Research Article

Received: 1 September 2009 Accepted: 3 September 2009 Published online in Wiley Interscience: 6 November 2009

(www.interscience.com) DOI 10.1002/xrs.1223

Estimation and account for matrix effects in

studying glass materials of cultural heritage by
X-ray spectral analysis
A. G. Revenko
Discussed are special features of the X-ray spectral analysis in solving different problems related to the study of glass materials
or objects, which are of archaeological, historical or artistic value. The following objects were considered: various dishes and
colored glass. The study of the chemical composition of particular materials, for example, obsidian or raw materials for the
production of glass is very often necessary to determine their sites. The increasing number of publications on these topics is
noted. The versions of sample preparation and the problem of the heterogeneity of materials under study are considered.
Essential attention was given to techniques for the conversion of experimental intensities into concentrations of elements
determined. The estimates of the matrix effects are given when analyzing certain kinds of glass with X-ray fluorescence analysis
(XRF). Copyright
c 2009 John Wiley & Sons, Ltd.

Introduction of a remaining material. It is desirable to retain the original

Specialists note that even in rather prosperous European countries
a destruction of precious objects of cultural heritage happens faster
than their restoration, conservation and study. Many reasons are
responsible for this: great financial needs, environmental changes,
wars, natural disasters, and finally, misunderstanding and simple
negligence.
Russia has a rich cultural heritage. This heritage includes both
relatively massive objects, for example, buildings and monuments,
and objects of rather small sizes including glassware, jewellery,
coins, glass and ceramic fragments, and others. All these are the
basis for the present and the future of our culture. When solving
problems, related to the conservation of the objects of cultural
heritage, it is necessary to permanently carry out many analytical
investigations, whose aim is:
the determination of a chemical composition;
the elucidation of a period and a location of product
manufacture and the affiliation;
the identification of particular objects;
the diagnostical study of the material of such objects before
the conservation or the choice of materials for the restoration.
For a number of articles the requirements to which the methods
have to correspond were formulated so that materials and objects
of historical and cultural value could be studied.[1 6] These
methods should be non-destructive, rapid, efficient, versatile,
flexible, sensitive and multielement.
The capabilities of X-ray spectral analytical method and efforts
of many scientists were widely applied when studying the objects
considered. In the literature one can find examples of the
application of X-ray spectral analytical method and its version,
X-ray fluorescence analysis (XRF), to the investigations of art
objects such as icons, frescoes, oil paintings, watercolors, wood-
, glass-, textile-, and paper-based paintings, various glassware,
jewellery, labor implements, coins, and others. The work of an
analyst is similar to the work of a forensic scientist. In both cases
material as obtained. It was not for nothing that in his annual
reviews the known specialist Ph. Potts devoted one chapter to the
application of XRF to archaeology and forensics.[7 9] Another fact
is of particular importance: conclusions drawn from the results
affect the destiny of people (in justice) or the ideas of analysts
studying the materials considered. Thus, it is very important to
obtain reliable results.
In this report only a small part of representative examples is given
which illustrate the possibilities of X-ray spectral analysis in the
considered field of application taken from the publications of the
last years. Additional references can be found in the literature.[10]
Principal attention is given to the works on the study of glass wares
and colorants for glass. Although the cited examples reflect mainly
the progress in XRF, some publications are also mentioned where
the authors applied other versions of X-ray spectral analysis.
The author of this work took part in the XRF study of raw
materials and the Pleistocene-Early Holocene exotic graphite
artifacts from the valley of Vitim river (the northern Baikal region)
and their mode of transportation, in determining the chemical
composition of archeological metal finds from the burial place
found on the banks of Lake Baikal (Bronze Age) and in other
investigations of similar kind. In the European Conference on
X-Ray Spectrometry (June 2006, Paris, France) 42 of 287 reports
dealt with the application of X-ray methods to the study of
objects of cultural and historical value. This fact reflects both
the total progress in instrumentation and the increased attention
of society to these problems. The examples of X-ray method
applications to the study of such objects showed that in a
number of cases the earlier-developed XRF techniques, which
Correspondence to: A. G. Revenko, Institute of the Earths Crust, SB, RAS,
Irkutsk, Russia. E-mail: xray@crust.irk.ru; agrevenko@yandex.ru
Article presented as part of the special issue X-Ray Spectrometry in Siberia and
Mongolia.
63

it is necessary to reconstruct the past using the minute fragments Institute of the Earths Crust, SB, RAS, Irkutsk, Russia

X-Ray Spectrom. 2010, 39, 6369 Copyright

c 2009 John Wiley & Sons, Ltd.

concentrated on other problems, could be used in the field
considered without substantial changes. This is true for the ceramic
and glass wares, alloys, and metallurgic slags. Similar problems
were solved in geological and research laboratories of the glass
industry. The difficulty of studying paintings and manuscripts, and
also the analysis of some materials without their destruction are to
some extent different when using micro-XRF spectrometers. For
satisfactory solution of such problems it is necessary to use the
recent theoretical and experimental developments. The author has
presented the preliminary considerations of the given problem in
several papers.[4 6,10]
XRF has been successfully applied to solve these problems. But
some questions appear. In particular, in the literature, examples
of comprehensive estimations of matrix effects in analyzing glass
materials by XRF have not been found. This report gives the
examples of the theoretical estimation of the effect of chemical
sample contents on intensities of X-ray fluorescence and scattered
characteristic radiation from an anode. The results of our calcu-
lations are given for the samples of ancient, volcanic (obsidians),
mosaic and iridescent glasses of different chemical compositions.
We have restricted ourselves mainly to two criteria in choosing
samples for calculations: (1) the sum of the determined element
contents should be close to 100%; (2) the contents of particu-
lar elements in them should be as maximum or minimum as
possible to establish a whole range of the variations in matrix
effects.
General Characteristics of Glass
Glass, nowadays, is a common term used for a wide group
of materials. It refers to natural glass (obsidian) and vitreous
phase materials like faience, glaze, Egyptian blue and others. The
main components of glass are Si, B, Al, P, Na, Ca, oxides, etc.
and metal oxides such as Li, K, Mg, Pb, Fe and so on. Glass
appeared in the Ancient Egypt or the Middle East about 5000
to 6000 years ago.[11,12] Its production technology is supposed to
have come either from the progress in the ceramics technology or
in processing vitreous slags obtained in the production of copper
or lead.[12] Glass is mainly made of quartz with the addition of Na,
K and Pb compounds to decrease the melting point, stabilizing
agents such as lime or alumina to increase the lifetime and to
avoid the solubility in water, and also colorants (Cu, Mn, Co)
and opacifying agents (Sn, Sb). Colorless glasses are sometimes
manufactured. Janssens et al.[1] note that although glasswares are
not so frequently found at archaeological sites as metallic and
stone artifacts, nevertheless, the use of silicate glass objects has
been known since prehistoric times.
Chemical glass composition is dependent on the raw materials
used and its production technology. It is natural that the
technology is substantially dependent on the particular time
period of glass production and geographical locations of glass
workshops. Therefore, results of chemical analysis of glass
fragments found at archaeological sites can be very useful in
the study of the glass production technology and its trade routes
in different historical periods. The possibilities of XRF provide its
wide use in studying such materials.
Swann[13] wrote a brief review of early publications on the
application of Particle induced X-ray emission (PIXE) to the study
of the chemical composition of Roman glass. In the Roman period
(IVI centuries) glass was made of sodium-lime mixture (Natron
64
period). The low Mg and K concentrations were characteristic of this
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c 2009 John Wiley & Sons, Ltd.
A. G. Revenko
period. Its ordinary composition was 6672% SiO2 , 1618% Na2 O
and 78% CaO. For Roman glass it is sufficient to know the contents
of main components to confirm its genetic assignment. Samples
of Roman glass were also studied in refs [14 19] . Mass et al.[20]
have presented interesting data, confirming the cooperation of
metalworkers with ancient glass makers. Freestone et al.[21] have
considered the possibility of other procedures of glass production
in the ancient times, different from the ones in ref. [1]. A small
number of publications is dedicated to the study of samples
of more ancient glass[22] or glass from the other sites such as
Russia,[23] the Lower Saxony, and Hesse.[24]
Information about the change in the glass production tech-
nology in the Middle Ages, and also articles on the study of
chemical compositions of these glasses with XRF can be found in
the publications.[25 31] Schreiner et al.[32] have discussed the most
important periods and subperiods in the development of glass
production technology in Northwestern Europe. One of the latest
papers by Schalm et al.[33] presents the hierarchical classification
of window glass fragments, based on the content of its main
components.
Natural volcanic glass (obsidian) is formed when the viscous
persilicic lava solidifies. Obsidians occur naturally in different colors
such as red, black, gray, sometimes with beautiful iridescence. They
are composed of SiO2 (about 75%), additives of Al, Na, K, Ca, Fe
and Mg oxides, and water (0.10.3%). The obsidians, formed of
a single lava stream, are usually chemically homogeneous; but
they somewhat differ in their composition at different locations.
Obsidians are abundant in the geographical sense. They are found
in all main volcanic zones of the Earth. Being a valuable material
for making stone implements obsidians were excavated in many
locations. This material of immense hardness (seven points on
the Mohs scale; it is harder than flint) was in great demand.
Obsidian was widely traded, sometimes up to 1000 km from
its deposits. Since the Lower Paleolith it was used for articles,
namely for making knives, arrowheads, and other sharp cutting
and stabbing objects. The study of the chemical composition of
obsidian is often required for the identification of its excavation
sites and transport routes. The paper by Negash et al.[34] is of
interest in which they present the results of XRF application
to the investigations of obsidians from some sites in Ethiopia.
This is one of the typical publications in this field. In obsidian
samples the ranges of the particular oxides are (in %): Al2 O3
10.514.9, SiO2 53.5579.65, K2 O 0.745.48, CaO 0.459.45, TiO2
0.12.6, MnO 0.10.54, and Fe2 O3 0.0911.7 (data from the
publication by Doelman et al.[35] ). We estimated the matrix effects
for these samples. The results are presented in the Section on
The theoretical estimation of the matrix effects for the glass
materials.
Instrumentation
To aid the investigations of objects of cultural and historical value,
it is appropriate to use conventional XRF instrumentation. The
characteristics of the particular models of X-ray spectrometers
can be found in the following monographs [refs [3645]]. The
different versions of X-ray spectral analysis, because of their
specific features, came to be used in a range of investigations:
electron-probe microanalysis (EPMA), PIXE and Total reflection
X-ray fluorescence (TXRF) units, energy-dispersive X-ray analyzers
(EDXRF), XRF using the synchrotron radiation for the excitation
of the fluorescence of a sample under study (SR-XRF) and XRF
X-Ray Spectrom. 2010, 39, 6369
Estimation and account for matrix effects in studying glass

using the capillary optics (-XRF). The -XRF term stands for the
approach, which allows the study of sample areas of dimensions
from a few microns to one hundred microns. This version
complements EPMA and PIXE, which are applied in investigations
of small objects. Before the advent of X-ray capillary lenses the
diaphragming of the primary beam of electrons (EPMA), protons
(micro-PIXE), or X-ray photons was used for the study of small-
sized objects. However this version of XRF was not advantageous
due to the substantial decrease in the X-ray intensity emitted by
atoms of the sample under analysis. The development of X-ray
spectrometers, based on the use of capillary optics, which allows
focusing X-rays in relatively small areas of samples analyzed,
has extended the possibilities of XRF and raised its appeal for
studying objects of historical and cultural value. Several research
groups and commercial enterprises that produce the analytical
instrumentation have used the combination of low-power X-ray
tubes with focusing capillary lenses and have proposed different
purpose X-ray spectrometers. The rapid development of X-ray
optics, detectors, and excitation sources is characteristic of the
past decade. This development has brought about advances in
the considered field of investigations. The characteristics of the
particular models of micro-XRF spectrometers are presented in
the publications.[2 6,46 50]
The Theoretical Estimation of Matrix Effects
for Glass Materials
Let us consider the estimations of the theoretical count-rate values
of the radiation of analytical lines of some elements determined in
glass and also the count-rate values of coherently and incoherently
scattered characteristic radiation from an anode (e.g. RhK ). The
theoretical count-rate values were computed using the program
presented in the publication by Finkelshtein and Afonin.[63]
The algorithm used in this program takes into account the
contribution of effects of secondary and tertiary fluorescence and
also the additional fraction related to the contribution of radiation
scattering from atoms of a sample analyzed.[64,65] Theoretical
calculations of the photo- and Auger electron contributions to
the generation of X-ray fluorescence were published by Ebel
et al[66,67] and Afonin et al.[68] These contributions were found to
be negligible in most real analytical applications (from tenths of
a percent to a few percent). For this reason the contributions of
photo- and Auger-electrons in the intensities of analytical lines
have not been taken into account in this paper.
Our calculation procedure is given in detail in refs [37,69 71] .
The K lines of elements Na through Ba and L -, L -lines of
elements Sn through Pb were chosen to calculate specific relative
count-rate values (Irel,j ):

Irel,j = (Isample,j /Ireference,j ) (C reference,j /C sample,j )

XRF Techniques Used
where
In the considered publications, the external standard,[16] Isample,j = X-ray fluorescence line j intensity from the sample;
the background standard,[19,23,28,30,51 54] and the fundamental Ireference,j = X-ray fluorescence line j intensity from the reference
parameter[1,17,26,29,31,55 59] methods have been applied. In using sample;
the Scanning electron microscopy (SEM) adaptation the conven- C sample,j = concentration of the element j in the sample;
tional ZAF (method accounting matrix effects with the separate C reference,j = concentration of the element j in the reference
introduction of corrections for the atomic number Z, absorption sample.
and fluorescence excitation by characteristic and bremsstrahlung The SGD-1A reference sample was used for calculating the ratio
spectra) version is applied,[23,60,61] which is suitable for the elec- of count-rate values of all analytical lines. The analyzed minor
tron excitation. Cox and Pollard[57] have proposed a computer element concentrations were assumed to be constant and equal
program where the simplified version of fundamental parameters to 0.01%. Table 2 presents the results of calculating (Irel,j ) obtained
is represented (they have neglected the difference in the mass for the mean composition of two samples of ancient glass from
absorption coefficients of primary radiation and the contribution Qumran,[72] the chemical compositions of which are given in
of selective excitation effect). They tested this version on glass
samples with contents of ZnO up to 0.4%, CuO up to 3%, and
PbO up to 0.7%. Medicus and Ackermann[58,59] have developed Table 1. Chemical composition of glass, obsidian samples and CRM,
a technique and software to correct for the matrix effects for in %
glass samples based on the fundamental parameter method us-
ing the conception of effective wavelength. Hoffmann et al.[25] Sample Na2 O MgO Al2 O3 SiO2 K2 O CaO TiO2 Fe2 O3
have also noted that in studying colored beads it is necessary Gl 1 16.5 0.2 2.5 69.6 0.8 8.4 0.1 0.5
to apply corrections for the difference in mass absorption coeffi- Gl 2 17.0 0.1 2.4 71.6 0.6 5.9 <0.1 0.4
cients when varying the Pb contents. Nevertheless, in a number Obs P 3.61 0.01 12.11 74.66 5.21 1.11 0.21 2.4
of publications there is no information about the procedures Obs B 3.0 0.01 14.91 53.55 0.74 9.45 1.6 11.72
used by authors to convert measured intensities of analytical Obs G 3.13 0.01 10.72 79.65 5.48 0.52 0.07 0.09
lines into concentrations of elements determined.[27,49,62] It is of Obs K 3.15 0.01 10.51 72.46 4.21 1.27 0.26 1.96
utmost importance to inform in considerable detail the analyt- NBS278 4.84 0.23 14.15 72.97 4.16 0.983 0.24 2.04
ical techniques used. For example, for the external standard, it JR-1 4.1 0.09 12.89 75.41 4.41 0.63 0.1 0.96
is necessary at least to list the comparison standards used. The JR-2 4.03 0.05 12.82 75.65 4.45 0.45 0.09 0.86
validity of this requirement will be shown further in a number of RGM-1 4.07 0.28 13.72 73.45 4.3 1.15 0.27 1.86
examples. AGV-1 4.26 1.53 17.15 58.84 2.92 4.94 1.05 6.77
From the point of view of matrix effects glass is close to some GH 3.85 0.03 12.5 75.8 4.76 0.69 0.08 1.34
types of rocks. These materials (glass and rocks) differ substantially
According to the information of authors the uncertainties (SD) are from
when large amounts of components such as PbO, SnO2 , CuO, Co, 0.02% for TiO2 , 0.10.3% for MgO, Al2 O3 , K2 O, MnO, Fe2 O3 to 0.5% for
Mn, and others that change glass characteristics, for example its Na2 O, CaO and 0.70.8% for SiO2 .
65

colorants, are added.

X-Ray Spectrom. 2010, 39, 6369 Copyright

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 A. G. Revenko

Table 2. Specific relative count-rate values (Irel ) SiK , CaK , TiK , FeK , Table 3. Chemical composition of the ancient mosaic glasses
ZnK , BaK , RhKcoh and RhKincoh for glass samples (the reference (Chiavari et al.[15] ), in %
sample is SGD-1A)
Sample Na2 O SiO2 CaO MnO Fe2 O3 CuO PbO SnO2 Sb2 O3
Sample SiK CaK TiK FeK ZnK BaK RhKK RhKHK
G111 11.24 60.4 8.23 0.50 0.30 0.01 8.45 3.82 0.05
SGD-1A 1.000 1.000 1.000 1.000 1.000 1.000 1.000 1.000 G112 22.43 61.8 7.23 0.42 0.89 0.11 0.10 0.01 2.13
Gl 1 1.149 0.991 1.046 1.212 1.608 1.698 1.728 1.428 G113 16.79 67.0 7.23 0.80 0.84 0.12 0.28 0.02 1.64
Gl 2 1.146 0.996 1.107 1.286 1.691 1.810 1.820 1.472 G114 22.78 62.2 7.00 0.71 0.82 0.09 0.14 0.01 1.52
Obs P 1.146 0.890 1.091 1.247 1.570 1.674 1.681 1.397 G115 25.42 61.8 5.03 0.30 1.33 0.22 0.09 0.02 1.00
Obs B 1.052 1.070 1.091 1.083 1.055 1.073 1.079 1.030 G116 24.31 60.8 7.13 0.63 0.71 0.78 0.35 0.11 0.24
Obs G 1.183 0.872 1.082 1.274 1.748 1.875 1.914 1.542 G117 24.10 60.6 7.13 0.53 0.68 1.07 0.57 0.19 0.18
Obs K 1.163 0.935 1.143 1.311 1.653 1.685 1.723 1.400 G118 23.42 61.1 7.16 0.54 0.73 1.01 0.58 0.14 0.18
NBS278 1.099 0.877 1.081 1.246 1.607 1.191 1.251 1.123 G119 22.73 60.8 8.44 0.82 1.13 0.10 0.11 0.01 0.41
JR-1 1.146 0.905 1.123 1.313 1.740 1.874 1.887 1.510 G120 17.89 63.0 11.01 0.93 1.08 0.11 0.13 0.04 0.09
JR-2 1.148 0.905 1.126 1.320 1.755 1.892 1.906 1.519 G121 17.60 63.3 7.91 0.66 1.05 1.45 1.66 0.07 0.31
RGM-1 1.127 0.910 1.115 1.280 1.641 1.732 1.764 1.444 G122 14.34 54.8 7.63 1.08 2.49 3.78 6.83 2.47 0.06
AGV-1 1.046 0.978 1.103 1.165 1.279 1.306 1.330 1.189 G123 18.43 63.6 7.84 1.43 1.22 0.32 1.62 0.01 0.01
GH 1.150 0.898 1.112 1.295 1.693 1.833 1.843 1.487 G124 13.76 65.6 5.15 0.48 1.67 2.47 4.90 0.57 0.35
G125 13.13 70.8 5.63 1.43 0.67 0.01 0.04
G126 12.45 66.7 7.82 2.59 0.65 2.39 0.01 0.11
G127 11.11 71.8 6.61 2.08 0.81 0.07 0.01 0.01
Table 1 (the sample Gl 1 corresponds to group 1, and the sample
G128 14.61 75.2 4.71 0.07 1.61 0.19
Gl 2 to group 2). According to the authors the uncertainties (SD)
G129 10.38 66.8 9.11 0.69 2.26 2.95 0.20 0.02 0.05
are from 0.02% for TiO2 , 0.10.3% for MgO, Al2 O3 , K2 O, MnO,
Fe2 O3 to 0.5% for Na2 O, CaO and 0.70.8% for SiO2 .
The evaluation was made under the following measurement
conditions: Rh-anode, 50 kV, d0 of Be window 100 m, the
reference sample SGD-1A. The table presents the specific relative Table 4. Specific relative count-rate values (Irel ) of some lines for
count-rate values (Irel ) of analytical lines, computed in the same ancient mosaic glass samples (Rh-anode, 50 kV, d0 = 100 m Be,
way as in the publications.[10,37,69 71] It is seen that for these SGD-1A reference sample)
samples Irel of all considered analytical lines are sufficiently close, Sample SiK CaK FeK CuK PbL1 SnK RhKcoh RhKincoh
and the difference ranges from 0.3 to 6.6% (SiK 0.3, CaK 0.5,
TiK 5.8, FeK 6.1, ZnK 5.2, BaK 6.6, RhKcoh 5.3, and G111 1.051 0.760 0.835 1.088 0.925 0.438 0.504 0.948
RhKincoh 3.1). Similar estimates made for four obsidian samples, G112 1.082 1.010 1.183 1.528 1.565 1.429 1.578 1.426
the chemical compositions of which are given in the ref [35] and G113 1.471 1.483 1.496 1.503 1.372 1.043 1.480 1.364
Table 1, have shown the wide scatter of Irel values (Table 2). The G114 1.527 1.540 1.563 1.588 1.276 1.122 1.572 1.406
lowest Irel values of all analytical lines except CaK - and TiK -lines G115 1.068 0.998 1.268 1.616 1.647 1.602 1.673 1.440
were obtained for the sample Obs B (only Irel of CaK -line of G116 1.567 1.580 1.535 1.529 1.479 1.362 1.500 1.325
this sample is maximum), and the highest ones did for Obs G. G117 1.548 1.560 1.483 1.451 1.372 1.250 1.402 1.283
The difference in Irel values was (in %): SiK 12.5, CaK 22.7, G118 1.538 1.550 1.477 1.444 1.371 1.247 1.395 1.281
TiK 5.6, FeK 21.1, ZnK 65.7, BaK 74.7, RhKcoh 77.4, G119 1.506 1.519 1.540 1.566 1.552 1.403 1.564 1.357
and RhKincoh 49.7. As an example, Table 2 gives Irel values for G120 1.117 0.991 1.127 1.426 1.453 1.487 1.478 1.300
seven CRMs of rocks: obsidian NBS278, rhyolites JR-1, JR-2, RGM-1, G121 1.426 1.435 1.304 1.192 1.054 0.985 1.095 1.135
andesite AGV-1, basalt BR, and granite GA. The contents of main G122 0.985 0.832 0.921 1.060 0.813 0.455 0.504 0.885
rock-forming elements of these CRMs,[73] and also four obsidian G123 1.425 1.434 1.369 1.252 1.125 1.098 1.149 1.158
samples from ref [35] are given in Table 1. Several of these CRMs G124 1.278 1.280 1.136 0.835 0.641 0.585 0.691 0.968
were used in calibrating the XRF techniques for the analysis of glass G125 1.524 1.537 1.574 1.620 1.676 1.621 1.646 1.386
samples.[30,74] The obtained data demonstrate that it is necessary G126 1.118 0.961 1.159 1.356 1.252 1.286 1.278 1.168
to take into account the matrix effects even if the colorants are G127 1.165 0.948 1.177 1.450 1.486 1.563 1.539 1.322
absent in the samples. G128 1.213 0.987 1.305 1.657 1.680 1.790 1.758 1.433
Table 3 presents the chemical composition of samples of ancient G129 1.321 1.328 1.187 1.184 1.183 1.164 1.188 1.121
mosaic glass,[15] and the Irel of their analytical lines within the
wavelength ranges from CuK to BaK are given in Table 4. It
is seen that Irel values of the analytical lines such as SnK vary
fourfold. As an example, Fig. 1 presents the intensity of FeK -line to understand that when developing the analytical techniques for
(in arbitrary units) versus the Fe2 O3 content for the mosaic glass objects of cultural heritage an analyst must aim to minimize errors
samples. It is seen that the points of samples with the smaller in determining the element contents for each sample under study.
Irel values are under the trend line. These are, in particular, G111 Data on the values of the mass absorption coefficients of
(0.835), G126 (1.159), G127 (1.177), G112 (1.183), G120 (1.127), and radiation of analytical lines, the contribution of enhancement by
G122 (0.921) samples. In turn, the points of samples with the higher atoms of particular samples, and the estimation of contribution
Irel values such as G125 (1.574), G114 (1.563), G119 (1.540), G128 of radiation scattering from atoms for all samples analyzed in
66

(1.305), and others are above the trend line. Here it is important the present work are available. However the main aim of this

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c 2009 John Wiley & Sons, Ltd. X-Ray Spectrom. 2010, 39, 6369
Estimation and account for matrix effects in studying glass
Figure 1. The intensity of FeK -line (in arbitrary units) versus the Fe2 O3
content for the mosaic glass samples.
Table 5. Chemical composition of an iridescent Loetz glass artifact
(sample L356, Mantler et al.[76] ), in %
Material Na Si Cl K Ca Ag
Bulk glass 2.4 34.3 0.4 12.0 5.4
Iridescent layer 2.0 30.7 0.7 11.0 0.6 1.1
Table 6. Specific relative count-rate values (Irel ) of analytical lines of
the iridescent Loetz glass artifact (Rh-anode, 50 kV, d0 = 100 m Be,
SGD-1A reference sample)
Material NaK SiK ClK KK CaK AgK
Bulk glass 1.112 1.314 0.984 0.906 0.741 1.286 1.275
Iridescent layer 1.002 1.104 0.776 0.661 0.557 0.317 0.741
publication is to demonstrate the necessity of taking into account
these effects when analyzing different glass samples with XRF.
The results of analyzing the iridescent glass are presented in a
number of publications.[75 77] Iridescent effect is obtained when a
very thin glass layer with a substantially different refraction index is
applied on a base material. Iridescent glass always attracts interest
for public and private collections. The most famous producers
of such a glass are Tiffany in USA (the patent dated 1881) and
Loetz in Austria (the patent dated 1898).[76] Because of increasing
trend of falsifications, objective methods for the classification and
identification of an origin of similar glass samples have become
active, which are based not only on aesthetic and style criteria but
also on the results of their chemical composition examinations.
Studies have shown that the thickness of surface layers of
iridescent Tiffany glass, iridescent Loetz glass, and present-day
glass are 50100 m, 100300 m, and 100250 m, respectively.
Table 5 presents data on the chemical composition of the
iridescent Loetz glass artifact (results for SEM-EDS and XRF). One
can see the substantial difference in Ca, Ag, and Pb contents
between the base and the coating. It is natural that this difference
in the chemical composition affects the specific relative count-rate
values (Irel ) of the analytical lines from the iridescent glass sample
and the base (Table 6). This difference is especially significant for
the KK -, CaK -, PbL -, and AgK -analytical lines.
Our estimates have demonstrated that the key factor, which
has an effect on the fluorescence intensity of analytical lines for
X-Ray Spectrom. 2010, 39, 6369 Copyright

the considered kinds of glass, is the difference in the absorption
of primary and fluorescence radiation. The contribution of tertiary
fluorescence for the glass samples under consideration can be
neglected. The contributions of secondary fluorescence and
scattering from atoms of samples for some analytical lines are
510% and more, therefore should be taken into account. It is
especially important when the chemical compositions of glass
samples under investigation are much different from the ones of
CRMs used.
The Problem of Heterogeneity of Materials
Studied
In ref [50] attention was given to the problem of heterogeneity
which becomes very pronounced when using SR-XRF and micro-
XRF spectrometers for the analysis of powder materials. It was
noted that some authors, applying these versions of XRF, have used
fundamental parameters not considering the need for satisfying
a number of conditions. In the case of colored glasses scientists
O Pb have found the presence of small copper metal spherules with
44.7 0.4
size less than a micron in the homogeneous glass matrix.[22,78] In
39.5 14.4 ref [18] it was noted that the size of copper particles, which ranged
from <50 nm to several hundred nm, defined the tone of glass.
Such variations in the particle sizes do not cause difficulty for most
analytical lines in the X-ray range. However it is important to keep
in mind that in certain samples of ancient glass inclusion of copper
particles of size of tens of microns is possible.[22]
When solving certain archaeological problems it is desirable to
take measurements without making changes to original samples.
PbL At the same time the particular glass fragments cannot meet the
requirements for perfect samples, such as a flat surface, saturated
layer, homogeneity, etc. Roedel et al.[48] have presented a brief
review of publications on estimation of the effect of particle
sizes on results of quantitative analysis of glasses using energy-
dispersive micro-XRF spectrometry. They have estimated this effect
for particles with sizes ranging from 50 m to more than 1 mm.
The complex dependence of the fluorescence radiation intensity
on this factor was noted. The intensity was dependent on the total
chemical composition of glass, the shape and volume of particles,
the energetic range, and the characteristics of used polycapillary
lenses. It is impossible to take into account all these factors
with simple approaches. In this publication, the conclusions of
Losev et al.[79,80] were experimentally confirmed that for coarse
particles the influence of particle sizes decreased significantly. For
example, for particle size of 1 mm the relative standard deviation
related to the sample homogeneity was in the range of 15%;
this is comparable to the results obtained for perfect samples.
In measuring samples of smaller particle sizes, in particular in
the range of 100 to 300 m, unsatisfactory results were obtained,
which can be considered only as qualitative data. The reduction in
particle sizes down to 50 m provided an acceptable accuracy.
The refs [16,61,72,81 86] present the investigations of variations in
a chemical composition of glass due to various factors related to
the environmental conditions. This is another factor, which makes
the acquisition of data on chemical glass composition difficult.
In these papers one can find information about the variations
in the chemical composition of glass due to the corrosion, and
recommendations on solving such problems.
We note finally that for glass samples of high Pb or Sn content
the thickness of the saturated layer dsat (an infinitely thick sample
or the information depth after Mantler [76,77] ) is no more than tens
67
c 2009 John Wiley & Sons, Ltd. www.interscience.com/journal/xrs

of microns even for short-wavelength radiation. For example, for
SnK from samples with high concentrations of high-Z elements
dsat is less than 100 m. It significantly differs from the similar
magnitude for rocks that are more than 1500 m (SGD-1 CRM).
The thicknesses of thin layers vary similarly. For example, in rocks
the thin layer is 22 and 1 m for SnK and CuK , respectively, [15] C. Chiavari, M. Martini, E. Sibilia, M. Vandini, Quaternary Science
whereas for glaze it is 0.17 and 0.01 m, respectively. Note that
the thicknesses of the surface layers of iridescent glass, glaze, and
enamels are all in the range of 100300 m.
Conclusion
The analysis of examples of X-ray method applications to the study
of glass materials or glass objects of archaeological, historical or
artistic value showed that in a number of cases, the XRF techniques,
already developed to solve other problems, can be used without
substantial changes. This is true in particular for volcanic glass
(obsidian) and Roman glass samples. Similar problems were solved
in geological and research laboratories in the glass industry. In
some cases, the authors have succeeded in finding satisfactory
solutions only with the combination of several methods. The study
and analysis of some materials without destructing samples is to
some extent different when using micro-XRF spectrometers. To
arrive at a satisfactory solution to such problems it is necessary
to use recent theoretical and experimental developments. It is
important to intensively compile a database for different kinds
of glass and its production location. The results of theoretical
estimate of the matrix effects with XRF for certain kinds of glass,
made in the present work, have demonstrated that it is necessary
to take into account these effects. It has been shown that the
specific relative count-rate values (Irel ) of the analytical lines of
some of the elements in the ancient glass and obsidian samples
differ by 24 times from the ones in mosaic or iridescent glass
samples.
Acknowledgements
The author is grateful to RFBR for financial support of this work
(grant No 07-05-01061); T. S. Andreeva is acknowledged for her
help with the preparation of the manuscript.
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