a brief history of the technique and its
application to archaeology, describes the physics behind the analytical
method, and explains how the method is generally employed to determine
the sources of archaeological materials.
Keywords: neutron activation analysis, nuclear reactions, cross-sections,
thermal neutrons, gamma-ray spectra, provenance, ceramics, clays,
obsidian, chert, multivariate statistics
1. Introduction
The application of chemical analytical methods to archaeo-
logical materials in support of provenance research has grown
rapidly over the past few decades. Provenance research en-
tails the use of compositional proles of artefacts and source
materials to trace individual artefacts from their nd spot to
their place of origin. The information obtained is used by
archaeologists to investigate questions regarding the location
of prehistoric production areas, the identication of routes of
trade and exchange of raw materials and artefacts, and the mo-
bility patterns of prehistoric peoples. Although a number of
techniques have been employed to characterize archaeologi-
cal materials, the analytical method with one of the longest
and most successful histories of application for provenance
research has been neutron activation analysis (NAA).
Neutron activation analysis is a sensitive technique useful
for qualitative and quantitative multi-element analysis of
major, minor, and trace elements present in many sample
matrices. With the exception of inductively coupled plasma-
3
http://www.missouri.edu/

glascock/archlab.htm
mass spectrometry (ICP-MS) on liquid samples, NAA offers
sensitivities that are superior to those possible by all other
analytical methods. Moreover, the accuracy and precision
of the technique are such that NAA is still one of the
primary methods employed by the National Institute of
Standards and Technology to certify the concentrations of
elements in standard reference materials. Applications of
NAA are by no means limited to archaeology, but include a
broad range of disciplines such as agriculture, geochemistry,
health and human nutrition, environmental monitoring and
semiconductors.
The NAA technique involves the irradiation of a sample
by neutrons to make the sample radioactive. After irradiation,
the gamma rays emitted from the radioactive sample are
measured to determine the amounts of different elements
present in the sample. As a result, NAA has a number
of advantages over most other analytical methods when
investigating archaeological specimens. First, it is nearly free
of any matrix interference effects because the vast majority
of archaeological samples are transparent to the probe, the
neutron, and the emitted analytical signal, the gamma ray.
Second, because NAA can be applied instrumentally (without
0957-0233/03/091516+11$30.00 2003 IOP Publishing Ltd Printed in the UK 1516
Neutron activation analysis and provenance research in archaeology
sample digestion or dissolution), there is little opportunity for
reagent or laboratory contamination. Third, the preparation
of samples from most matrices (especially geological sample
types) for analysis by NAA is extremely easyin most
instances a portion of the sample need only be weighed and
place in an appropriate container. In contrast, the difculty
of achieving complete digestion of geological samples for
analysis by ICP-MScan be challenging and the labour costs are
much greater. Finally, although nuclear reactors are becoming
less available while ICP-MS instruments are becoming
more widely available, many reactors offer competitive low-
cost analyses on projects involving collaborative academic
research.
This paper presents a brief history of NAA and its
application to archaeology, describes the physics behind the
NAA technique, and explains how the method is generally
employed to determine the provenance of archaeological
materials. The nal section presents a few examples of NAA
applied to recent archaeological studies.
2. A brief history
The notion that nuclear reactions might be used for quantitative
analysis rst occurred to Georg Hevesy and Hilde Levy in
1936 when they exposed rare-earth salts to a naturally emitting
Ra(Be) neutron source (Ehmann and Vance 1991). They found
that many of the rare-earth elements became highly radioactive
upon bombardment with neutrons, and the radiation emitted
from the different elements decreased according to different
time constants. From this discovery, they recognized the
potential for identifying elements present in mixtures of
samples through measurement of different radiations and half-
lives of the radioactive elements.
The 1950s and 1960s saw the construction of nuclear
reactors with neutron uxes sufcient to allow sensitivities for
NAA at levels of interest to solving real analytical problems.
In addition, there were improvements in the sophistication
and sensitivity of instrumentation used to make nuclear
measurements, and hundreds of experiments were performed
to measure the basic nuclear parameters (i.e. reaction cross-
sections, half-lives, gamma-ray abundances and branching
ratios) associated with nuclear reactions.
The potential of NAA as an archaeological tool was rst
recognized by Robert Oppenheimer in the autumn of 1954,
when he suggested its use to Dodson and Sayre of Brookhaven
National Laboratory (BNL) as a possible way to establish the
provenance of archaeological ceramics (Harbottle 1976). The
experimental work was undertaken by Sayre and reported to
archaeologists and chemists at Princeton in 1956 (Sayre and
Dodson 1957). At around the same time, a group at Oxford
began experimenting with the use of NAA on pottery and
coins (Emeleus 1958, Emeleus and Simpson 1960). The initial
applications were hampered by the poor resolution of available
detection systems (e.g. Bennyhoff and Heizer 1965), but the
advent of lithium-drifted germanium Ge[Li] detectors in the
early 1960s offered signicant improvements in resolution and
prompted a urry of archaeological applications (Harbottle
1976). It is interesting to note that a paper by Sayre (1965)
on the analysis of ancient glass was the rst to report the use
and advantages of the Ge[Li] detector in NAA.
Perlman and Asaro (1969) provided a description of the
standard-comparator method of NAAas applied to provenance
determination at the Lawrence Berkeley Laboratory (LBL).
Archaeologists turned more frequently to NAA during the
1970s and 1980s to determine the sources of pottery, obsidian,
chert and other materials (Hughes et al 1991, Kuleff and
Djingova 1990, Neff and Glascock 1995). The NAA
laboratories at BNL and LBL were joined by laboratories at
the University of Michigan, University of Toronto, Hebrew
University, National Institute of Standards and Technology,
University of Missouri, and a number of smaller university
research reactors. By the early 1990s, NAA was regarded as
the technique of choice for provenance research (Bishop et al
1990, Gilmore 1991).
Although the late 1980s and 1990s, saw reactor
decommissioning and retirements of key personnel which
concluded a number of the major programmes (i.e. BNL,
LBL, the University of Toronto and Hebrew University), the
demand for NAA has not decreased. Fortunately, although
there are fewer places to perform NAA today, the remaining
programmes have been able to increase their capacity such that
access to NAA is still readily available.
3. Theory
3.1. Nuclear reactions
Nuclear reactions occupy a central role in all methods of
activation analysis. In a nuclear reaction, an incident particle
(e.g. neutron, proton or alpha particle) interacts with a target
nucleus either by scattering or by absorption. The diagram
showningure 1illustrates a typical nuclear reaction involving
absorption of the incident particle followed by the emission
of both particles and prompt gamma rays and by production
of a radioactive nucleus. If the incident particle is a thermal
neutron, a prompt particle is rarely emitted. If the reaction
involves an incident fast neutron or a charged particle, a prompt
particle is always emitted. In either case, prompt gamma rays
will always occur. The reaction can also be described by the
expression
a + A [X] b + B + Q (1)
or in shorthand notation A(a, b)B. Where the symbol a
represents the incident particle, A is the target nuclide, [X] is
the compound nucleus in a state of excitation, B is the product
nuclide (often radioactive), b is the exiting particle or radiation,
and Q accounts for the amount of energy released or absorbed
during the reaction. If Q is positive, the reaction is called
exoergic. If Q is negative, the reaction is called endoergic.
Nuclear reactions caused by neutrons are typically
exoergic, and the required threshold energy is zero. Thus,
the reaction can take place when the incident neutron has a
kinetic energy of nearly zero. This is the situation for thermal
neutron capture or (n, ) reactions. When the incident neutron
energy exceeds the threshold energy for a reaction involving
particle emission, reactions such as (n, p), (n, ), (n, n

), and
(n, 2n) are possible. In most applications involving neutron
activation analysis, the product nuclide B is radioactive and is
followed by emission of one or more delayed gamma rays.
Techniques based on measurement of the prompt and
delayed radiation are referred to as prompt gamma neutron
1517
M D Glascock and H Neff
Figure 1. Diagram illustrating of the nuclear processes occurring
during interaction of an incident neutron, proton or other nuclear
projectile with a target nucleus.
activation analysis (PGNAA) and delayed gamma neutron
activation analysis (DGNAA), respectively. The latter
technique is frequently referred to as instrumental neutron
activation analysis (INAA) when the procedures employed do
not involve extra pre- or post-irradiation steps such as chemical
separations.
3.2. Reactor neutron spectrum and reaction cross-sections
Reactors based on the ssion of
235
U offer the most intense
neutron sources currently available for NAA. The spectrum of
neutrons in a reactor consists of three parts as illustrated in
gure 2. In the high-energy region, neutrons still have most
of their original energy from ssion (e.g. roughly 26 MeV)
and are frequently called the primary ssion neutrons or fast
neutrons. Fast neutrons lose energy rapidly through elastic
scattering with moderating materials in the reactor, such as
water and graphite. Neutrons in the energy range from 0.5 to
1 MeV are commonly referred to as epithermal neutrons and
have been partially slowed down. The distribution of neutrons
in the epithermal region approximates a 1/E slope. Below
energies of 0.5 eV, the neutrons are usually referred to as
thermal neutrons. Thermal neutrons have approximately the
same velocity (v) distribution as the molecules and atoms of
their surroundings (i.e. a MaxwellBoltzmann distribution) of
the form
dn
dv
=
4n
v
3
0

v
2
e
(v/v0)
2
. (2)
In a typical light moderated reactor, the uxes of epithermal
and fast neutrons are on the order of 23% and 710%
respectively of the thermal neutron ux. Neutron uxes are
generally expressed in units of neutrons cm
2
s
1
.
Tabulations of cross-sections for thermal neutronreactions
assume a velocity of 2200 m s
1
which is the most probable
neutron velocity for neutrons at 20

C and corresponds to a
most probable energy of 0.0253 eV. Reaction cross-sections
are usually expressed in barns (b) where 1 b = 10
24
cm
2
.
For most nuclides at lowneutronenergies the cross-section
for the (n, ) reaction obeys a 1/v law as shown in gure 3.
Although there are small deviations from the 1/v shape in the
cross-section curves for some nuclides, the average thermal
neutron cross-section
t h
is assumed to be approximately the
same as the cross-section at exactly 2200 m s
1
.
As neutron energies increase above 0.5 eV, the cross-
section curves for most target nuclides are characterized by a
number of resonance peaks added on top of the 1/v curve. The
energies of the resonance peaks coincide with the excited states
Figure 2. A typical neutron energy spectrum from a nuclear ssion
reactor.
Figure 3. Cross-section versus energy for a common neutron
capture (n, ) reaction involving thermal and epithermal neutrons.
of the compound nucleus. To facilitate calculation of reaction
rates in the 1/E-ux region an epithermal cross-section I
(also called the effective resonance integral) is dened by the
expression
I =

0.5 eV
(E)
E
dE. (3)
Because both thermal and epithermal neutrons can induce
(n, ) reactions, a non-rigorous but commonly used expression
for the total reaction rate for a particular nuclide assuming n
target atoms in the sample is given by
R = n[
t h

t h
+
epi
I ] (4)
where
t h
and
epi
are the thermal and epithermal neutron
uxes respectively. In most cases, the thermal and resonance
cross-sections are similar in magnitude, but the number of
thermal neutrons is much greater. Therefore, thermal neutron
activation generally accounts for a majority of the induced
activity in most elements. Examples of nuclides illustrating
the range of variability of thermal neutron (n, ) reaction
cross-sections are
27
Al (0.226 b),
45
Sc (26.3 b),
58
Fe (1.31 b),
138
Ba (0.405 b) and
164
Dy (2725 b).
At higher neutron energies, the cross-sections for (n, )
reactions are very small, and nuclear reactions that result in the
1518
Neutron activation analysis and provenance research in archaeology
ejection of one or more particles(n, p), (n, ), (n, n

), and
(n, 2n) reactionsdominate. These transmutation reactions
occur only when the neutron energy is above the minimum
threshold energy E
T
required for the particular reaction to
occur. Because the neutron energy distribution is complex
at high energies, the average cross-section for a fast neutron
reaction
f
is dened by the expression

f
=

ET
(E)(E) dE

ET
(E) dE
. (5)
Using this average cross-section, the total reaction rate for a
fast neutron reaction is given by
R = n
f

f
(6)
where
f
is dened the average fast neutron ux. There are
only a few instances in which fast neutrons are important in
NAA. Among these are the measurement of nickel using the
58
Ni(n, )
58
Co reaction and corrections to (n, ) reactions for
several light-mass elements (e.g. Na, Mg, Al) frominterference
due to fast neutrons.
3.3. Radioactive decay
Radioactive decay is the spontaneous transformation of atoms
by emission of particles or gamma rays from the nucleus,
or of x-rays after capture of shell electrons by the nucleus.
Radioactive decay is a statistical process. For a sample
containing a large number of radioactive atoms, there is no
way to predict which atom will be next to decay, but the
decay characteristics of the entire sample can be described.
The number of atoms that decay per unit of time is dened
as the activity A and is dened by the fundamental law of
radioactivity
A =
dN
dt
= N (7)
where N is the number of radioactive atoms and is the decay
constant.
The value of is different for each species of radionuclide.
An equation describing the time dependence of the number of
atoms of the radionuclide is
N(t ) = N
0
e
t
(8)
where N
0
is the number of radioactive atoms at time t = 0.
Therefore, the process of radioactive decay is an exponential
law, and the activity of the radionuclide is controlled by a
characteristic property known at the half-life (i.e. the period
of time during which half of the original atoms of that nuclide
have decayed). The half-life is related to the decay constant
according to
t
1/2
=
ln 2

=
0.693

. (9)
The half-lives of different radionuclides range from
milliseconds to several times the age of the universe.
For NAAusing delayed gamma rays, the number of atoms
decaying during the post-irradiation measurement period is
measured. The number of radioactive atoms present at anytime
depends on the total number of radioactive atoms produced
during irradiation less the number that decayed both during the
irradiationandinthe interval betweenthe endof irradiationand
the beginning of measurement. Thus, the rate of production,
half-life, length of irradiation (T
i
), length of decay (T
d
), and
length of measurement (T
c
) are important factors for NAA.
Mathematically, the rate of change in the number of
radioactive atoms during irradiation is the difference between
the rate of production and the rate of decay, i.e.
dN
dt
= R N. (10)
Assuming there were no radioactive atoms present at t = 0, the
number of radioactive atoms present at the end of irradiation
(EOI) is
N
EOI
=
R

(1 e
Ti
). (11)
In general, measurement of radiation emitted from a sample
made radioactive does not begin immediately after irradiation,
but after a period of decay. Under normal conditions, short
decay times are used for radionuclides with short half-lives and
long decay times are used when the half-life is long. The long
decay time allows possible short-lived nuclides with initially
high activities time to become insignicant. The equations
describing the number of radioactive atoms present at the
start of the counting period (SOC) and end of counting period
(EOC), respectively, are
N
SOC
= N
EOI
e
Td
=
R

(1 e
Ti
)e
Td
(12)
and
N
EOC
= N
EOI
e
Td
(1 e
Tc
) =
R

(1 e
Ti
)
e
Td
(1 e
Tc
). (13)
3.4. Decay schemes and gamma-ray spectroscopy
In NAA, the radioactive nuclei produced usually decay into
daughter nuclei by emitting beta particles. The daughter nuclei
created are often in excited states, and undergo emission of
one or more gamma rays before arriving at a ground state.
Measurement of these gamma rays yields the information
necessary to determine the abundances of elements in the
irradiated sample.
The decay schemes of nuclei range from simple to
complex. A simple decay scheme is exemplied by the decay
of
28
Al (t
1/2
= 2.24 min), which is produced by the irradiation
of
27
Al (e.g. Parry (1991), gure 4.2). The
28
Al nucleus decays
via

emission into the 1779 keVexcited state of the daughter

nucleus
28
Si. In this case, the transition from excited state to
ground state always leads to emission of a gamma ray with an
energy of 1779 keV and branching ratio of 100%. Other decay
schemes are more complex.
Gamma rays interact with matter in several ways, one
of which is an absorption process in which the energy of
the gamma ray is transferred to photoelectrons inside a
semiconductor detector. In general, the energies of gamma
rays from a neutron-irradiated sample will range up to
about 3200 keV, creating a spectrum of gamma rays whose
characteristics are representative of the sample. The spectrum
of gamma rays measured from a sample of pottery is shown in
gure 4.
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M D Glascock and H Neff
Figure 4. Gamma-ray spectrum for a pottery sample made radioactive by NAA and counted with a high-purity germanium detector.
The actual number of gamma rays collected by the high-
purity germanium (HPGe) semiconductor detector used to
measure them is smaller than the total number of decays due
to several factors:
(1) The intensities (gamma-ray branching ratios) of emitted
gamma rays are in many cases less than 100%.
(2) Some of the emitted gamma rays do not reach the detector.
Due to the isotropic nature of gamma-ray emission, only
those headed in the direction of the detector can be
measured.
(3) Aportion of the gamma rays will pass through the detector
without interacting, especially high-energy gammas. In
other cases, some of the gamma rays lose part of their
energy by Compton scattering and pair production effects,
thus contributing to the gamma continuum beneath the
photopeaks of primary interest.
The second and third factors comprise a characteristic of the
detector called the geometric efciency . At energies above
200 keV, the log of efciency approximates a linear function
of the log of energy
log = b log E

+ log a (14)
where constants a and b are dependent on the sample-to-
detector distance and dimensions of the detector crystal.
Various techniques are used to extract qualitative and
quantitative information from gamma-ray spectra. Given a
gamma-ray spectrum, the rst task is to identify the nuclides
responsible for the various peaks and the second task is
to determine the peak areas. Peak identication can be
accomplished by consulting a number of compilations of decay
schemes and tables listing the associated gamma-ray energies
and branching ratios (Erdtmann and Soyka 1979, Firestone
et al 1996, Glascock 1998). For most peaks, the peak area
(sometimes called the signal) can be determined by summing
the total number of counts under the peak and subtracting an
estimated background as follows
S = T B. (15)
However, for overlapping multiplets, peak tting routines
relying on the Gaussian shapes of peaks are commonly used to
determine the areas of individual peaks. The measured activity
is then calculated by dividing the peak area by count time.
The uncertainty in peak area is reported by calculating
the relative standard deviation in per cent. One of the
more common measures of standard deviation is given by the
expression
%s.d. = (100

S + 2B)/S. (16)
The limit of detection for a peak depends on how well the
background is known. The usual denition for the detection
limit is based on the two-sigma (95%) probability that a peak
should be observed above the background.
3.5. Calculating concentrations
In order to convert measured activities into concentrations
for the sample one can use an absolute method by which
knowledge of all nuclear and experimental parameters is
necessary such that the following equation expressing the
activity present at any time can be used
A =

m
M
N
A

(
t h

t h
+
epi
I )P

SDC (17)
where m = mass of sample (g), M = atomic
weight (g mol
1
), N
A
= Avogadros number (6.02
10
23
molecules mol
1
), = isotopic abundance, P

=
intensity of the measured gamma ray, = efciency of the
detector at the energy of the measured gamma ray, S =
irradiation factor (1 e
Ti
), D = decay factor (e
Td
) and
C = count factor (1 e
Tc
).
However, the absolute activation analysis procedure is
rarely used in archaeology where comparator methods are
normally preferred. The equation used to calculate the mass
of an element present in the unknown relative to a comparator
standard of known concentration is
A
sam
A
st d
=
m
sam
(e
Td
)
sam
m
st d
(e
Td
)
st d
(18)
1520
Neutron activation analysis and provenance research in archaeology
where A = activity of the sample (sam) and standard
(std), m = mass of the element and T
d
= decay time.
When performing short irradiations, the irradiation, decay
and counting times are normally identical for all samples and
standards (i.e. the steps are performed on individual samples
and standards sequentially and all counting is performed in
a reproducible geometry) such that all time-dependent and
geometric factors will cancel. Thus, the previous equation
simplies to
c
sam
= c
st d
W
st d
W
sam
A
sam
A
st d
(19)
where c = concentration of the element insample andstandard
and W = weight of sample and standard.
The majority of laboratories involved in NAA utilize
one or more multi-element calibration standards. The
basic procedure is to collect gamma-ray spectra for both
unknowns and standards under conditions that are as similar
as possible, then to use one of the equations above to calculate
concentrations of the various elements whose peaks appear
in the gamma spectra. Quality control or check standards
are generally included in each irradiation in order to provide
an independent check on the quality of the data and in
order to identify mistakes, such as weighing errors in the
standards. Certiedreference standards canbe purchasedfrom
the National Institute for Standards and Technology. Non-
certied standards can also be obtained from the United States
Geological Survey and other sources.
4. Methodology
4.1. The provenance postulate
The basic proposition underlying chemistry-based provenance
determination was understood by the early 1970s (e.g. Bieber
et al 1976, Harbottle 1976, Perlman and Asaro 1969, Sayre
et al 1971). But, it was Weigand et al (1977) who rst
stated explicitly that the effort to link artefacts to sources
through compositional analysis depends on the postulate
that there exist differences in chemical composition between
different natural sources that exceed, in some recognizable
way, the differences observed within a given source. Today,
this statement is known as the provenance postulate by
archaeologists. It is interpreted to mean that the raw material
source for responsible for an artefact can be successfully
determined through chemical analysis as long as between-
source chemical differences exceed within-source differences.
Source determination efforts based on the provenance
postulate can follow one of two separate paths as explained
by Neff (2000) and illustrated in gure 5. If the sources
are localized and relatively easy to identify, as in the case of
volcanic obsidian ows, rawmaterials fromthe known sources
are usually characterized and then artefacts of unknown
provenance can be compared to the range of variation of the
known source groups. On the other hand, if sources are
widespread, as is especially true in the case of ceramic raw
materials, the prospects of sampling and characterizing most or
all of the possible sources are impractical. As a result, ceramic
provenance researchgenerallyinvolves analternative approach
by which reference groups are created from the unknown
ceramic samples. In this more common approach to ceramic
Figure 5. Two approaches to provenance determination.
sourcing, individual raw material samples are compared to the
range of variation between ceramic reference groups.
4.2. Suitability of different archaeological materials
As mentioned previously, obsidian artefacts are relatively easy
to source by chemical analysis. In addition to the fact that most
obsidian sources are extremely homogeneous, the volcanic
sources are limited geographically to certain regions. Obsidian
is high in silica, but the trace and minor element constituents
sometimes differ by orders of magnitude between sources.
If all possible sources have been sufciently characterized,
the reliability of matching an obsidian artefact to its proper
source is excellent and the number of elements required to
identify the source may be very small. However, the reliability
of obsidian sourcing is sometimes challenged by processes
such as weathering and erosion which may distribute obsidian
cobbles far from their source vent or by obsidian sources with
multiple ows, between which the differences may be subtle.
For the latter, the determination of larger numbers of elements
by a high-precision multi-element technique such as NAA can
be essential.
Chert and int are sedimentary rocks high in quartz
that were commonly used in tool making and for which
source determination by chemical characterization is often
challenging (Luedtke 1992). Hoard et al (1992, 1993)
successfully differentiated several archaeologically important
Oligocene-age chert outcrops in the Great Plains, and Malyk-
Selivanova et al (1998) were successful in separating chert
bearing formations from Alaska. On the other hand, efforts to
differentiate between different chert outcrops in Belize have
failed to produce reliable source distinctions, the whole area
being essentially a single chert source (Cackler et al 1999).
Clearly the geographic extent and geological context of chert
sources are crucial to determining whether chert provenance
analysis will yield answers to archaeological questions.
Clays are so ubiquitous and their geological histories
are so varied that the reliability of distinguishing between
natural sources varies widely. In general, if the parent rock
contributions andweathering histories of twoargillaceous soils
or sediments are sufciently distinct, then the provenance
postulate will apply. Unfortunately, geological processes
of clay formation often do not create discrete, chemically
homogeneous sources but instead produce extensive deposits
that vary in composition both vertically and horizontally.
1521
M D Glascock and H Neff
More generally, in sedimentary clay deposits, the proportions
of material from different source rocks may vary gradually
across horizontal space, while textural variation and chemical
weathering may create vertical differentiation within a
single stratigraphic column. Such conditions highlight the
importance of explicitly identifying the geographic scale at
which the source is conceived (Neff 2000). After manufacture,
the use of an artefact and post-depositional processes may
modify its chemistry. Lithic materials (i.e. rocks) are rarely
affected by this problem, but for ceramic compositional studies
diagenetic alteration is always a potential concern.
Steatite, pipestone, turquoise, limestone, marble, basalt,
ancient glass, native copper, coins and other archaeological
materials have been analysed by NAA with various degrees
of success for archaeological interpretation (Harbottle 1976,
Mead 1999, Truncer et al 1998).
4.3. Analytical procedures
In our laboratory, preparation of archaeological specimens
for instrumental NAA begins by removal of soil and other
foreign materials adhering to the surface. For lithic samples,
we usually obtain the analytical sample from clean interior
fragments after breaking or crushing the specimen. For
ceramics, the procedure involves burring away the surface with
a tungsten carbide tool to remove glazes or slip material that
may be contaminated by weathering or other post-depositional
processes. Lithic samples need only be fragmented into small
chips 2550 mg in size, while the interior paste froma ceramic
sherd must be ground to a ne powder and homogenized.
Individual samples are prepared for short and long irradiations
by weighing into clean polyethylene and high-purity quartz
vials (i.e. low blanks) respectively. All sample weights are
recorded to the nearest 0.01 mg. Reference standards are
similarly prepared.
A series of two irradiations and three gamma counts are
performed. The short irradiation is carried out on the samples
and standards in polyethylene vials using the pneumatic tube
irradiation systemat the Missouri University Research Reactor
(MURR) (ux of 8 10
13
neutrons cm
2
s
1
) in which
the samples are sequentially irradiated for 5 s, decayed for
25 min and counted for 12 min. The nine short-lived elements
measured are Al, Ba, Ca, Dy, K, Mn, Na, Ti and V. The samples
and standards in quartz vials used for long irradiation are
bundled together in batches of 3550 samples, four unknowns
and three quality control standards and irradiated in the reactor
pool (ux of 510
13
neutrons cm
2
s
1
) using 24 h for pottery
or 70 h for lithic artefacts. After a 7-day decay, the samples
are counted for 2000 s (the middle count) to measure seven
medium-lived elements, including As, La, Lu, Nd, Sm, U and
Yb. Following an additional 3- or 4-week decay, the samples
are counted again for 10 000 s. This last measurement yields
the following 17 long-lived elements, including: Ce, Co, Cr,
Cs, Eu, Fe, Hf, Ni, Rb, Sb, Sc, Sr, Ta, Tb, Th, Zn and Zr.
Standards and quality controls made from SRM-1633a
Coal Flyash, SRM-278ObsidianRock, SRM-688Basalt Rock,
and Ohio Red Clay have been irradiated and counted with each
batch of samples. These reference materials have been used
continually since the laboratory began in 1988. If necessary,
corrections or adjustments to batches of samples in the 50 000
specimen database can be made to account for any observed
drift in the analytical data.
4.4. Evaluation of data
The volume of compositional data generated in most NAA
studies of archaeological materials is substantial (ranging
up to 35 elements). As a result, multivariate statistical
methods are often required to quantify the similarities and
differences between specimens and groups of specimens.
Compositional groups can be viewed as centres of mass in the
compositional hyperspace describedbythe data. Anindividual
group is characterized by the location of its centroid and the
unique correlations of element concentrations to one another.
Pattern recognition methods such as cluster analysis, plots of
the original data in two or three dimensions, and principal
components analysis (PCA) are customary approaches to data
handling. These methods are described extensively elsewhere
(Baxter 1994, Davis 1986, Glascock 1992, Neff 2002) and will
be described only briey here.
Cluster analysis is a general term that applies to a variety
of specic techniques but the essential components are a
measure of the similaritydissimilarity between specimens
(i.e. distance) and an algorithm that groups specimens on the
basis of the dened measure. The results of cluster analysis are
generally presented in the form of dendrograms that show the
order and level of specimen clustering. Because interpretation
of dendrograms is highly subjective, it is normally only used
to identify possible groups after which other techniques are
employed for group renement and classication.
Bivariate and trivariate plots are used to examine the
correlations between variables, identify obvious groups and
detect outlier specimens. Condence ellipses (e.g. probability
intervals) are usually drawn around groups to emphasize
the differences between groups or to show the associations
between individual specimens and known groups.
PCA involves a transformation of the dataset on the
basis of eigenvector methods to determine the magnitude and
direction of maximum variance in the dataset distribution in
hyperspace. The PCA transformation provides a new basis
for viewing the entire data distribution to reveal structure not
readily observed when plotting the original variables.
Cluster analysis and many other multivariate approaches
to data handling are dependent on the use of Euclidean
distances to measure the dissimilarity between specimens.
However, Euclidean distances are not always the best approach
when working with geochemical data because they do not
account for the correlations between variables. Instead, a
distance measure known as the Mahalanobis distance (MD)
is very useful. The MD is dened as the squared Euclidean
distance between the specimen and group centroid, divided by
the group variance in the direction of the specimen. The MD
from a specimen k to the centroid of a group of specimens A
is written as follows:
D
2
k A
=
n

i =1
n

j =1
[C
i k
A
i
]I
i j
[C
j k
A
j
] (20)
where A
i
and A
j
are the mean concentrations of elements i
and j in the group and I
i j
is the i j th element of the inverse of
the variancecovariance matrix. The MDstatistic incorporates
1522
Neutron activation analysis and provenance research in archaeology

Figure 6. Map of the Mesoamerican region showing the locations

of major obsidian sources. The sources in Guatemala are: (1) San
Lorenzo, (2) San Martin Jilotepeque, (3) San Bartolome Milpas
Altas, (4) Laguna de Ayarza, (5) El Chayal, (6) Sansare, (7) Jalapa,
and (8) Ixtepeque. The sources in Mexico are: (9) Pico de Orizaba,
(1) Guadalupe Victoria, (11) Zaragoza, (12) Paredon, (13) Santa
Elena, (14) Tulancingo, (15) Tepalzingo, (16) Otumba,
(17) Malpais, (18) Pachuca, (19) Zacualtipan, (20) El Pariaso,
(21) Fuentezuelas, (22) Ucareo, (23) Zinapecuaro, (24) Tequila,
(25) Magdalena, and (26) Teuchitlan.
information about the correlations between pairs of elements
as derived by the off-diagonal terms of a variancecovariance
matrix, which simple Euclidean distance does not. Thus, it
permits calculationof the probabilitythat a particular specimen
belongs to a group based not only on its proximity to the group
centroid but also on the rate at which the density of data points
decreases away from the centroid in that direction.
5. Examples
5.1. Sourcing obsidian artefacts from Chichen Itza
The Maya civilization was famous for its knowledge of
astronomy and for developing a writing system. The Maya
of the Classic period (AD 300900) built cities throughout
Figure 7. Bivariate plot of Na versus Mn showing 421 obsidian artefacts from the site of Chichen Itza projected against the 95%
condence ellipses for sources in Mexico and Guatemala.
the lowlands of northern Guatemala and southern Mexico,
including the Yucatan Peninsula. Chichen Itza, in northern
Yucatan, was occupied during the Classic and subsequent
Early Postclassic period, when central Mexicoan people are
thought to have intruded into the Maya area. Since Chichen
Itza is located approximately 700 kmfromthe nearest obsidian
sources in Guatemala and more a 1000 km from the sources
in central Mexico (gure 6), changes in relative frequencies of
obsidian provide evidence about changing interaction patterns
of the sites inhabitants.
A collection of 421 artefacts from Chichen Itza and
nearby sites was submitted to the Archaeometry Lab for
NAA by a collaborator (Geoffrey Braswell). The samples
were analysed using a short-irradiation NAA procedure earlier
proven successful for this region (Glascock et al 1994) and
were compared to a database of previously analysed obsidian
sources. Figure 7shows a bivariate plot of Mnversus Na for the
Chichen Itza artefacts compared to 95%probability condence
ellipses for nine sources located in Guatemala and Mexico.
The comparison was highly successful with sources for nearly
all of the artefacts securely established. Nineteen (i.e. 4.5%)
of the artefacts with the lowest probabilities of membership on
the Mn versus Na plot were submitted to the long-irradiation
procedure. Examination of the additional data found that 17
of the artefacts agreed with the most likely sources suggested
by the short-irradiation procedure. The two remaining samples
were foundtobe tektite (i.e. a type of glass thought to be caused
by the impact of meteorites) instead of obsidian.
The Chichen Itza example illustrates that obsidian
provenance studies can be very valuable to archaeologists
interested in studying long-distance interactions between
prehistoric humans in the form of trade and exchange. Many
interesting questions about the inhabitants of Chichen Itza and
their contacts with peoples living near the obsidian sources can
be examined with the data from obsidian provenance studies.
In this case, the importance of interactions with central Mexico
was established conclusively. Other objectives of obsidian
1523
M D Glascock and H Neff
Figure 8. Map of the Ica and Rio Grande river drainages in
southern Peru where the Nasca civilization prospered.
research are to say something about the people who used
obsidianandwhytheir exploitationor trade patterns changedin
antiquity. A comprehensive database of obsidian sources such
as that we have established at MURR is essential to answering
questions such as these.
5.2. A pilot study on pottery from southern Peru
The Nasca culture developed along the coast of southern
Peru during the Early Intermediate Period (about AD 1750).
The Nasca ceramic tradition is distinguished by a neware
polychrome pottery, found throughout the southern coastal
region and renowned for its elaborate iconography, artistic
style and technical quality. The primary centres of Nasca
Figure 9. Biplot showing both the pottery samples and the element vectors on principal components 1 and 2 for the three Nasca pottery
subgroups identied by INAA. The magnitude and direction of the vectors represent the contribution of individual elements to the principal
components. Projections of the vectors on to the axes are equal to the coefcients calculated by PCA. Condence ellipses shown on the plot
have been drawn at the 90% probability level for each group.
cultural development were located along the Ica and Grande
drainages (gure 8).
Recently, a MURR collaborator (Kevin Vaughn)
conducted excavations at the Early Nasca (AD 1450)
domestic site of Marcaya. Ceramic data and radiocarbon dates
from the site indicate a relatively short span of occupation
(Vaughn 2000). Marcayas ceramic assemblage consists of a
highpercentage of neware pottery, especiallywhencompared
to other sites in the central Andes. Visual examination of the
neware pastes under low-power magnication identied three
different paste types designated paste type A, Band C. To date,
no evidence of pottery production has been found at Marcaya.
A sample of 100 excavated pottery sherds from Marcaya
was submitted to MURR for NAA to determine if the pottery
assemblage exhibited compositional variation. A total of 32
of the 33 elements normally sought by NAA were measured.
The sole exception was the element nickel, which we found
below our limit of detection by NAA in all 100 specimens.
The data were transformed to base-10 logarithms
and submitted to PCA. The transformation to logarithms
before PCA serves to make the data more normally
distributed and compensates for the different weighting
effects caused by using high concentration (e.g., Al and Fe)
and low concentration (e.g. rare-earth elements) elements
simultaneously. Examination of biplots of the samples
and element vectors against the rst and second principal
components (see gure 9) and the rst and third principal
components showed that the majority of specimens fell
into a single homogeneous compositional group, designated
group 1, with a relatively small number of specimens
clustering separately. The main group was evaluated and
rened using methods described in greater detail elsewhere
(see Glascock 1992, Neff 2000). Specimens with probabilities
of membership in group 1 of less than 1% were excluded.
Some of the specimens not assigned to group 1 were clearly
associated with two other distinct clusters of specimens
1524
Neutron activation analysis and provenance research in archaeology
Figure 10. Bivariate plot of samarium versus lanthanumfor the three Nasca pottery subgroups with condence ellipses drawn at the 90%
probability level.
designated group 2 and group 3. Small sample sizes prevented
testing the latter groups as rigorously as group 1. Figure 10
shows a bivariate plot of the data for the elements lanthanum
and samarium with the different pottery groups surrounded
by 90% condence ellipses. Fourteen of the 100 specimens
were not assigned to any of the groups. Unassigned sherds
from paste types A and B (not shown) were found to have less
than 0.000 0005% probabilities of membership in group 1.
The lack of analyses of clay sources precludes making
a strong conclusion that the pottery was not locally made.
However, the data from this investigation serve as an
initial database against which future pottery analyses can be
compared. The Nasca study demonstrates the strong need for
surveys of raw material sources followed by compositional
analysis.
6. Summary
After more than three decades of successful application in the
eld of archaeology, the reliability of NAA-based provenance
determination has been rmly established. In addition to its
sensitivity, accuracy and precision, the success of NAA is due
to the versatility of the method and the ease of preparing
archaeological materials for analysis. Archaeologists have
relied on NAA studies of artefacts to investigate human
activities such as trade and exchange, population mobility and
settlement patterns. Although the number of NAA labs has
decreased in recent years, the capacities of the remaining NAA
labs have been increased to keep pace with the still growing
demand.
Acknowledgments
The authors acknowledge their collaborators Geoffrey
Braswell and Kevin Vaughn who supplied the samples of
obsidian and pottery used as examples in this paper. The
National Science Foundation has supported the Archaeometry
Laboratory at MURR on a continuous basis since 1988.
The current grant number is BCS-0102325. We are very
appreciative of this support.
References
Baxter M J 1994 Exploratory Multivariate Analysis in Archaeology
(Edinburgh: Edinburgh University Press)
Bennyhoff J A and Heizer R F 1965 Neutron activation analysis of
some Cuiculco and Teotihuacan pottery: archaeological
interpretation of results Am. Antiquity 30 348
Bieber A M Jr, Brooks D W, Harbottle G and Sayre E V 1976
Application of multivariate techniques to analytical data on
Aegean ceramics Archaeometry 18 59
Bishop R L, Canouts V, Crown P L and De Atley S P 1990
Sensitivity, precision, and accuracy: their roles in ceramic
compositional data bases Am. Antiquity 55 537
Cackler P R, Glascock M D, Neff H, Iceland H, Pyburn K A,
Hudler D and Hester T R 1999 Chipped stone artefacts, source
areas, and provenance studies of the northern Belize
chert-bearing zone J. Archaeol. Sci. 26 389
Davis J C 1986 Statistics and Data Analysis in Geology (New York:
Wiley)
Ehmann W D and Vance D E 1991 Radiochemistry and Nuclear
Methods of Analysis (New York: Wiley)
Emeleus V M 1958 The technique of neutron activation analysis
applied to trace element determination in pottery and coins
Archaeometry 1 6
Emeleus V M and Simpson G 1960 Neutron activation analysis of
ancient Roman potsherds Nature 185 196
Erdtmann G and Soyka W 1979 The Gamma Rays of the
Radionuclides: Tables for Applied Gamma Ray Spectroscopy
(New York: Verlag Chemie)
Firestone R B, Shirley V S, Baglin C M, Chu S Y and Ziplin J 1996
Table of the Isotopes Vol I and II, 8th edn (New York: Wiley)
Gilmore G R 1991 Sources of uncertainty in the neutron activation
analysis of pottery Neutron Activation and Plasma Emission
Spectroscopic Analysis in Archaeology: Techniques and
Applications (British Museum Occasional Papers No 82) ed
M J Hughes, M R Cowell and D R Hook (London: British
Museum)
Glascock M D 1992 Characterization of archaeological ceramics at
MURR by neutron activation analysis and multivariate
statistics Chemical Characterization of Ceramic Pastes in
Archaeology ed H Neff (Madison: Prehistory Press)
1525
M D Glascock and H Neff
Glascock M D 1998 Activation analysis Instrumental Multielement
Chemical Analysis ed Z B Alfassi (Dordrecht:
KluwerAcademic)
Glascock M D, Neff H, Stryker K S and Johnson T N 1994 Sourcing
archaeological obsidian by an abbreviated NAA procedure
J. Radioanal. Nucl. Chem. 180 29
Harbottle G 1976 Activation analysis in archaeology Radiochemistry
vol 3, ed G W A Newton (London: The Chemical Society)
Hoard R J, Bozell J R, Holen S R, Glascock M D, Neff H and
Elam J M 1993 Source determination of White River group
silicates from two archaeological sites in the Great Plains Am.
Antiquity 58 698
Hoard R J, Holen S R, Glascock M D, Neff H and Elam J M 1992
Neutron activation analysis of stone from the Chadron
formation and a Clovis site on the Great Plains J. Archaeol. Sci.
19 655
Hughes M J, Cowell M R and Hook D R (ed) 1991 Neutron
activation analysis procedures at the British Museum Research
Laboratory Neutron Activation and Plasma Emission
Spectroscopic Analysis in Archaeology: Techniques and
Applications (British Museum Occasional Papers No 82)
(London: British Museum)
Kuleff I and Djingova R 1990 Activation analysis in archaeology
Activation Analysis vol 2, ed Z B Alfassi (Boca Raton, FL:
Chemical Rubber Company)
Luedtke B E 1992 Archaeologists Guide to Chert and Flint (Los
Angeles, CA: Costen Institute of Archaeology, University of
California)
Malyk-Selivanova N, Ashley G M, Gal R, Glascock M D and
Neff H 1998 Geologicalgeochemical approach to sourcing of
prehistoric chert artifacts, northwestern Alaska
Geoarchaeology 13 673
Mead A H 1999 Design analysis and chemical characterization of
non-tubular stone pipes of the Great Plains and Eastern US
PhD Dissertation University of Missouri, Columbia
Neff H 2000 Neutron activation analysis for provenance
determination in archaeology Modern Analytical Methods in
Art and Archaeology (Chemical Analysis Series) vol 135, ed
E Ciliberto and G Spoto (New York: Wiley)
Neff H 2002 Quantitative techniques for analyzing ceramic
compositional data Ceramic Production and Circulation in the
Greater Southwest: Source Determination by INAA and
Complementary Mineralogical Investigations ed
D M Glowacki and H Neff (Los Angeles, CA: Costen Institute
of Archaeology, University of California) Monograph 44
Neff H and Glascock M D 1995 The state of nuclear archaeology in
North America J. Radioanal. Nucl. Chem. 196 2
Parry S J 1991 Activation Spectrometry in Chemical Analysis
(Chemical Analysis Series vol 119) (New York: Wiley)
Perlman I and Asaro F 1969 Pottery analysis by neutron activation
Archaeometry 11 21
Sayre E V 1965 Renement in methods of neutron activation
analysis of ancient glass objects through the use of lithium
drifted germanium diode counters Proc. VII Int. Congr. on
Glass (Brussels, June 1965)
Sayre E V, Chan L-H and Sabloff J A 1971 High-resolution gamma
ray spectroscopic analyses of Mayan Fine Orange pottery
Science and Archaeology ed R H Brill (Cambridge, MA: MIT
Press)
Sayre E V and Dodson R W 1957 Neutron activation study of
Mediterranean potsherds Am. J. Archaeol. 61 35
Truncer J, Glascock M D and Neff H 1998 Steatite source
characterization in eastern North America: new results using
instrumental neutron activation analysis Archaeometry 40 23
Vaughn K J 2000 Archaeological investigations at marcaya: a
village approach to nasca sociopolitical and economic
organization PhD Dissertation University of California, Santa
Barbara
Weigand P C, Harbottle G and Sayre E V 1977 Turquoise sources
and source analysis: Mesoamerica and the Southwestern USA
Exchange Systems in Prehistory ed T K Earle and
J E Eriscon (New York: Academic)
1526