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FLUORESCENCE
SPECTROMETRY AND
ITS APPLICATIONS TO
ARCHAEOLOGY
X-RAY
FLUORESCENCE
SPECTROMETRY AND
ITS APPLICATIONS TO
ARCHAEOLOGY
An Illustrated Guide
10 9 8 7 6 5 4 3 2 1
From Mary Kate Donais: For my father, Roy, for his encouragement and
guidance at the early stages of my scientific career. And for my husband,
Craig, for his support and patience so I can continue to pursue my passions
as a scientist, researcher, and educator.
From David B. George: For Linda who puts up with much and with-
out whom not much would get done.
From both authors: We would like to thank our colleague Prof. Sarah
Glenn of the Saint Anselm College Philosophy Department for editing the
manuscript and making many suggestions. She is the consummate philos-
opher and scholar with interests in many things in her quest to figure out
what the nature of the universe is and how we should behave in it.
Abstract
KEYWORDS
atomic spectroscopy, cultural heritage, elemental analysis, Etruscan cul-
tural material, excavation, field archaeology, materials characterization,
Roman material culture, X-ray fluorescence spectrometry, XRF
Contents
List of Figures xi
List of Tables xv
Preface xvii
Acknowledgments xxi
1 Theory and Basic Principles 1
1.1 X-ray Fluorescence Spectrometry 1
1.2 Field Applications in Archaeology 8
2 Instrumentation 13
2.1 Instrument Fundamentals 13
2.2 Wavelength Dispersive Instruments 19
2.3 Energy Dispersive Instruments 20
2.4 Portable Instruments 21
2.5 Micro X-Ray Fluorescence Instruments 22
2.6 Other Instrument Considerations 23
2.7 Safety 24
2.8 Practical Aspects for Archaeology and Conservation 24
References24
3 Data Collection 27
3.1 Introduction 27
3.2 Samples and Sample Preparation 27
3.3 Instrument Considerations 30
3.4 Instrument Parameters 32
3.5 Specifics Related to Archaeology 33
References35
4 Considerations for Data Collection in the Field 37
4.1 Introduction 37
4.2 Protocols 38
x • Co ntents
not even heard of the term in the early 2000s when the other coauthor, a
classical archaeologist, approached her to consider collaborating on some
bronze coin analyses. Many projects and publications later, this collabo-
ration continues to develop and grow. The chemist has learned about the
Etruscan and Roman cultures and has expanded her chemical knowledge
to include mineral pigments, ancient glass production, and historic con-
struction materials. The archaeologist has learned about reference materi-
als, quality control, calibration methods, and multivariate statistics. This
collaboration has changed the way both of us now approach our research
and has led us to embrace the multidisciplinary, liberal arts aspect of the
work that allows us to continuously expand our own knowledge while also
guiding our students in their own efforts to do so.
Much of archaeology’s excitement lies in its mystery and the esthetic qual-
ities of the finds. Some of the challenge to conducting instrumental analy-
ses on artifacts, however, is that the work may require partial destruction
of the sample. Preference is therefore given to nondestructive techniques
that leave the cultural heritage intact and unchanged. X-ray fluorescence
(XRF) spectrometry is one such technique.
XRF spectrometry has been applied to archaeology research for
many years. Most of the early work was conducted in a controlled labo-
ratory setting on samples collected from a site. In recent years significant
advances within instrument component technology has led to an ever-
expanding array of commercial portable XRF instruments. These research
toys are relatively inexpensive compared to other atomic spectroscopic
techniques, thus leading to their purchase by many archaeology research
teams. The effective use of a field-based portable XRF and its data can
be very different compared to a laboratory-based XRF depending on the
research design and hypothesis. It is our hope that this book will serve as
a resource for anyone interested in using XRF spectrometry for archaeol-
ogy, especially those using portable instruments for on-site research.
While still in the early stages of writing this book, it became apparent
that we needed to choose a time period to focus the included materials.
Preface • xix
Our research spans from the Etruscans in the 6th century BCE to the late
antique in the eighth century CE, so most examples and information will
cover this range. On occasion for specific reasons of illustration, chapter
materials may expand into more recent history. So by no means is this
book an all-encompassing exploration of how XRF spectrometry contrib-
utes to archaeology research but is instead illustrative of useable data from
our excavations. Also along the way we shall discuss the epistemological
issues inherent in the data and statistical models, and say something about
human action. The reader can then use this information as it applies to
their specific archaeological sites and artifacts.
REFERENCE
Artioli, G. 2010. Scientific Method and Cultural Heritage. New York: Oxford
University Press.
Edwards, H. G. M., and P. Vandenabeele. 2012. Analytical Archaeometry - Selected
Topics. Cambridge: RSC Publishing.
Einstein, A. 1951. “Autobiographical Notes.” In Albert Einstein: Philosopher-
Scientist, ed. P.A. Schil pp, 2–95. New York, NY: Tudor Publishing Company.
Pollard, A. M., C. Heron, and R.A. Armitage. 2017. Archaeological Chemistry.
London: Royal Society of Chemistry.
Price, T.D., and J.H. Burton. 2012. An Introduction to Archaeological Chemistry.
New York: Springer.
Acknowledgments
XRF spectrometry uses X-rays to disrupt electrons from the orbital shells
described above. Atoms in a given sample are first impacted with high
energy photons from an X-ray source. If the specific energy of these pho-
tons exceeds the energy binding an inner electron in the K shell to the
nucleus of the atom, that inner electron may be ejected from the atom to
create an ion. This process is illustrated in Figure 1.1a. Since it is missing
an electron from its innermost shell, the atom is now quite unstable. Sta-
bility is restored by filling the hole in the K shell. To do this, an electron
from the L shell drops into the hole in the K shell; in the process, the atom
can release its excess energy one of two ways. One way is in the form of
a photon (the fluorescence) with a characteristic X-ray energy specific to
the element’s identity. This process of transition from the L to the K shell
is referred to as the Kα energy, in which K represents the shell to which the
electron falls (K) and α represents a transition from one shell further out.
This process is illustrated in Figure 1.1b. Other electron transitions also
take place, as for example, a Kβ photon is released when an electron falls
two shells from the M shell to the K shell, or when an electron falls from
the M to the L shell in Lα X-ray fluorescence.
The resulting Kα and Kβ X-rays, along with other possible X-rays
with characteristic energies that will be discussed later in this chapter,
are then detected by a photon transducer. The data the transducer collects
can then be used to identify each element since, as noted earlier, elements
have characteristic energy signatures. Not all elements in the periodic
table produce detectable XRF signals, though. Both H and He have only
K shell electrons, so they cannot produce X-ray fluorescence. The fluores-
cence yield for the first few light elements (Li, B, C, N, O) is low because
Theory and Basic Principles • 3
Incident X-Ray
radiation
L
Ejected
M K-Shell
electron
(a)
L-Shell electron
fills vacancy
K Kα
X-Ray
L emitted
(b)
1.1.4 SPECTRA
Because each element in the periodic table has unique characteristic elec-
tron binding energies for their K and L shells, each element has a corre-
sponding unique set of XRF peaks. XRF analysis of a sample containing
multiple elements produces results referred to as an XRF spectrum. This
spectrum is a plot of energy in units of KeV on the x-axis versus signal
intensity on the y-axis. The peaks that appear in the plot have specific
energy values that can be used to identify which elements are present. A
simple XRF spectrum collected with an EDXRF is shown in Figure 1.2.
First, note the elements present in this green pigment sample—Cal-
cium (Ca), Iron (Fe), Copper (Cu), and Strontium (Sr). Each element is
characterized by two peaks in the spectrum, the Kα and Kβ, in a ratio of
about 5:1. Also note that the energies associated with each spectral peak
increase with Z value (atomic number): lower atomic number elements
like Calcium (Ca) have lower energies for a given peak, while higher
atomic number elements like Strontium (Sr) have higher energies. It is
important to keep in mind that the XRF energies for the light elements that
may be present in the sample (C, O, N certainly) are all below 1 keV in
Theory and Basic Principles • 5
12
Cu Kα
Fe Kα
10
Relative intensity 8
Ca Kα
6
Sr Kα
4
Cu Kβ
Fe Kβ
Ca Kβ
Sr Kβ
2
0
0 5 10 15
Energy (KeV)
energy and are not detected, and hence not in the spectrum because of their
low fluorescence yield. In addition, at these energies one is probing only
very close to the sample surface (further explained at the end of this sec-
tion) and the detection system has poor efficiency in the low energy range.
The data collection software provided with commercial XRF spec-
trometers allows for easy identification and labeling of elemental peaks
within spectra. Lastly, note that areas under the peaks for each element are
directly proportional to that element’s concentration in a sample and can
therefore be used to determine the amount of each element in a sample.
This process is not straightforward, however, for several reasons. First,
since the yields are very different for different elements, it is not just a
question of comparing the relative intensities from different peaks. Sec-
ond, the sample matrix has a significant effect on the XRF signal intensity
of an element in that sample matrix being measured. A number of different
calibration methods have been developed for XRF spectrometry and are
discussed in Chapter 5.
Some elements such as Lead (Pb) and Mercury (Hg) have inner elec-
tron-binding energies too high to be removed using the source X-ray ener-
gies/voltages available on many commercial XRF instruments. Therefore,
no Kα and Kβ signals can be accessed and detected for these higher Z
elements. Instead, electrons are removed from the higher L shell, so Lα and
Lβ X-rays with similar energies are produced by their removal. Figure 1.3
shows a spectrum for a sample that contains both lower Z and higher Z
elements to illustrate the occurrence of both Kα/Kβ and Lα/Lβ X-ray signals
within one analysis. In samples that contain a variety of elements across a
wide atomic number range, it is important to carefully examine all signals
within an XRF spectrum so ensure correct element identifications. Some
6 • X-RAY FLUORESCENCE SPECTROMETRY
elements produce only Kα/Kβ X-ray signals, some produce only Lα/Lβ, and
some produce both Kα/Kβ and Lα/Lβ. Additionally, Kα/Kβ and Lα/Lβ X-ray
signals can occasionally overlap and lead to elemental interferences or
overlaps as shown in Figure 1.3. Note how the Mn Kβ overlaps with the
Fe Kα; this makes the Fe Kα peak appear larger which could lead to cal-
culation of an inaccurate concentration value for Fe in the sample if the
interference is not taken into account. Lastly, note the Pb Lα at 10.5 KeV
and the Pb Lβ at 12.6 KeV. It is easy to misidentify the Pb Lα peak as Arse-
nic (As) considering the As Kα is also at 10.5 KeV. However, Arsenic does
not produce a signal at 12.6 KeV which if present in the XRF spectrum
verifies the presence of Lead and not Arsenic.
A number of unwanted and/or interfering peaks can also be observed
in XRF spectra. A very broad Bremsstrahlung peak with a maximum at
about two-thirds of the applied X-ray energy is typically present for lower
density samples such as soils and mortars. Bremsstrahlung means “break-
ing” and refers to the high voltage electrons striking the X-ray source tar-
get which causes this radiation background to be emitted from the target
as they slow down. That radiation, along with the wanted characteristic
radiation of the target, strikes the sample. Some of the radiation is then
backscattered to the detector and causes the Bremsstrahlung peak. For low
density samples, the Bremsstrahlung peak is more prominent due to the
weaker sample characteristic signals for these types of matrices. Rayleigh
peaks (elastic scatter, meaning no loss of energy) and Compton peaks
(inelastic scatter, meaning loss of energy) may also be observed in XRF
spectra, their prominence depending on the sample type. Rayleigh peaks
are more significant for higher density samples such as metallic artifacts,
Fe Kα + Mn Kβ
12
Sr Kα
10
Relative intensity
8
Mn Kα
6
Sr Kβ
4
Ca Kα
Pb Lβ
Fe Kβ
Pb Lα
2
Ca Kβ
0
0 5 10 15
Energy (KeV)
whereas Compton peaks are more significant for lower density samples.
Both signals result from the X-ray tube source target, Rh in many cases,
and produce Kα and Kβ peaks with energies at (Rayleigh) or slightly less
(Compton) than those expected for the target element; note that the Comp-
ton signal for Rh looks like a Ru signal according to its energy value.
Sum peaks can be observed for high concentration elements within a
sample and result from two photons simultaneously arriving at the detec-
tor. For example, a sample high in Copper (Cu) may exhibit a sum peak at
16.12 KeV which results from the detection of two Kα X-rays each with
an energy of 8.06 KeV. Lastly, Silicon (Si) escape peaks occur at 1.74
KeV (the X-ray peak characteristic of Si) less than the energy value of the
parent peak and at 10 percent or less the height of the parent peak; these
are caused by loss of energy due to silicon fluorescence from the detector
Si material. The spectrum in Figure 1.4 illustrates many of these unwanted
and possibly interfering XRF spectral signals for a high Lead (Pb) sample.
When examining spectra from different sample types one must keep
in mind the depth from which the XRF signal originates. This is the prob-
ing depth. To detect the presence of a specific element, X-rays must first
penetrate far enough into the sample to reach an atom and remove its inner
electron. The characteristic energies specific to that element then travel out
of the sample, enter the spectrometer, and are measured by the transducer.
XRF spectrometry probes between a small fraction of a micron (µm) up
to the millimeter range of the sample surface depending on which char-
acteristic energies are being accessed and used, and the sample matrix.
There is less probing depth for the lower energy lines (peaks) because the
characteristic X-rays are absorbed and/or scattered more while exiting the
sample. This is in contrast to electron beam-induced X-ray fluorescence
12
Pb Lα
Pb Lβ
10
Relative intensity
8
Rh Compton
and Rayleigh
6 scatter peaks
Escape peaks
4
Sum peaks
2
0
0 5 10 15 20 25 30
Energy (KeV)
Figure 1.4. Example of scatter peaks, sum peaks, and escape peaks.
8 • X-RAY FLUORESCENCE SPECTROMETRY
As is the case with any research technique, the use of XRF has its lim-
itations, and knowledge of these limitations is essential to the design of
research projects that incorporate it. Of particular interest are the limita-
tions of the portable instruments typically used for field work. As noted in
Section 1.1.2, XRF as a technique is not particularly efficient at measuring
low-Z elements. Thus any element lighter than Titanium (Ti, which has a
Z of 22) presents difficulty which may or may not be overcome through
the adoption of procedures that take both instrument and sample condi-
tions into account. Indeed a number of elements important within archae-
ology research such as Phosphorus (P) and Sodium (Na) are particularly
challenging to measure via portable XRF (Hunt and Speakman 2015), and
others with Z between 21 and 30 (e.g., Vanadium, Chromium, Cobalt, and
Nickel) yield semiquantitative results at best (Hunt and Speakman 2015).
These limitations affect three areas of archaeology in practice. The
first is survey, the second is excavation, and the third is conservation.
1.2.1 SURVEY
1.2.2 EXCAVATION
process disturbs lower strata such that material from them is brought up
and placed on top of more recent ones. In these cases, however, natural or
human actions leave evidence (often very subtle) of that action in the soil.
To control for this, archaeologists look for ways to define the changes
that these actions produce. Observation of alterations in the soil with
regard to color, consistency, and composition is essential in detecting such
disturbances. A change in color, consistency, and/or composition provides
evidence for an event (natural or human) that has brought about a change
in the soil. This is called a stratum or a locus depending on preferred ter-
minology. As mentioned earlier, these loci or strata are significant because
they both give context to artifacts or features and indicate changes pro-
duced by natural or human causes. It is the relationship between the loci
that serves as the foundation for knowledge of site formation. Through
careful observation of the soil with regard to color, composition, and con-
sistency, a researcher can avoid the removal of either too little of the soil
(undercutting) or too much of it (overcutting), which allows for a correct
understanding of the relationship among the loci. The process of removing
the soil matrix is best described as “cleaning dirt off of dirt.” Sweeping
with a brush, troweling, shoveling, or any other method of cleaning the
surface of the locus is necessary to reveal any changes in color, composi-
tion, or consistency. The soil comprising a locus can then be sampled by
sifting and by floatation. This allows for the recovery of small items as
well as archaeobotanical and archaeozoological remains.
1.2.3 CONSERVATION/PRESERVATION
After excavation, two issues confront archaeologists. The first is the study
of finds, or the material recovered by excavation. Both features and arti-
facts must be subject to study, and both must be studied in the aggregate
(e.g., in the case of most of the sherds) and, in some cases, individually
(e.g., in the case of a unique artifact). XRF is useful in the study of arti-
facts, often because elemental composition may be utilized to aid in deter-
minations such as whether an artifact was produced locally or whether the
accretion of minerals in a water feature is caused by a particular source
of water.
Another issue is conservation, restoration, and preservation of finds.
Artifacts (e.g., fresco with pigments) need to be treated in a way that stops
decay or degradation of the material, and the best way of achieving this
depends on their nature and on the nature of the matrix from which they
have been removed. This is a more obvious concern with artifacts, but
Theory and Basic Principles • 11
features such as walls also degrade once they are exposed to the elements
by excavation. In cases where trenches are not backfilled after excava-
tion, information about the composition of features may suggest the best
ways to preserve them. Even in situations in which trenches are backfilled,
knowledge of both the composition of features and of the fill material
available may influence decisions about what fill is best. XRF can be use-
ful when some conservation is necessary to preserve finds, whether arti-
facts or features, because an understanding of the chemical composition of
finds can provide insight into the best methods of conservation.
REFERENCES
Hunt, A.M.W., and R.J. Speakman. 2015. “Portable XRF Analysis of Archaeo-
logical Sediments and Ceramics.” Journal of Archaeological Science 53,
pp. 626–38. doi:http://dx.doi.org/10.1016/j.jas.2014.11.031
Index