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Spectrochimica Acta Part B 62 (2007) 1123 – 1129

www.elsevier.com/locate/sab

Study of archaeological ceramics by total-reflection X-ray fluorescence

spectrometry: Semi-quantitative approach
R. Fernández-Ruiz a,⁎, M. García-Heras b,c
a
Universidad Autónoma de Madrid, Facultad de Ciencias, Servicio Interdepartamental de Investigación,
Modulo C-9, Laboratorio de TXRF, Crta. Colmenar, Km 15, Cantoblanco, E-28049, Madrid, Spain
b
Instituto de Historia-CSIC, C/Serrano, 13. E-28001, Madrid, Spain
c
CENIM-CSIC, Avda. Gregorio del Amo, 8. E-28040, Madrid, Spain
Received 28 December 2006; accepted 24 June 2007
Available online 23 August 2007

Abstract

Total-reflection X-ray fluorescence spectrometry has been compared with Instrumental Neutron Activation Analysis in order to test its potential
application to the study of archaeological ceramics in the archaeometric field. Two direct solid non-chemical sample preparation procedures have been
checked: solid sedimentation and solid chemical homogenization. For sedimentation procedure, total-reflection X-ray fluorescence allows the analysis
of the elemental composition with respect to the size fraction but not the average evaluation of the composition. For solid chemical homogenization
procedure, total-reflection X-ray fluorescence provides precise (from 0.8% to 27% of coefficient of variation) and accurate results (from 91% to 110% of
recovery) for 15 elements (Cr, Hf, Ni, Rb, Al, Ba, Ca, K, Mn, Ti, V, Cu, Ga, Y and Fe) with an easy sample preparation process of the solid clay and
without previous chemical treatment. The influence of the particle sizes has been checked by total-reflection X-ray fluorescence sample angle scans and
anomalous behaviors have been found for three additional detected elements: As, Sr and Zn, which can be attributed to interference effects of the mineral
grain sizes of their associated chemical phases in the total-reflection X-ray fluorescence interference region. The solid chemical homogenization
procedure produces data useful for archaeological interpretation, which is briefly illustrated by a case-study. Finally, the decantation procedure data can
be also useful for size chemical speciation and, consequently, for alternative environmental total-reflection X-ray fluorescence applications.
© 2007 Elsevier B.V. All rights reserved.

Keywords: TXRF; INAA; Archaeological ceramics; Size fraction; Compositional characterization

1. Introduction new information from emerging techniques. Nevertheless, the

The determination of the composition of ancient ceramic
samples has a special relevance to the construction of heuristic
models concerning the production and distribution of these
materials in the past. Currently, this kind of study constitutes
about one third of all archaeometric research that is carried out
on an international scale [1]. Since the 1970s, the analytical tool
most often used and accepted for the archaeological community
has been INAA, because of its ability to provide the required
levels of accuracy, precision and detection limits for its
application in archaeological ceramics studies. The large number
of analyses already performed by several INAA laboratories also
provides an important data bank which can be compared with
⁎ Corresponding author. Fax: +34 914973529.
E-mail address: ramon.fernandez@uam.es (R. Fernández-Ruiz).
0584-8547/$ - see front matter © 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2007.06.015
wide use of this analytical method has not yet overcome, in some
cases, drawbacks such as high cost, or difficulty of access to a
suitable nuclear reactor for sample irradiation [2]. As alter-
natives, less expensive and more accessible methods have been
employed such as traditional XRF, AAS or ICP-OES. One of the
challenges facing current archaeometric research on ceramics is
the intra-regional differentiation of pottery production centers, a
subject that requires large and accurate sets of data on the
composition of ceramics. Therefore, the establishment of new
analytical tools or the development of those already proven
requires both correct standardization and normalization with
international accepted analytical techniques, such as INAA, in
order to assure the validity of the analytical results [3–5].
TXRF main features and potential applications can be found in
the paper of Prange [6] or the excellent book of Klockenkämper
[7]. Previous investigations, carried out by Klockenkämper et al.
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1124 R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129
[8], Cariati et al. [9] or Fernández-Ruiz et al. [10–12], were the
departure point for this investigation. The best approach to the
ideal TXRF thin film criteria for a solid particle deposition is that
the following three fundamental requirements are fulfilled: (1)
chemical homogeneity of the solid particles, (2) average particle
sizes around 1 μm and lower than 10 μm [13], and (3)
homogeneous spatial distribution of the deposited particles on
the sample carrier.
To provide the TXRF validation for this type of studies, a
reference clay material analyzed routinely by INAA was
employed as reference material, Ohio Red Clay from Resco
Products, Inc, Oak Hill, OH, USA (Ohio Red Clay-2 hereafter).
This sample was habitually used as batch control by the team of
the University of Missouri-Columbia in their INAA analyses
[14]. This work presents the results obtained in the comparison
of both techniques (INAA and TXRF) for the Ohio Red Clay-2
reference sample and also, the investigations carried out for the
samples preparation and optimization for TXRF analysis. The
application of the final TXRF procedure developed was applied
for evaluating a real archaeological case.
2. Experimental section
2.1. Instrumentation
Three main techniques have been used in this work. TXRF
for the analysis of the samples; quasi-elastic light scattering
spectroscopy (QELS) for the determination of the distribution
of particle sizes in suspension of the analyzed samples and
scanning electron microscopy (SEM) for the investigation of the
final size, distribution and homogeneity of particles deposited
on the flat carrier.
The analysis by TXRF was performed by using a Seifert
EXTRA-II spectrometer (Rich Seifert & Co, Ahrensburg,
Germany), equipped with a molybdenum X-ray fine focus
lines, and a Si(Li) detector with an active area of 80 mm2 and a
resolution of 157 eV at 5.9 keV (Mn Kα). The measurements
were performed working at 50 kV and filtered with a 50 μm Mo
Fig. 1. QELS spectra of aqueous sample distribution of Set-1, Set-2 and Set-3.
foil, adjusting the intensity so that a count rate of about 5000 cps
was achieved and an acquisition time of 1000 s. TXRF 8030C
spectrometer (Cameca, France) was also used with the objective
of undertaking studies of angular dependence of signal intensity
for some elements. This spectrometer combines a 3 kW X-ray
tube with a Mo/W alloy anode with a W/C double-multilayer
monochromator and in addition allows the variation of the
incidence angle by tilting the sample holder unit.
The QELS system used in this study was the AutoSizer IIc of
Malvern Instruments Ltd., equipped with a He–Ne 5 mW laser,
a photo-multiplier and a processing electronic system controlled
by the Malvern AutoSizer computer package. The SEM
equipment used was the Philips XL-30 equipped with a W
source, detectors of secondary and backscattering electrons and
a vacuum working lower than 4 × 10− 4 Pa.
2.2. Procedure of sedimentation
2.2.1. Samples preparation
Keeping in mind the three main requirements mentioned in
the Introduction section, and as a first approach to the problem,
it is possible to obtain different clay size fractions by the
sedimentation method. Three sets of samples (5 samples each)
were prepared from the Ohio Red Clay-2 reference sample.
First, the sample was ground for 30 min in an agate mortar.
Then 100 mg of the ground sample was poured into a test-tube
and mixed with high-purity water (Milli-Q, 18.2 MΩ) up to
10 ml. Next, the test-tube was placed in an ultrasonic bath for
30 min in order to disaggregate and homogenize the sample.
Once this process was carried out, the sample was left to settle
for 12 h. Finally, aliquots of 1 ml were taken, measured from the
base, at three different depths (15 cm in Set-1; 10 cm in Set-2;
and 5 cm in Set-3) in order to obtain an average distribution of
different particle sizes (always lower than 10 μm and with an
average size around 1 μm as postulated in the second main
requirement). Thus, the following three particle size sets were
obtained: Set-1, lower than 2 μm; Set-2, between 0.05 and
5 μm; and Set-3, between 0.1 and 10 μm. Fig. 1 shows the three
size distributions obtained by QELS.
From 2 to 5 μl of each fraction of particles was deposited on
a quartz sample support and dried on a ceramic hot plate. All
manipulations were made in an A-100 class laminar flow
chamber.
2.2.2. Results and discussion
In these conditions the samples were analyzed by TXRF.
Link Analytical AN-10000 computer package was used to
deconvolute the registered spectra. Once the element areas were
obtained, they were converted into relative mass units using the
equation
SFe Ax
mx ¼ mFe ð1Þ
Sx AFe
where m is the relative mass of a given element, A is the peak
area, S is the relative sensitivity and the index x and Fe denotes
each element analyzed and element chosen as reference
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R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129
Fig. 2. Representative TXRF spectrum from Ohio Red Clay-2 reference sample.
respectively. The S values are known since they were measured
by means of standard solutions, while the rest of the parameters
are experimental ones [12].
TXRF analyses were performed for the elements As, La, Nd,
U, Co, Cr, Cs, Hf, Ni, Rb, Sc, Sr, Zn, Al, Ba, Ca, K, Mn, Ti, V,
Si, Cu, Ga, Y and Fe. From the 25 elements evaluated, a total
number of 18 were chosen for routine analysis. Si was rejected
because the sample support was made of quartz, which involved
a Si random rise which was difficult to quantify. This fact could
be avoided by using plastic sample supports. Nonetheless, it
was preferred to use a quartz sample support due to its lower
background contribution. Co was also rejected because, in this
case, it was seriously interfered by the high intensity of Fe K
lines signal. La, Nd, U, Cs and Sc were rejected because they
were close to the detection limits that TXRF presents for this
matrix.
A relative mass value of 100 was associated to the Fe signal
(mFe). Fe was chosen because it is always present in clays and
ceramics of archaeological interest and it usually shows a
clearly differentiated peak in TXRF spectra as Fig. 2 shows.
The results of the Ohio Red Clay-2 reference sample
analyzed by INAA in the Archaeometry Laboratory at MURR
were expressed in ppm. For this reason, they were renormalized
in order to make the results comparable with those obtained by
TXRF. Thus, using the equation
cx
%vs Fex ¼ 100
cFe
for the same group of elements it was possible to transform
quantitative data cx (ppm) into semi-quantitative results
expressed as % vs Fe.
Fig. 3 shows the TXRF results obtained for Set-1, Set-2 and
Set-3 compared with INAA measurements, all expressed as
relative concentrations in % vs Fe.
The results obtained in Fig. 3 show that different behaviors
were present for the elements evaluated. Enrichments of the
elements As, Al, Rb, Sr and K; impoverishments of the
elements Mn and Ti; U-up behavior for the element Ba; and
finally, U-down behavior for the elements Cr, Hf, Ni, Zn, Ca, V,
1125
Cu, Ga and Y, with respect to the particle size fraction analyzed
were found. In the case of the enrichments, the fraction of larger
particle sizes (Set-3, between 0.1 and 10 μm), was higher for
these elements. In the case of the impoverishments, the fraction
of lower particle sizes (Set-1, between 0.01 and 2 μm) was
higher for these elements. In the case of U-up behavior, the
fraction of medium particle sizes (Set-2, between 0.05 and
5 μm) was the lowest for this element. In the case of U-down
behavior, the fraction of medium particle sizes (Set-2, between
0.05 and 5 μm) was higher for these elements.
The behaviors observed experimentally can be explained
considering the heterogeneous nature of the clay. Clays are
multi-layered mineral mixtures in which there are differences in
mineral and chemical composition between particles of different
sizes. This fact implies that the densities of micro particles can
be different. This finding contradicted the first main require-
ment of our approach by lost of chemical homogeneity.
Therefore, from the quantitative point of view the method of
sedimentation can be rejected to analyze this kind of material by
TXRF. On the other hand, the procedure developed could open
the way to evaluate the chemical composition of a generic solid,
based on its size and it could have interest in environmental
pollution studies (e.g., chemical analysis of polluted soils or
urban aerosols to diagnose air pollution from traffic and
factories).
Three elements, not analyzed by INAA in this material, Cu,
Ga and Y, have been determined by means of TXRF. From the
archaeological point of view, this fact is of great relevance since
an increase of the number of analyzable elements in an
archaeological material implies an increase of the number of
variables able to solve its geographical origin.
2.3. Procedure of solid chemical homogenization
In order to resolve the phenomenon of segregation produced
by the procedure of sedimentation and to comply with the first
ð2Þ
Fig. 3. Relative mass fraction for the 19 elements analyzed by TXRF for the
three different particle size fractions (Set-1, Set-2, Set-3) compared with INAA
results. Error bars obtained with n = 5 for TXRF and n = 20 for INAA.
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1126 R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129
Fig. 4. SEM micrographs of depositions according to different sample suspension agents. a–b: Ohio Red Clay-2 in high-purity water. c–d: Ohio Red Clay-2 in toluene.
e–f: Archaeological pottery sample in high-purity water.
main requirement, it was decided to prepare a new set (Set-CH)
in which the sedimentation problems were diminished.
2.3.1. Sample preparation
First, the sample was ground by an agate mortar until it had a
particle size lower than 30 μm. Then it was ground again for 1 h
by using a vibration micro-pulverizer equipped with a ball and
base of agate. Afterwards, 1 ml of high-purity water was added.
Next, the mix was poured into a test-tube in which high-purity
water was added up to 10 ml. The sample was homogenized for
1/2 h by ultrasonic disaggregation in order to disperse possible
agglomeration of particles. Finally, the particle size distribution
in suspension was checked by using QELS until it had the
required distribution and, therefore, was in accordance with the
second main requirement. When the sample had this size
distribution, it was again homogenized and, maintaining the
agitation always constant, 5 μl of the suspension was placed on
the quartz flat carrier and dried on a ceramic hot plate. All
manipulations were made in an A-100 class laminar flow
chamber.
2.3.2. SEM verification
In order to verify the third main requirement, different kinds
of depositions were generated on quartz sample supports and
observed by SEM after gold metallization. The first one was a
suspension in water, showing a distribution of concentric rings
in shape, probably associated with an edge effect in the liquid–
solid interface during the water evaporation process (Fig. 4-a,
b). In order to obtain a distribution of particles that were isolated
and homogeneous, we experimented with different agents of
different surface tensions, particularly with toluene and high-
purity water. It was established that toluene provided the best
distribution (Fig. 4-c, d). Nevertheless, it was noticed that this
agent seriously distorted the analytical determinations. Probably
the observed quantitative analytical distortion can be attributed
to the mountain effect, at micro particle level, that can be
appreciated in Fig. 4-d. This effect produces the lost of the thin
film geometry and the appearance of the energy dependent
matrix effect, which is in agreement with the experimental
observations. As a result, we finally decided to use high-purity
water, even though such a water did not strictly comply with the
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R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129 1127

Table 1 unequivocally detected as the spectrum associated with the

Ohio Red Clay-2 elemental relative mass fraction expressed as % vs Fe for reference material shown (Fig. 1). Previous results (Fig. 3)
INAA and TXRF
present the same systematic increase in the relative concentra-
Element INAA σ (n = 20) CV (%) TXRF σ (n = 5) CV (%) Accuracy tions of As, Sr and Zn with respect to INAA values. This implies
% vs Fe % vs Fe Recovery that the systematic increase is independent of the average
(%) particle size fraction analyzed. One possible explanation can be
As 0.028 0.002 7.2 0.040 0.002 4.3 146 attributed to high variations in the sizes of mineral phases
Cr 0.18 0.01 5.6 0.180 0.010 5.8 101 present in the clays and associated to As, Zn and Sr as Prange et
Hf 0.015 0.001 6.9 0.013 0.004 27.0 91
al. suggest [15].
Ni 0.14 0.03 21.4 0.150 0.009 5.8 107
Rb 0.36 0.02 5.6 0.354 0.004 1.0 98 A deeper study of this discrepancy was carried out in order to
Sr 0.05 0.06 106.0 0.131 0.004 2.8 249 understand the differences found. By means of the TXRF 8030c
Zn 0.18 0.02 11.1 0.284 0.009 3.2 157 spectrometer, a sample-angle scan of one representative sample
Al 185 6 3.2 171 4 2.4 92 of the Set-QH was carried out. The scan was performed from
Ba 1.1 0.3 26.3 1.24 0.06 4.5 109
0.25 to 2.25 mrad, around the critical angle for quartz, with a
Ca 3.0 0.4 13.3 2.81 0.04 1.4 93
K 64 16 25.1 69.3 0.8 1.1 109 step of 0.1 mrad and a measurement time per step of 100 s. Fig.
Mn 0.51 0.01 2.0 0.50 0.01 1.9 98 5 shows the angular behavior of the following elements: Fe, Ti,
Ti 12.0 0.6 5.0 12.35 0.10 0.8 103 Rb, K, As, Sr and Zn. The different curves were normalized at
V 0.39 0.01 2.6 0.43 0.01 2.3 110 the critical angle for quartz, defined as the inflection point of the
Cu n.m a n.m n.m 0.040 0.005 12.7 n.e b
angular curve, located at around 1.87 mrad.
Ga n.m n.m n.m 0.050 0.002 3.6 n.e
Y n.m n.m n.m 0.08 0.01 12.5 n.e The angular behavior for the representative elements that
Fe 100 — reference 100 — reference present good accuracy (Fe, Ti, Rb and K) is very similar (see
a
Not measured. Fig. 5) and is in agreement with the analytical results (see
b
Not evaluated. Table 1). In contrast, the angular behavior for the inaccurate
elements (As, Sr and Zn) presents strong differences with
respect to the Fe behavior chosen as reference. The angular
third main requirement for clays. In practice, water offered the behavior of the elements As, Sr and Zn presents strong
best analytical results. oscillations in its signals. These oscillations are typical when the
The final objective of this study was the application to particle sizes are lower than 100 nm [15] and they are usually
ceramic materials. Due to this fact, we tested the behavior of a associated to the appearance of X-ray interference effects in the
pottery sample using water as suspension agent. Fig. 4-e and f interference region of TXRF. In this case, the solid particles
shows the aspect of an archaeological pottery preparation associated to As, Sr and Zn should be in the range between 20
suspended in water, where a homogeneous distribution of the and 50 nm to explain the observed modulation of their angular
deposition can be observed. dependence.

2.3.3. Results and discussion 2.4. Application to an archaeological case-study

Semi-quantitative results were obtained by replicating 5
analyses of the same Ohio Red Clay-2 reference material. From an analytical point of view, the primary objective of
Table 1 shows the results of the 18 elements chosen for routine this study was to assess the compositional variability of the
analysis in Set-CH. Data were acquired the same way as that for
Set-1, Set-2 and Set-3.
Results show that, in this case, the accuracy for Cr, Hf, Rb,
Ni, Al, Ba, Ca, K, Mn, Ti, Fe and V with respect to INAA values
was excellent, as is shown in Table 1. The accuracy was
evaluated by measuring the recovery percentage with respect to
the INAA values. For the previous 12 elements the recoveries
vary from 91% for Hf to 110% for V. The precisions obtained in
the measurements by TXRF were evaluated by measuring the
coefficients of variation (CV) expressed as percentages. TXRF
CVs vary from 0.8% for Ti to 27% for Hf, whereas in the
analysis by INAA CVs vary from 2% for Mn to 106% for Sr.
These analytical aspects do not imply that TXRF is a more
powerful tool than INAA, but that TXRF may offer both
precision and accuracy comparable with and, in some cases,
better than INAA.
It is important to note the disagreement between the INAA
and TXRF values for the elements As, Sr and Zn. For these Fig. 5. Sample angle scans versus integrated areas for Fe, Ti, Rb, K (circles) and
elements, TXRF presents a high sensitivity and they are Sr, Zn and As (triangles). Continuous lines are B-Spline interpolation.
 Author's personal copy
1128 R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129
Fig. 6. (a) Plot of the first two principal components scores derived from analysis
of the 24 pottery EP samples plus results of the 2 standards. ST-1 INAA results
and ST-2 TXRF results for Set-QH. (b) Weight of the 17 variables taken into
account.
pottery ensemble provided by some archaeological excavations,
as a possible indicator of different sources or production units.
In this archaeological case, a study carried out by TXRF on
ceramic materials from the Celtiberian archaeological site of El
Palomar (Aragoncillo, Guadalajara, Spain) is briefly illustrated.
The settlement is located in the Upper Jalón Valley, adjacent to
the Upper Duero Valley in the north-eastern part of the Spanish
Central Meseta. A total of 24 representative samples from the
different percentages of each fabric or type of ceramic
manufacture present in the settlement were analyzed (EP-1 to
EP-4 Fabric 1; EP-5 to EP-8 and EP-13 to EP-21 Fabric 2; EP-
22 to EP-24 Fabric 3; EP-9 to EP-12 Fabric 4). Analyses were
carried out by TXRF according to the solid chemical
homogenization procedure mentioned above for Set-QH. Two
statistical procedures were used in the exploration of data:
cluster analysis and principal components analysis. Both were
carried out on log-transformed data on the concentrations of 18
elements determined, excluding Fe, in order to balance the
difference of magnitude between the major and trace elements
[16]. We also introduced the values of the standard in the
statistical analysis, either those obtained by INAA or by TXRF
(Set-QH). We used such values in order to check the capability
of TXRF to discriminate groups of different composition.
2.4.1. Results and discussion
The cluster analysis employed the average linkage of the
mean Euclidean distances matrix. The resulting dendrogram
suggests that the data set had two parts, one of them constituted
by standard measurements, and the other constituted by the 24
samples analyzed. Within the latter, it may be observed that
samples are separated into two sub-groups. There are sherds
from Fabrics 2, 3 and 4 in both sub-groups, whereas only in the
first one sherds appear to belong to Fabric 1. Further clarity was
introduced as a result of the use of principal components
analysis. The three first components summarized 71.89% of the
total variation in the data. In Fig. 6a, the plot represents sample
scores with respect to the two first components. Three distinct
groups can be observed. All samples belonging to Fabric 1
appear on the left. The rest of the fabrics appear at the center.
The two standards plot on the upper part of the diagram.
Correlations between the variables responsible for these
associations may be seen in Fig. 6b. The first component
summarized 45.29% of the total variation. Four elements were
positively correlated with this one: Ba, V, Hf and Mn, whereas
Al, Ti, Rb and Cr had a negative correlation. The second
component summarized 18.48% of the total variation. Cu, Ni,
Rb and Cr had a positive correlation and Zn, Sr, K and Ga had a
negative correlation. Finally, the third component (not repre-
sented in the figures) had Y, Ni, Cr and Cu correlated in a
positive way, whereas Ca, As and K had a negative correlation.
Therefore, the discrimination of fabric 1 was related to the first
component (Fig. 6a).
To summarize, the statistical analysis showed two distinct
associations. One group was constituted by fabric 1, and one
group was formed by the remainder of the fabrics. The
compositional variability observed seems to reflect a high
homogeneity in the sherds analyzed, which might indicate a
local provenance. The presence of two associations in the data
set may be related either to the exploitation of two different
sources of raw materials or to the presence of different
production units. The percentages of fabric 1 in the total pottery
ensemble, as well as typological forms associated to this fabric,
do not suggest a foreign origin for this type of manufacture.
Therefore, the local character of these productions is suggested
in a preliminary way. This indicates that this pottery could have
been manufactured in the geographical area where El Palomar is
located. However, it is not possible to establish that pottery was
elaborated in the archaeological site itself, particularly in view
of the absence of remains related to pottery production. Finally,
it is evident that the inclusion of analytical data for the standard
Ohio Red Clay-2 (ST-1, INAA results and ST-2, TXRF results)
has revealed the ability of the TXRF technique to detect
compositionally different groups.
3. Conclusions
The method of sedimentation can be rejected to analyze this
kind of material by TXRF for archaeological applications.
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R. Fernández-Ruiz, M. García-Heras / Spectrochimica Acta Part B 62 (2007) 1123–1129
However, the TXRF procedure developed could be a fruitful
avenue to evaluate the chemical composition speciation of a
generic solid, based on its size and it could have interest in
environmental pollution studies.
A reliable sample preparation process is needed for
application of TXRF to the analysis of archaeological ceramic
materials and the chemical homogenization approach complies
with this requisite. This procedure implies that the ceramic
sample has chemical homogeneity, average particle size around
1 μm and lower than 10 μm, and a chemically homogeneous
distribution of its particles. The final procedure can be
summarized as follows: homogenization of the samples by a
high grinding process, suspension of the fine-ground mixture of
the whole sample in high-purity water, ultrasonic disaggrega-
tion of such suspension, and deposition with continuous
agitation of an aliquot of that suspension on a flat carrier. The
more important aspects are the following: the chemical
homogenization procedure has proved to be quick, relatively
easy, and inexpensive and, in addition, does not require any
chemical manipulation.
The analysis was performed for 18 elements: Al, Ca, K, Ti,
Fe (majors); Mn, Zn, Sr, Rb, Cr (minors) and As, Hf, Ni, Ba, V,
Cu, Ga and Y (traces). The results obtained show a high
accuracy for Cr, Hf, Rb, Ni, Al, Ba, Ca, K, Mn, Ti, Fe and V.
The recoveries (accuracy) obtained vary from 91% for Hf to
110% for V. The precisions obtained vary from 0.8% for Ti to
27% for Hf, whereas in the analysis by INAA they vary from
2% for Al to 106% for Sr.
TXRF results for the elements As, Sr and Zn presented an
unexpected inaccuracy with respect to INAA values. These
unexpected values were studied more deeply by means of angle-
scan measurements and an anomalous behavior was found.
Such behavior has been associated to the presence of particle
sizes between 20 and 50 nm corresponding to mineral phases
associated to As, Sr and Zn and therefore, the associated
interference effects explain and justify the differences observed
between TXRF and INAA values.
The archaeological case-study shows that TXRF is a useful
technique for the determination of the compositional attributes
of ceramics. The comparison of these results with data
previously obtained from the clay reference material clearly
shows the ability of the technique to distinguish groups of
different compositional nature. On the other hand, TXRF has
provided analytical values comparable to those provided by
INAA for 15 elements. Three additional elements (Cu, Ga and
Y) present in the Ohio Red Clay-2 standard were determined by
TXRF, even though they were not analyzed by INAA.
At the current stage of our research, TXRF provides semi-
quantitative results. This fact is not a serious drawback for
archaeological applications as the archaeological case-study
demonstrates. In any case, we are currently working in the
development of new TXRF strategies which will be certainly able
to quantitatively analyze this kind of materials in the next future.
1129
Acknowledgements
The authors wish to express their gratitude to Dr. Hector Neff
and Dr. Michael D. Glascock (Archaeometry Laboratory at the
Missouri University Research Reactor Center) for giving them
permission to use a Ohio Red Clay-2 standard as well as data of
their measurements by neutron activation.
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