X-RAY

FLUORESCENCE
SPECTROMETRY AND
ITS APPLICATIONS TO
ARCHAEOLOGY
 X-RAY
FLUORESCENCE
SPECTROMETRY AND
ITS APPLICATIONS TO
ARCHAEOLOGY
An Illustrated Guide

MARY KATE DONAIS AND

DAVID B. GEORGE

MOMENTUM PRESS, LLC, NEW YORK

X-Ray Fluorescence Spectrometry and Its Applications to Archaeology

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 Dedication

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

X-ray fluorescence (XRF) spectrometry is a nondestructive elemen-

tal analysis technique utilized in many industrial and research settings.
Developments in instrument components and design have allowed appli-
cations of XRF spectrometry to expand beyond the laboratory and into
field settings such as museums and archaeological excavation sites.
This book serves as a practical guide for the application of XRF
­spectrometry to the study and understanding of archaeology. Early chap-
ters serve as both an introduction to XRF theory and instrumentation
as well as an introduction to field applications and practical aspects of
archaeology and conservation. These early chapters thus provide those
new to XRF and/or new to field archaeology a solid foundation on which
to base further study. Based on recent trends within field archaeology,
information specific to portable instrumentation also is included in early
chapters in addition to a later separate chapter devoted to data collec-
tion in the field including both field labs and archaeological sites. The
chapter devoted to data discusses qualitative and quantitative approaches,
applications of various statistical methods to XRF data, and then relates
these data types and statistical methods back to the types of archaeo-
logical questions that are possible to answer through XRF analysis.
With statistics playing an ever-increasing role in data evaluation, new
and experienced users of XRF spectrometry will find the statistics over-
view particularly helpful in expanding how data can be interpreted
and p­ resented. The book concludes with individual chapters devoted
to specific archaeological sample types including pigments, ceramics,
glass, construction materials, and metallurgical materials. Each of these
­material-specific chapters includes a section relating that material type
back to the archaeology itself. Numerous examples, figures, and spectra
are provided within these chapters.
viii  •   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

4.3  Computer or PDA 40

4.4 Sample Collection for Control of Data 41
4.5 Case Study: Coriglia, Castel Viscardo 41
References46
5   Data 47
5.1  Qualitative Analysis 47
5.2  Quantitative Analysis 50
5.3 Other Approaches to Data Evaluation 57
5.4 Examples from Archaeological Work 67
References76
6   Pigments 79
6.1 Background 79
6.2  Identification of Pigments 84
6.3  Pigment Sourcing 90
6.4 Discussions Relating to Archaeological Work 91
References92
7   Ceramics 95
7.1  Ceramic Production 95
7.2 Paste/Fabric 98
7.3  Painted Decorations 102
7.4  Slip and Glaze 103
References106
8   Glass 107
8.1 Background 107
8.2  Roman Glass 111
References116
9   Construction Materials 119
9.1  Cements, Mortars, and Concretes 119
9.2 Stone 125
References127
10   Metallurgical Materials 129
10.1 Background 129
10.2 Slag 130
10.3 Coins 132
10.4  Water System with Lead Pipes 136
References139
Summary 141
About the Authors 143
Index 145
 List of Figures

Figure 1.1. (a) Ejection of inner electron to create hole. (b) Release

of Kα X-ray when hole is filled. 3
Figure 1.2. Simple XRF spectrum for a green pigment. 5
Figure 1.3. Sample XRF spectrum with both K and L signals. 6
Figure 1.4. Example of scatter peaks, sum peaks, and escape peaks. 7
Figure 2.1. Diagram of X-ray tube. 15
Figure 2.2. Effect of primary filter on spectra. 16
Figure 2.3. Diagram of a WDXRF. 19
Figure 2.4. Diagram of an EDXRF. 21
Figure 2.5. (a) Portable XRF in a stand. (b) Using a portable XRF
in a tripod in the field. 22
Figure 4.1. (a) Aerial view of Coriglia excavation site. (b) Aerial
view of ­Coriglia excavation site. 42
Figure 4.2. Coriglia Trench C. 44
Figure 4.3. (a) Coriglia Trench C with terraced wall loci labels.
(b) 3-D scores plot for Trench C terraced walls. 45
Figure 5.1. Example of peak identification in instrument software. 48
Figure 5.2. Select portions of a reference material certificate
of analysis. 55
Figure 5.3. (a) 2-D scatter plot of Element A concentration versus
Element B concentration. (b) 2-D scatter plot of Element
A/Element C versus Element B/Element C
concentrations.60
Figure 5.4. Hypothetical data table for ANOVA description. 61
Figure 5.5. Hypothetical dendrogram. 66
Figure 5.6. (a) 2-D scatter plot of two red pigments. (b) 3-D scatter
plot of three hydraulic cement floors. 69
xii  •   List of Figures

Figure 5.7. Data table for ANOVA. 71

Figure 5.8. ANOVA output table. 72
Figure 5.9. PCA scores plot. 73
Figure 5.10. PCA loadings plot. 74
Figure 5.11. Cluster analysis dendrogram. 75
Figure 5.12. Scores plot for fused ochre pigment data. 76
Figure 6.1. Spectra for pigments on Etruscan architectural
terracotta.85
Figure 6.2. Spectra for architectural terracotta fabric and pigment. 86
Figure 6.3. Spectra for pigments on Roman fresco fragment. 87
Figure 6.4. Spectra for red and pink pigments. 88
Figure 6.5. Spectra for green earth from two different sources. 89
Figure 7.1. (a) Example of earthenware. (b) Example of stoneware. 96
Figure 7.2. (a) Example of Roman common ware. (b) Example of
Roman fine ware. 97
Figure 7.3. Etruscan black bucchero pottery sherds. 97
Figure 7.4. Spectra of different ceramic fabrics. 100
Figure 7.5. PCA scores plot of nonlocal pottery types. 101
Figure 7.6. Spectra of pigments on painted decorative ceramic
“The Warrior.” 103
Figure 7.7. Examples of red figure and black figure. 104
Figure 7.8. Spectrum of yellow glaze inside vase. 105
Figure 8.1. Examples of Roman glass. 112
Figure 8.2. Spectra of red tesserae under low-voltage and
high-voltage conditions. 113
Figure 8.3. Spectra of silica-soda-lime and silica-soda-lime-lead
glasses.114
Figure 8.4. Spectra of three types of green glass. 115
Figure 9.1. Example of opus reticulatum.120
Figure 9.2. Example of opus signinum.121
Figure 9.3. Example of a beaten tufa floor. 121
Figure 9.4. Example of a hypocaust. 122
Figure 9.5. Eastern apse wall showing two construction types. 123
Figure 9.6. PCA scores plot for mortars corresponding to two
construction types on eastern apse wall. 124
 List of Figures   •   xiii

Figure 9.7. PCA scores plot for mortars and bricks on eastern

and western apses walls. 124
Figure 9.8. Examples of ancient roads. 126
Figure 10.1. Kiln, Coriglia Trench C. 131
Figure 10.2. Spectrum of slag from Coriglia. 132
Figure 10.3. Medieval industrial space. 133
Figure 10.4. Spectra of three coins found at the Coriglia
excavation site. 135
Figure 10.5. (a) Coriglia Trench C aerial view showing drainage
trough (arrow) and location of fistulae (box) and
(b) Close up of fistulae and keys. 137
 List of Tables

Table 5.1. Example CRMs for archaeological sample types 56

Table 6.1. Summary of pigments 80
Table 8.1. Examples of bulk elemental compositions of
preindustrial/historic glasses 109
Table 8.2. Visual glass properties and associated minerals 110
 Preface

WHY USE INSTRUMENTAL MEASUREMENTS FOR

ARCHAEOLOGY RESEARCH?

For most archaeologists who regularly attend professional conferences

and follow the current literature, the integration of instrument-based
­measurements into archaeological research designs is not new or surpris-
ing. Entire journals such as the Journal of Archaeological Science, Archae-
ological and Anthropological Sciences, Archaeometry, and the Journal of
Cultural Heritage are devoted to the scientific approach to archaeology
and many other journals are routinely publishing on the topic. A number
of recurring conferences are available to the thousands of researchers who
work within this focused and exciting research field to share information
with each other.
For others, however, the application of instrumental methods to
archaeology may seem exotic for a variety of reasons including the
­theoretical basis behind operation of the equipment, and the reliance on
statistical and mathematical models to understand the data that have been
collected into a usable set. General resources are available that describe
how these spectroscopy, chromatography, electrochemistry, mass spec-
trometry, microscopy, nuclear, and imaging/visualization techniques can
be used to gain information regarding archaeological materials and sites
where the questions are not always intuitively obvious (Pollard, Heron,
and Armitage 2017; Artioli 2010; Edwards and Vandenabeele 2012; Price
and Burton 2012). Given that there are teleological differences between
archaeometric need to put the “right number” on something and the
archaeological aim to reconstruct human life ways, one of the issues we
shall examine will be that relationship and how to construct a research
design to serve the archaeological aim. Indeed the authors did not under-
stand the potentials of the connections themselves. A coauthor of this
book, an analytical chemist by training, was new to archaeometry and had
xviii  •   Preface

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.

WHY USE X-RAY FLUORESCENCE

SPECTROMETRY FOR ARCHAEOLOGY?

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.

CHOOSING A FOCUS FOR THE BOOK

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.

ARCHAEOLOGY VERSUS CHEMISTRY

Archaeology is not a natural science as chemistry is. Its main concern is

not the characterization of material reality but rather what that material
reality reveals about human life in the past. It is nevertheless scientific
insofar as it employs empirical data to derive conclusions. This means
that archaeology and other disciplines, including chemistry, may employ
the same data to answer different questions and therefore to arrive at very
different kinds of conclusions. XRF data can be common to chemistry
and archaeology, but the conclusions each derives from it are essentially
different.
Awareness of the differences in the types of conclusions that may be
derived from one set of data is critical to effective use of XRF in archae-
ology. It reflects a fundamental concern of all scientific endeavors, namely
the relationship of theory and data. Neither data nor theory alone is suffi-
cient for science because raw data are meaningless and theoretical specu-
lation untethered by data is, as Einstein says, “empty phantasy” (Einstein
1951). Only the synthesis of the two produces scientific conclusions. Per-
haps the most difficult aspect of any scientific investigation therefore is
determining how data relate to theoretical concerns, that is, what data can
be used to draw valid conclusions about a given question and how they
may be used to accomplish this.
This concern is central to the use of XRF in archaeology. XRF data
do not in itself provide evidence relevant to archaeological research, nor
for that matter do the conclusions drawn by chemists as such. Instead, it
is up to the archaeologist to ascertain how XRF data relate to a particu-
lar research objective and plan data collection so that data serve as evi-
dence to support or refute specific conclusions. We have tried through the
course of the book to provide general information about XRF and more
xx  •   Preface

specific information about its use on different materials in our excavations

to ­provide examples of data collection and analysis driven by archaeolog-
ical concerns. It is our hope that this will provide other researchers with
the knowledge they need to plan and employ XRF in their own research.

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

Many students contributed to the research presented in this book. Some

analyzed samples in our college labs and never set foot on the excavation
sites. Others operated instruments and collected sampling information as
participants in the field school. And still others took the data steps further,
conducting statistical analyses, summarizing findings in reports and the-
ses, and helping edit publications on our findings. We wish to thank all of
these students, no matter how small or large their contributions, for their
efforts have helped lead us to where we are today as researchers.
 CHAPTER 1

Theory and Basic Principles

1.1 X-RAY FLUORESCENCE SPECTROMETRY

1.1.1  ATOMIC STRUCTURE

Spectroscopy is the study of the interaction of electromagnetic radiation

with matter. Scientists across a wide range of research fields employ many
different spectroscopic techniques which allow for the study of atoms,
ions, and molecules in various materials, from simple naturally occurring
substances such as water to more complex biological tissues and prod-
ucts of human activity. While spectroscopy is the observation of how light
interacts with matter, spectrometry is the actual measurement of the radia-
tion resulting from a physical system being impacted by that light in order
to obtain information about that system. X-ray fluorescence spectrometry
is one method employed in spectrometry. It involves the collection of radi-
ation emitted by samples as a result of exposure to X-rays.
The theoretical foundation of X-ray fluorescence is atomic structure,
so a brief review of that structure is necessary for the description of X-ray
fluorescence (XRF) spectrometry below. Each element in the periodic
table of the elements has a unique atomic number (Z), which is the num-
ber of protons in its nucleus. These protons, which have a positive charge,
together with the neutrons, which are neutral and are also found in the
nucleus, comprise most of the mass of an atom. The space surrounding
the nucleus contains negatively charged electrons equal in number to the
protons for all atoms with a neutral charge. These electrons are in shells
at specific distances from the nucleus. Each shell can be occupied by a
specific maximum number of electrons, and, since each element contains a
unique total number of electrons, each element also has a unique electron
shell configuration. This means that a given element has a unique energy
signature or pattern that can be measured via spectroscopy.
2  •   X-RAY FLUORESCENCE SPECTROMETRY

The reason for this is found in the distribution of electrons around

the nucleus. The innermost electron shell, known as the K shell, contains
electrons most strongly bound to the nucleus since their proximity to the
nucleus results in the strongest attraction between these positive (pro-
tons) and negative (electrons) particles. As the distance of a shell from
the nucleus increases, the attraction between the nucleus and the electrons
decreases, so electrons in the shells that follow the K shell (the L shell,
M shell, and so on) are less tightly bound to the atom. Because of the
differences in levels of attraction among the shells, a variety of processes
related to the energy and location of electrons occur when electromagnetic
radiation hits an atom.

1.1.2 ABSORPTION AND EMISSION IN XRF

SPECTROMETRY

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)

Figure 1.1.  (a) Ejection of inner electron to create hole.

(b) Release of Kα X-ray when hole is filled.

Auger decay processes are more highly favored over fluorescence. As Z

increases, the Auger yield decreases and the fluorescence yield increases,
thus making higher Z elements such as Iron (Fe) and Lead (Pb) more eas-
ily detected via X-ray fluorescence spectrometry. The end result is that all
elements heavier than Lithium (Z = 3) are detectable via XRF depending
on spectrometer design, detector type, and concentration of element in the
sample.

1.1.3  INSTRUMENT BASICS

XRF spectrometry instrument design falls into two general categories:

wavelength dispersive (WDXRF) and energy dispersive (EDXRF).
4  •   X-RAY FLUORESCENCE SPECTROMETRY

­ enchtop and laboratory-based instruments are more typically WDXRF

B
designs whereas the portable and handheld instruments are EDXRF
designs. The main difference between these two instrument types is in
the ways in which X-rays are directed at the sample and then how the
resulting fluorescence is collected. WDXRF instruments utilize a mono-
chromator that detects narrow bands of wavelengths of light. They can be
adjusted to scan different wavelengths in succession across the desired
X-ray range. This requires larger instruments with moving parts, so
WDXRF instruments are typically not suitable to field work. In addition,
WDXRF instruments provide much higher spectral resolution, allowing
distinction between some closely spaced peaks which is not possible in
EDXRF. In EDXRF, it is therefore sometimes not possible to distinguish
between some of the elements.
EDXRF instruments on the other hand employ a source-detector
system that allows for simultaneous collection of all X-ray photons as
opposed to more slowly scanning across a wavelength range. They do not
therefore need the moving parts that the WDXRF instruments do. This
makes them more rugged for field work but with greater challenges due
to their lower resolution. No matter which design fits your research and
application needs best, all XRF instruments have an X-ray source, filters,
and a detector.

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)

Figure 1.2.  Simple XRF spectrum for a green pigment.

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)

Figure 1.3.  Sample XRF spectrum with both K and L signals.

 Theory and Basic Principles   •  7

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

(EDS), another X-ray technique often used in combination with scan-

ning electron microscopy (SEM). The probing depths observed for this
technique are hundreds of angstroms to only a few microns, much more
shallow, compared to XRF. These significantly smaller probing depths are
controlled by the energy of the primary electron going into the sample and
the sample density.

1.2  FIELD APPLICATIONS IN ARCHAEOLOGY

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

The research design of a given archaeological project may involve any

of several types of field survey. The first decision faced by researchers
is whether a survey should be intensive or extensive. Intensive survey
requires teams to walk specific tracts of land documenting the features
and artifacts. Extensive survey on the other hand covers more area, usu-
ally to answer larger questions of land use and site distribution. The sec-
ond choice that must be made on the basis of the research objective(s)
is whether a survey will be systematic or nonsystematic. If a systematic
survey is conducted, straight line paths called transects are laid out and
data are collected along them. If the survey is nonsystematic, data are
collected randomly over the surface. The type of data recorded depends on
whether the researcher is employing a nonintrusive or an intrusive survey.
 Theory and Basic Principles   •  9

In nonintrusive surveys, features and artifacts are only noted, counted,

and, depending on the research questions, their positions may be tagged
by global positioning system (GPS) and mapped in a geographic infor-
mation system (GIS). As the name implies, intrusive survey entails more
than merely noting the distribution of artifacts, and it may include digging
test pits to determine if and at what depth there are cultural materials or
features from which samples may be removed for analysis. Finally, pros-
pecting is a search for particular features or artifacts and usually reflects a
hypothesis as to what is in the area, whereas sampling within an intrusive
survey is usually random and does not necessarily reflect a hypothesis.
Field survey has made good use of a number of technological tools,
including drones, light detection and ranging (LIDAR), GIS, GPS, vari-
ous geophysical surveying techniques, and of course XRF. Portable XRF
has proven useful in sourcing clays and sediments as well as analyzing
ceramics in field survey. It has been particularly useful in nonintrusive
surveys because it is nondestructive. More detailed discussion of the use
of portable XRF in survey archaeology is found in Chapter 4.

1.2.2 EXCAVATION

While features (e.g., walls) within an archaeological site must be exam-

ined in place or in situ, artifacts must be collected. Features are permanent:
they are therefore given their own locus numbers. But artifacts are moved
out of the context in which they are found, so identifying and recording
that specific context is critical. To facilitate this process, artifacts are col-
lected only after their location is recorded. Once collected, artifacts are
kept in bins according to their location or locus (plural is loci), which are
designated by numbers.
Since it is the soil matrix that gives a context to features and artifacts,
the process of excavation is first and foremost one of attempting to under-
stand what natural actions or human activity caused the soil to be as it is.
Of particular importance in the investigation of soil is one of the funda-
mental principles of archaeology, the law of superposition. The principle
has its origins in the 17th century work of Danish scholar Nicolas Steno.
Steno, whose interests ranged from anatomy to geology, first observed that
in geological phenomena, strata on top are more recently deposited than
the deeper strata below them. There are exceptions to this general rule:
natural events such as earthquakes may create fissures and displace lower
strata so that they are situated above more recent ones. Strata can also
be altered by human activity, for example by the digging of a well. This
10  •   X-RAY FLUORESCENCE SPECTROMETRY

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

A lighter matrix samples, 52

Absorption, 2–3
Accuracy, 50–51, 56
Alloys, 50, 129, 130, 134
Analysis of variance (ANOVA)
advantage, 62
data table, 70, 71
F statistic values, 62
hypothetical data table, 61
one-way, 61
output table, 70, 72
replicate data sets, 61
two-way, 61, 62
Artifact peaks
Bremsstrahlung peak, 6
Compton peak, 6, 7
escape peak, 7
identification, 48
interferences, 49
Rayleigh peak, 6, 7, 49
Sum peak, 7
Atomic structure, 1–2
Auger decay processes, 3
Austerotates, 91
B slip and glaze, 103–106
Beaten tufa floor, 120–121
Black figure, 104
C accuracy, 56
Calibration
fundamental parameters method,
53
mathematically based calibration
method, 53
matrix-specific instrument, 50
standard addition calibration, 52
Cement
concrete core, 120
hydraulic, 68–70, 122
vs. mortar, 119
Ceramics
black bucchero pottery sherds,
97–98
broken, 98
common ware, 96, 97
earthenware, 95–96
fine ware, 96, 97
painted decorations, 102–103
paste/fabric
archaeological studies,
101–102
chemical character, 98
firing temperature, 99
PCA scores plot, 100, 101
site of production, 100
XRF spectra, 99, 100
stoneware, 95–96
Certified reference material
(CRM), 40
archaeological sample types, 56
confidence interval, 57, 67–68
cultural heritage work, 54
146  •   Index
laboratory-produced quality
control samples, 55
NIST SRM 1881a Portland
Cement, 54, 55
t-test, 57
Cluster analysis
agglomerative analysis, 65
dendrogram, 74, 75
drawback, 66
nonhierarchical methods, 65
quality, 66
single XRF analysis, 64
Coins
archaeological work, 136
Coriglia excavation site, 135
elemental composition, 134
Etruscan and early Republican
periods, 135
fourrées, 134
identification, 133
metallic composition, 134
pottery, 132
Roman coins, 134
Confidence interval (CI), 57,
67–68
Conservation, 10–11
Construction materials
concrete
archaeological work, 125
beaten tufa floor, 120–121
cement, 119
core, 120
hypocaust floors, 121–122
mortar, 119
opus reticulatum, 120
opus signinum, 120, 121
PCA scores plot, 123, 124
spatial association, 122–123
XRF data, 123–125
stone
archaeological work, 127
decoration, 126
decorative, 125
Etruscans, 125–126
roads construction, 126
structural, 125
waterproof construction material,
120
D
Data collection
archaeology
elemental analysis, 34
on-site data collection, 34
overheating and cooling, 34
personnel involved in work,
35
power source, 34
research design, 33
site conditions and
transportation, 35
instrument considerations
energy dispersive models,
30–31
manual quality, 31–32
purchase decisions, 31
software, 31
wavelength dispersive
instrument, 30–31
instrument parameters, 32–33
portable X-ray fluorescence
spectrometry
advancements, 21
case study, 41–45
control of data, 41
industrial users, 22
personal digital assistant,
40–41
removable personal data
assistant, 22
sample type, 37
in situ data collection, 38–40
uses, 9
samples and sample preparation
clean samples, 28
cultural heritage field, 27
destructive sample
preparation techniques, 29
dimensions and size, 28
infinitely thick, 30
 Index   •   147

lighter elements, 30 software, 47–48

lower density samples, 30
minimally invasive sampling,
27
proper containment of
samples, 28
sample homogeneity, 29
Data evaluation
analysis of variance
advantage, 62
data table, 70, 71
F statistic values, 62
hypothetical data table, 61
one-way, 61
output table, 70, 72
replicate data sets, 61
two-way, 61, 62
cluster analysis
agglomerative analysis, 65
dendrogram, 74, 75
drawback, 66
nonhierarchical methods, 65
quality, 66
single XRF analysis, 64
2-D and 3-D scatter plots, 58–59,
68–70
deconvolution, 58
multi-technique studies, 66–67,
75–76
principal component analysis
advantages, 64
computer applications, 63
fully validated, 72
loadings plot, 63, 74
low explained variance, 63
multivariate analysis
technique, 64
principal components, 62–63
scores plot, 73
qualitative spectral evaluation
artifact peaks, 48–49
interference correction, 50
matrix-specific instrument
calibration, 50
peak identification, 48
spectral overlaps, 49
quantitative spectral evaluation
calibration process, 50, 52–53
certified reference material,
54–57
elemental concentrations, 51
factory calibrations, 50
semiquantitative analysis, 51
sample set size, 58
spreadsheet-based applications,
58
Data fusion, 67, 75
Decorative stone, 125
Decorative terracotta, 96, 103
Drone, 39
E
Emission, 2–3
Energy dispersive X-ray
fluorescence (EDXRF)
spectrometry, 3–4
advantage, 21
cost, 21
semiconductor detector, 20
X-ray source, 21
Excavation, 9–10
Extensive survey, 8
F
Fabric, 98–102
Filters
characteristic energy signatures,
15
elements, 16
primary, 16
secondary, 16
Floridicolores, 91
Fourrées, 134
Fresco pigment, 38, 63, 68, 70,
73–76, 79, 86
Fusion, 67, 75
G
Gas-filled detectors, 17
148  •   Index
Geographic information system
(GIS), 9
Glass
bulk composition, 108–109
colorants and decolarants,
109–111
composition, 107
opacifiers, 109–111
Roman glass
archaeological work, 115–116
examples, 111, 112
green glass, 115
production, 112
red tesserae, 113–114
silica-soda-lime and silica-
soda-lime-lead glasses, 114
sourcing, 108
types, 108
visual properties, 110–111
Glaze, 103–106
Global positioning system (GPS),
9 M
H method, 53
High purity germanium (HPGe)
detector, 18
Hydraulic cement, 68–70, 122
Hypocaust, 121–122
Hypocaust floors, 121–122
I Republican periods, 135
Inductively coupled plasma atomic
emission spectroscopy
(ICP-AES), 55
Instrumentation
automated analysis options, 23
energy dispersive instruments,
20–21
filters, 15–16
micro-XRF, 22–23
portable XRF instruments, 21–22
practical aspects, 24
safety, 24
transducers, 16–18
wavelength dispersive
instruments, 19–20
X-ray sources
radioisotope sources, 14
synchrotron radiation, 14
X-ray tube, 14–15
Intensive survey, 8
Intrusive survey, 9
K
Kiln
bricks, 120
ceramic production, 95, 106
in Coriglia Trench C, 131
redox conditions, 104
L
Lead pipes, 136–139
Lithium-drifted silicon (Li(Si))
detector, 18
Mathematically based calibration
Metallurgical materials
coins
archaeological work, 136
Coriglia excavation site, 135
elemental composition, 134
Etruscan and early
identification, 133
metallic composition, 134
pottery, 132
Roman coins, 134
metallic objects, 129–130
slag
archaeological work, 132
iron ore processing, 130–131
kiln unearthed, 131–132
quantitative analysis, 131
water system with lead pipes
archaeological work,
138–139

corrosion, 138
Trench C fistulae, 137
XRF analyses, 137–138
Micro-XRF (µ-XRF) instruments,
22–23
Mortar
calcium and iron in, 43
calibration approach, 52
vs. cement, 119
eastern apse wall, 123, 124
elemental concentrations, 51
PCA scores plot, 124
Roman production technique, 43
sample analysis, 38–39
sample preparation, 29, 30
zinc in, 68
N case study, 41–45
Neutron activation analysis
(NAA), 55
Nonintrusive survey, 9
Nonsystematic survey, 8
O sample type, 37
Opacifiers, 109–111
Opus incertum, 120
Opus latericium, 120
Opus quadratum, 120
Opus reticulatum, 120
Opus signinum, 120
P 40
Painted decorations, 102–103
Paste, 98–102
Percent error, 55, 56
Pigments
archaeological work, 91–92
black, 82
blue, 80
brown and gray, 83
chemical characterization, 79
green, 83
mineral-based, 79
organic, 79
Index   •   149
purple, 83
red, 81
sourcing, 90–91
spectra
architectural terracotta fabric
and pigment, 86
Etruscan architectural
terracotta, 84, 85
green earth, 89
red and pink pigments, 88
Roman fresco fragment, 87
synthetic, 79
white, 80
yellow, 82
Portable X-ray fluorescence
spectrometry
advancements, 21
control of data, 41
industrial users, 22
personal digital assistant, 40–41
removable personal data
assistant, 22
in situ data collection
certified reference materials,
40
controlled environment, 38
data organization and backup,
40
portable XRF data collection,
sampling location cleaning,
39
sampling location recording,
39
sampling location scouting
and marking, 38–39
supplies, 38
uses, 9
Precision, 23, 29, 60, 61
Preservation, 10–11
Principal component analysis
(PCA), 44
150  •   Index
advantages, 64
computer applications, 63
fully validated, 72
loadings plot, 63, 74
low explained variance, 63
multivariate analysis technique,
64
principal components, 62–63
Protocols
certified reference material
analyses, 40
data backup and organization, 40
portable XRF data collection,
39–40
recording of sampling locations,
39
sampling location scouting and
marking, 38–39
supplies, 38
Q 20
Qualitative spectral evaluation
artifact peaks, 48–49
interference correction, 50
matrix-specific instrument
calibration, 50
peak identification, 48
software, 47–48
spectral overlaps, 49
Quantitative spectral evaluation
calibration process, 50
fundamental parameters
method, 53
lighter matrix samples, 52
mathematically based
calibration method, 53
standard addition calibration,
52
certified reference material
accuracy, 56
archaeological sample types,
56
confidence interval, 57,
67–68
cultural heritage work, 54
laboratory-produced quality
control samples, 55
NIST SRM 1881a Portland
Cement, 54, 55
t-test, 57
elemental concentrations, 51
factory calibrations, 50
semiquantitative analysis, 51
R
Red figure, 104
Road, 126, 136
S
Safety, 24
Scatter plots, 68–70
Scintillation counter, 17
Secondary filters, 16
Sequential instruments, WDXRF,
Si(PIN) diode detectors, 18
Silicon drift detectors (SDDs), 18
Simultaneous design, WDXRF, 20
Slag
archaeological work, 132
iron ore processing, 130–131
kiln unearthed, 131–132
quantitative analysis, 131
Slip, 103–106
Sources
radioisotope sources, 14
synchrotron radiation, 14
X-ray tube, 14–15
Sourcing
glass, 109
ores, 130
pigment, 90–91
Spectral overlaps, 49
Standards, 54–57
Stone
archaeological work, 127
decoration, 126
decorative, 125
 Index   •   151

Etruscans, 125–126 gas-filled detectors, 17

roads construction, 126 scintillation counter, 17
structural, 125 semiconductor, 18
Structural stone, 125 t-test, 69
Survey
extensive, 8 W
intensive, 8 Wavelength dispersive X-ray
intrusive, 9 fluorescence (WDXRF)
nonintrusive, 9 spectrometry, 3–4
nonsystematic, 8 collimator, 19
systematic, 8 instrument designs, 19–20
technological tools, 9 resolution, 20
Systematic survey, 8 sequential instruments, 20
simultaneous instruments, 20
T
Terracotta X
Etruscan architectural, 84, 85 X-ray fluorescence (XRF)
fabric and pigment, 86, 91 spectrometry
and lime mixture, 120 absorption and emission, 2–3
terra sigillata, 101–102 in archaeology
Trench C fistulae, 137 conservation/preservation,
Terra sigillata, 101–102 10–11
Tessera(e) excavation, 9–10
colors and characteristics, 113 survey, 8–9
mosaic creation, 111–112 atomic structure, 1–2
silica-soda-lime-lead type glass, EDXRF instruments, 3–4
114 spectra, 4–8
silica-soda-lime type glass, 114 WDXRF instruments, 3–4
Transducers X-ray tube, 14–15