Spectrochimica Acta Part B 59 (2004) 1877 – 1884

www.elsevier.com/locate/sab

Comparison of a portable micro-X-ray fluorescence spectrometry with

inductively coupled plasma atomic emission spectrometry for the ancient
ceramics analysis
D.N. Papadopouloua, G.A. Zachariadisa, A.N. Anthemidisa, N.C. Tsirliganisb, J.A. Stratisa,*
a
Laboratory of Analytical Chemistry, Faculty of Chemistry, Aristotle University, GR-54124, Thessaloniki, Greece
b
Archaeometry Laboratory, Cultural and Educational Technology Institute, Tsimiski 58, GR-67100, Xanthi, Greece

Received 10 February 2004; accepted 24 August 2004

Available online 12 October 2004

Abstract

Two multielement instrumental methods of analysis, micro X-ray fluorescence spectrometry (micro-XRF) and inductively coupled plasma
atomic emission spectrometry (ICP-AES) were applied for the analysis of 7th and 5th century B.C. ancient ceramic sherds in order to
evaluate the above two methods and to assess the potential to use the current compact and portable micro-XRF instrument for the in situ
analysis of ancient ceramics. The distinguishing factor of interest is that micro-XRF spectrometry offers the possibility of a nondestructive
analysis, an aspect of primary importance in the compositional analysis of cultural objects. Micro-XRF measurements were performed firstly
directly on the ceramic sherds with no special pretreatment apart from surface cleaning (micro-XRF on sherds) and secondly on pressed pellet
disks which were prepared for each ceramic sherd (micro-XRF on pellet). For the ICP-AES determination of elements, test solutions were
prepared by the application of a microwave-assisted decomposition procedure in closed high-pressure PFA vessels. Also, the standard
reference material SARM 69 was used for the efficiency calibration of the micro-XRF instrument and was analysed by both methods. In
order to verify the calibration, the standard reference materials NCS DC 73332 and SRM620 as well as the reference materials AWI-1 and
PRI-1 were analysed by micro-XRF. Elemental concentrations determined by the three analytical procedures (ICP-AES, micro-XRF on
sherds and micro-XRF on pellets) were statistically treated by correlation analysis and Student’s t-test (at the 95% confidence level).
D 2004 Elsevier B.V. All rights reserved.

Keywords: Ancient ceramics; Micro-XRF; Inductively coupled plasma; Multielement methods

1. Introduction lytical characteristics such as high precision, sensitivity and

The study of cultural objects, such as ancient ceramics,
involves the application of a wide range of instrumental
methods of analysis which enable the extraction of objective
information. Such scientific information, in conjunction with
the archaeological information, offers an integrated scientific
methodology that may be effectively used in provenance or
characterization studies of archaeological materials [1,2].
Inductively coupled plasma atomic emission spectrome-
try (ICP-AES) is often used for the multielement analysis of
ancient ceramics because it presents some excellent ana-
* Corresponding author. Tel.: +30 2310997843; fax: +30 2310997719.
E-mail address: jstratis@chem.auth.gr (J.A. Stratis).
0584-8547/$ - see front matter D 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.sab.2004.09.001
selectivity [3–5]. However, in the ICP-AES analysis, the
samples should be in an aliquot form thus a part of the
original ceramic sample is permanently destroyed by the
application of a digestion method. X-ray fluorescence
(XRF), on the other hand, is a multielement, sensitive and
nondestructive method that is commonly used for the
analysis of archaeological materials [6–8]. In addition, the
development of portable energy-dispersive X-ray spectro-
meters has received considerable scientific attention. Several
spectrometers have been constructed and numerous applica-
tions have been reported many among them concerning
archaeological materials [9]. The emphasis that was given to
the development of these systems was based on the expec-
tations that portable X-ray spectrometers would create new
1878 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884

fields of application and contribute significantly to the The aim of the present work was to investigate and
progress of provenance studies [9]. evaluate the ability of the employed portable micro-XRF
More recently, microscopic analytical methods (micro- instrument for the in situ multielement and quantitative (Si,
X-ray fluorescence spectrometry, electron probe micro- Fe, Ca, K, Mn, Ti) analysis of ancient ceramic samples. The
analysis and secondary ion spectroscopy) have rapidly been obtained results were compared with those from ICP-AES
developed. These methods offer new abilities in the material analysis after microwave-assisted digestions. The mean
analysis and are more frequently included in archaeometric elemental concentrations were compared by correlation
studies [10,11]. analysis and Student’s t-test. In addition, the standard
Micro-XRF is the microscopic equivalent of bulk XRF reference material (SARM 69) was used for the efficiency
and it is a suitable analytical method for the analysis of calibration of the micro-XRF instrument and was analysed
cultural objects because, apart from its nondestructive by both methods. In order to verify the calibration of the
character, micro-XRF is a fast, accurate, sensitive, universal, micro-XRF, the reference materials NCS DC 73332,
versatile and multielement analytical method [1,10–13]. Its SRM620, AWI-1 and PRI-1 were analysed.
principal advantages are the minimization of sample
preparation, the ability to operate in air and to perform a
localised nondestructive analysis of microscopic areas over 2. Experimental
the surface of large objects [11,14].
Various forms of micro-XRF may be used depending on 2.1. Instrumentation and operational conditions
the scientific questions of each investigation. Synchrotron
micro-XRF has the advantage of offering intense radiation; The XRF spectrometer used in this work is a portable and
it is often used in XRF microprobe analysis of ancient compact micro-XRF unit based on the prototype model that
ceramics, but it requires big and expensive facilities [15,16]. was developed under the EU project bCOPRAQ (Compact
On the other hand, laboratory micro-XRF instruments can Portable Roentgen Analyser Project), with the difference
operate with either X-ray tubes or radioisotopic sources. The that the X-ray optics include a straight monocapillary lens
most recent development in the micro-XRF technique is the instead of a polycapillary one. Straight monocapillaries act
construction of small, compact and portable micro-XRF as wave-guides and X-rays are transported without the 1/r 2
instruments in contrast with the bench-top instruments [17]. losses that normally occurs in a collimator. The instrument
These portable instruments are expected to contribute, to a consists of a side-window X-ray tube with Mo anode (Series
large extent, to the analysis of archaeological findings 5011 XTF, Oxford Instruments) and maximum voltage/
because they offer the advantage of their in situ analysis in current of 50 kV/1 mA. The nominal beam diameter is b150
places where the artefacts are normally located (museums, Am at the position of the sample. The micro-XRF
galleries and archaeological sites). spectrometer and the experimental setup are shown in Figs.
The construction of small and portable micro-XRF 1 and 2, respectively. The samples (either in sherd or pellet
instruments involves a critical selection of the appropriate
components such as X-ray sources, focusing optics and
detectors [18]. In their primary form, microbeams were
produced by a collimator system. However, after the most
recent developments in the field of capillary optics,
polycapillary and monocapillary lenses have become an
essential part of the micro-XRF instrumentation [19–21].
Ancient ceramics are the most common archaeological
findings and they carry a significant historical content. A
large variety of analytical methods can be applied for their
analysis and comparative results between different analy-
tical methods are often reported in the scientific literature
[22,23].
Micro-XRF instruments with a compact and portable
construction have been used for the analysis of historical
metallic objects, multicolored items, industrial materials,
forensic glasses, gold artifacts, bronze statuettes and paint
layers [17,19,24,25]. However, no applications have still
been reported on ancient ceramics by a similar instrument
with monocapillary optics. In addition, micro-XRF has not
been fully characterized in comparison with more traditional
instrumental methods, such as ICP-AES, for the analysis of
ancient ceramics. Fig. 1. Micro-XRF spectrometry system.
 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884 1879

Table 1
Micro-XRF spectrometer operating conditions
Tube conditions 35 kV, 0.9 mA
Tube Mo mini-focus
Real time acquisition 300 s
Beam diameter (at sample position) b150 Am
X-ray optics Monocapillary
Detector Si(Li), Peltier cooled

count rate is sufficiently high, at around 30–35 kV, so as any

Fig. 2. Schematic diagram of the experimental micro-XRF geometry.
form) are placed on a rotating holder mounted on a
computer-controlled XYZ-motorized stage which can move
in steps of 0.1 mm and have a maximum travel distance of 5
cm in the X, Y direction and 2.5 cm in the Z direction. The
angle of incidence of the primary X-ray beam on the sample
surface is 488 (relative to the surface). Thus, the geometry
can be accurately reproduced in each measurement. A solid
state Si(Li) Peltier-cooled detector (8 Am Be window, 3.5
mm2 active area, 300 Am nominal thickness and resolution
of 149–166 eV at the Mn K a energy) is used for the
detection of the secondary fluorescence X-rays positioned at
908 relative to the primary beam. The relative angle between
the X-ray tube and the detector is fixed by the manufacturer
and cannot be altered (except by using specific setup
procedures). A long-distance optical microscope is placed
on the detector and X-ray tube plane and is used in order to
locate the focal spot on the sample surface.
All micro-XRF measurements were performed in a point
scan mode on several points which were selected so as to
cover the whole surface of the sample (in either sherd or
pellet form). In particular, 10 measurements were performed
per each sample (average dimension of sherds was 22 cm2
and the diameter of pellets was 30 mm). Reported
concentrations are mean values of the 10 measurements
per sample. The elements of interest were identified by their
characteristic X-ray lines in the energy range of 0–25 keV.
The operating conditions during the micro-XRF measure-
ments are summarised in Table 1.
The current and voltage values were chosen based on the
results of a preliminary investigation concerning the effect
of voltage value on the intensity of the characteristic peak
further increase in the voltage was not regarded as essential.
Finally, the required increase in the acquisition time, in
order to improve the low-intensity characteristic X-ray lines
of trace elements (such as Ni, Zn, Cu, etc.) is not reasonable.
Thus, the acquisition time was kept in the present value and
their quantification was omitted.
A Perkin-Elmer Optima 3100XL Series spectrometer
was used for the ICP-AES analysis. The elements deter-
mined by ICP-AES were detected in two different emission
lines. Based on the precision and sensitivity observed in
each emission line, the following were chosen: Si at 251.611
nm, Fe at 238.204 nm, Ca at 317.933 nm, Ti at 336.121 nm
and Mn at 259.372 nm. Potassium was determined by FAES
because, in the available ICP instrument, the polychromator
range was 165–403 nm. The operating conditions of the
ICP-AES spectrometer are described in Table 2.
The microwave-assisted digestions were performed in a
MARS 5 microwave oven (CEM, USA, 1200 W). The
device is equipped with a Teflon-coated cavity and a
removable 12-position sample carousel. The samples were
digested in high-pressure closed Teflon PFA vessels (HP-
500 Plus type, maximum temperature=483 K, maximum
pressure=2.4 MPa, volume=100 ml) which are placed in
high-strength outer sleeve assemblies. The microwave
power output is managed through direct feedback from
temperature (EST-300 Plus probe) and pressure (ESP-1500
Plus) probes, providing precise control of the chemical
reactions. The vessels are equipped with special caps
(Autovent Covers) that are used for the secure release of
the excess pressure.
Table 2
Operating conditions of Perkin Elmer Optima 3100 XL ICP-AES
instrument
RF generator 40 MHz, free-running
RF incident power Optimized
Sample uptake rate 1 ml min 1
Argon flow rates Auxiliary 0.5 l min 1;
nebulizer 0.8 l min 1; plasma 15 l min 1

areas. For the six elements that were determined in the Air flow rate (shear gas)
present study, we found that the characteristic peak area Viewing mode
values approach an upper limit value (cps) around a voltage Torch, injector, id
Nebulizer
of 30 kV and any further increase in voltage does not Sample propulsion
influence the intensity of the characteristic X-ray lines Sample flow rate
significantly. Although for elements such as Mn and Fe, we Spray chamber
noticed a further increase in the characteristic peak areas Polychromator/resolution
after a respective increase in the voltage value, the recorded Detector
18 l min 1
Axial
Fassel type, Alumina, 2.0 mm
Gem tip cross flow
Peristaltic pump, three channel
Optimised
Scott double pass
Echelle/0.006 nm at 200 nm
Segmented-array charge-coupled (SCD)
1880 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884
2.2. Samples and reference materials
Six ceramic sherds (A2, A4, A14, A17, A25 and A35)
from the excavation in the ancient cemetery of Abdera
(North Greece) were used. Samples A2, A4, A25 and A35
date back to 7th century B.C. and samples A14 and A17
date back to the 5th century B.C. None of the sherds
presented decoration over its surface. Samples were dried
overnight at 105 8C prior to the analysis.
The standard reference material SARM 69 (prepared and
distributed by MINTEK South Africa and the Department
of Geology, University of Free State) was used as a
calibration standard in the micro-XRF and was analysed
by both micro-XRF and ICP-AES. Moreover, the synthetic
silicate standard reference material, NCS DC 73332 (China
National Analysis Center for Iron and Steel), the SRM620
(NIST, Soda Lime Flat Glass) and the reference materials
AWI-1 and PRI-1 (both from Group of Instrumental
Geochemistry, Fonds National de la Recherche Scientifi-
que/Nationaal Fonds voor Wetenschappelijk, FNRS-
NFWO) were analysed by micro-XRF in order to verify
the calibration.
2.3. Sample preparation
The micro-XRF measurements were performed directly
on the ancient ceramic sherds and on pressed pellets. In the
first case, the only preparation step followed was the
removal of the external layer with a drill and a tungsten
carbide cutter in order to eliminate the possible surface
contamination effects. The sample surface was not po-
lished. This was not considered necessary since in micro-
XRF the beam size is in the order of microns (Am).
Moreover, although this treatment partially revokes the
nondestructive character of the micro-XRF analysis, it was
followed at the present work for comparison reasons. In the
second case, subsamples were cut-off from the ceramic
samples and they were finely powdered in an agate mortar.
The powdered ceramic samples were then sieved and the
fraction with an average grain size b93 Am was isolated.
Pressed pellets were finally prepared by thoroughly mixing
this fraction of the powdered ceramic samples with a
cellulose binder in a 4:1 (sample/binder) ratio and pressing
was performed using a 11-ton hydraulic press. The grain
size fraction of b93 Am was selected to match the grain size
of the calibration standard. In the calibration and quanti-
fication procedure of a micro-XRF spectrometer, it is
important that the analyzed standards and samples have
similar grain size distributions. All standard reference
materials were prepared in pressed pellets by a similar
procedure as the ceramic samples.
For the ICP-AES analysis, subsamples were cut off from
the initial sherds and were then finely powdered in an agate
mortar. Decomposition of the silicate matrix was performed
in a microwave oven in closed pressurized vessels. In
particular, 0.1 g of each powdered sample was placed in a
Teflon PFA digestion vessel and a mixture of 5 ml HF 40%
m/m and 5 ml HNO3 69.5% m/m was added. The exact
decomposition procedure followed has been described
previously [26]. The standard reference material SARM69
was analysed in a similar way. Multielement, matrix-
matched standards were used for the quantitative determi-
nations (in 0.5 mol l 1 in HNO3).
3. Results and discussion
3.1. Micro-XRF calibration and spectra evaluation
The evaluation of micro-XRF spectra in order to extract
quantitative results involves taking into account a number
of factors each possessing an impact on the final result
[1,27,28]. Heterogeneity of the different particle sizes and
elemental distributions of the samples can influence
significantly the final results in the micro-XRF analysis.
In practice, micro-X-ray spectra that are acquired from
several points on the surface of a ceramic sherd can
present qualitative (different peaks) and quantitative
(different intensity) differences. On the contrary, when X-
ray spectra are acquired from several points on the surface
of a pellet, the spectra are always qualitatively and
quantitatively similar (Figs. 3 and 4, respectively). The
acquired spectra in the current measurements include also
the Compton and Rayleigh scattering lines of Mo as well
as the K a line of Zr, which is a component element of the
detector collimator.
The calibration procedure in the micro-XRF spectrome-
try, for the quantitative analysis of ceramics is a complicated
procedure since a number of parameters such as surface
irregularities, crystal structure, grain size, geometry and
absorption of the X-rays, influence the final result [1,20,29].
Moreover, there is a lack of ceramic SRMs specifically for
micro-XRF analysis. After each measurement, the spectra
were deconvoluted by a dedicated software (WinAxil
software package v 4.0.1.) in order to determine the
fluorescence intensities of chemical elements [30,31]. These
intensity data were then quantified automatically by a
fundamental parameter correction procedure. In particular,
spectral data are processed by the method of least squares
fitting, where the optimum values of x 2 (the weighted sum
of squares of the differences between a chosen model and
the measured spectrum) are found iteratively (Marquardt
algorithm). A suitable background estimation model was
also chosen (smooth filter). This is an important step in the
quantitative evaluation of samples since several fitting
procedures may be applied [32–34]. Smooth filter model
compares the content y i of a channel i with the mean m i of
the two neighboring channels (channels i 1 and i+1,
respectively). If the value m i is smaller than the channel
content y i , the content of channel i is replaced by the mean
m i . Repetition of this process for the whole spectrum
gradually causes the peak to be stripped away. The used
 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884 1881

Fig. 3. Micro-XRF spectrum acquired from two different points (a and b) on the surface of sample A2 in the form of sherd.

software allows the calibration of the system by the
fundamental parameters method with a single standard and
the quantitative analysis of samples in a compare mode
where it is assumed that the calibration standard and
samples have similar matrix compositions. The type of the
X-ray tube excitation is calculated and stored by the
software, after relevant data (type of tube window, measure-
ment conditions) are entered.
The obtained precision of micro-XRF analysis was high
for all six elements (in terms of relative standard deviation,
RSD%) and it ranged between 0.15% and 1.04%. The
precision was determined by taking several measurements
on different points (12 points) over the calibration standard
and by repeating the measurements several times in each
point (10 repetitions in each point). All spectra were then
fitted and precision was determined by calculating weighted
average peak areas and the respective weighted standard
deviation for each element.
In order to verify the overall quality of the calibration and
to compare micro-XRF with an already accepted method,
the calibration standard was reevaluated as a sample using
the obtained calibration parameters. The reevaluated con-
centration values together with the certified values and
obtained values by ICP-AES analysis are given in Table 3.
Mean elemental concentrations determined by micro-XRF
present a slight positive deviation. Light elements like Na
and Al cannot be analysed by the available micro-XRF
system. It is important to notice, that laboratory built A-XRF
instruments are most often used for the analysis of low to
medium atomic number elements (Si–Cu), while heavier
elements that are present in low concentrations are not often
investigated [1,29]. Although a higher number of elements
were determined for the SARM69 by the ICP-AES, we
report only the concentrations of six analytes in Table 3 for
comparison purposes.
For the verification of the micro-XRF calibration, a
synthetic silicate (NCS DC 73332) and two sedimentary
rock reference materials (AWI-1 and PRI-1) were ana-
lysed. In addition, micro-XRF was applied for the analysis
of SRM620. Although this is a glass standard reference
material, it is important to observe the performance of the
present micro-XRF spectrometer for the analysis of
another silicate matrix. The results of the above analyses
are given in Table 4. The relative errors of the micro-XRF
mean values range between 0% and 10% for the majority
of cases.

Fig. 4. Micro-XRF spectrum acquired from two different points (a and b) on the surface of sample A2 in the form of pellet.
1882 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884

Table 3
Comparison among micro-XRF, ICP-AES and certified values for the standard reference material SARM 69 (concentrations in %m/mFS.D.)
SiO2 K2 O CaO TiO2 MnO Fe2O3
micro-XRF 69.1F0.8 2.20F0.01 2.33F0.03 0.889F0.039 0.149F0.001 8.36F0.06
ICP-AES 67.3F3.6 2.00F0.03 2.38F0.02 0.699F0.011 0.119F0.002 6.35F0.21
Certified 66.6F0.5 1.96F0.04 2.37F0.04 0.777F0.008 0.129F0.002 7.18F0.075

3.2. Analysis of ancient ceramic sherds
Results from the quantitative analysis (in %m/m oxide
concentrationFS.D.) of the six ancient ceramic sherds
determined by the three analytical procedures, that is,
ICP-AES after microwave-assisted digestion, micro-XRF
applied directly on the ceramic sherds (micro-XRF-s) and
micro-XRF applied on pressed pellets (micro-XRF-p), are
presented on Table 5. Precision of micro-XRF analysis for
the six different samples (in terms of relative standard
deviation, RSD%), ranged between 1.1% and 5.6% for Si,
between 2.9% and 4.7% for Fe, between 1.1% and 5.8% for
Ca, between 0.8% and 3.9% for Ti, between 0.1% and 4.2%
for K and between 0.2% and 5.8% for Mn. For the ICP-AES
analysis, precision ranged between 1.2% and 5.6% for Si,
between 2.9% and 4.7% for Fe, between 1% and 5.8% for
Ca, between 0.8% and 3.9% for Ti, between 0.2% and 4.2%
for K and between 0.2% and 5.8% for Mn.
The mean oxide concentrations were subjected to linear
correlation analysis, and linear correlation coefficients for
each element oxide were calculated in each one of the three
comparison pairs: ICP-AES vs. micro-XRF-s, ICP-AES vs.
micro-XRF-p and micro-XRF-s vs. micro-XRF-p. For the
first two comparison pairs, it was found that correlation
coefficients are low for the majority of elements. Notable
exceptions were noticed for SiO2 and K2O (correlation
coefficients 0.76 and 0.84 respectively). In addition, for
CaO, TiO2 and K2O in the pair micro-XRF-s vs micro-XRF-
p, strong correlation was noticed (correlation coefficients
0.97, 0.99 and 0.81 respectively), while for Fe2O3 in the
same pair, a moderate correlation was noticed (correlation
coefficient 0.71).
In overall, elemental concentrations that were determined
by micro-XRF both on ceramic sherds and on pressed
pellets correlate strongly for three out of the six elements
(CaO, TiO2 and K2O) and moderately for one element
(Fe2O3). Only for Mn, the correlation coefficients were very
low for all comparison pairs. This differentiation can be
attributed to spectral interferences that exist in the micro-
XRF analysis. In particular, the K b1 X-ray line of Mn at
6.490 keV may interfere with the K a1 and K a2 lines of Fe at
6.403 and 6.390 keV, respectively [32]. The interference is
affecting primarily Mn while for Fe the effects are limited
due to its significantly higher concentration (1:100 ratio in
the particular samples).
For the same comparison pairs, mean oxide concen-
trations for each ceramic sample, were treated with a
Student’s t-test, at the 95% confidence level. In the
majority of cases, the mean oxide concentrations from the
three different analytical procedures differed significantly
for all comparison pairs (that is ICP-AES vs. micro-XRF-s,
ICP-AES vs. micro-XRF-p and micro-XRF-s vs micro-
XRF-p). Only for samples A2, A4 and A17, the concen-
tration of TiO2 as it was determined by micro-XRF-s and
micro-XRF-p presented statistically not significant diffe-
rences. Moreover, for the same comparison pair and for

Table 4
Comparison between micro-XRF, certified and recommended values for the reference materials NCS DC 73332, SRM620, AW-I and PR-I (concentrations in
%m/mFS.D.)
SiO2 K2O CaO TiO2 MnO Fe2O3
SRM620
Micro-XRF 78.30F0.36 0.35F0.00 5.96F0.09
Certifieda 72.08F0.08 0.41F0.03 7.11F0.05

NCS DC 73332
Micro-XRF 67.20F0.90 1.05F0.01 1.11F0.04 0.120F0.005 0.088F0.002 3.89F0.02
Certifiedb (72) (1.35) (1.80) 0.100F0.003 0.100F0.002 (4.0)

AW-I
Micro-XRF 59.45F0.90 3.06F0.04 0.73F0.07 0.95F0.03 0.16F0.00 7.93F0.06
Recommended 60.46F0.55 3.06F0.09 0.69F0.07 0.92F0.05 0.14F0.01 7.21F0.17

PR-I
Micro-XRF 64.50F0.98 3.40F0.04 2.70F0.07 0.67F0.02 0.06F0.00 3.32F0.02
Recommended 68.60F0.35 3.79F0.21 2.49F0.16 0.71F0.03 0.04F0.01 3.32F0.13
a
SRM620 is not certified for MnO oxide concentration. The certified concentrations for TiO2 and Fe2O3 oxide are low (0.018% and 0.043%, respectively)
and were not quantified by the current micro-XRF measurement conditions.
b
Values in parenthesis are recommended values.
 D.N. Papadopoulou et al. / Spectrochimica Acta Part B 59 (2004) 1877–1884 1883

Table 5
Comparative results of the chemical composition of ancient ceramic sherds from ancient Abdera (%m/mFS.D.)
Sample Method SiO2 Fe2O3 CaO MnO TiO2 K2Oa
A4 ICP-AES 51.35F2.89 3.49F0.11 2.11F0.12 0.031F0.002 0.646F0.005 0.27F0.00
micro-XRF-s 39.91F0.45 6.04F0.03 3.84F0.10 0.070F0.002 0.609F0.013 0.83F0.01
micro-XRF-p 41.11F0.45 6.66F0.03 3.39F0.07 0.095F0.002 0.604F0.013 1.04F0.01
A25 ICP-AES 54.01F0.62 3.69F0.13 1.04F0.01 0.025F0.001 0.490F0.007 1.62F0.07
micro-XRF-s 60.46F0.61 5.25F0.03 1.42F0.04 0.068F0.002 0.573F0.015 2.03F0.03
micro-XRF-p 41.81F0.47 5.65F0.03 1.61F0.04 0.085F0.002 0.598F0.014 1.73F0.01
A17 ICP-AES 56.74F0.81 4.52F0.15 0.37F0.06 0.026F0.000 0.594F0.008 1.17F0.02
micro-XRF-s 54.40F0.75 5.77F0.04 2.35F0.08 0.089F0.003 0.553F0.016 1.68F0.02
micro-XRF-p 43.34F0.54 6.27F0.03 1.99F0.04 0.094F0.002 0.565F0.010 1.51F0.01
A35 ICP-AES 52.00F1.37 5.26F0.25 1.68F0.08 0.047F0.001 0.720F0.023 1.56F0.01
micro-XRF-s 48.56F0.79 6.80F0.05 1.25F0.05 0.080F0.003 1.000F0.030 2.05F0.02
micro-XRF-p 39.40F0.49 7.05F0.04 1.48F0.03 0.098F0.002 0.824F0.020 1.80F0.01
A2 ICP-AES 49.91F2.50 4.80F0.17 3.63F0.11 0.036F0.001 0.598F0.006 1.06F0.00
micro-XRF-s 38.25F0.53 4.70F0.03 3.04F0.09 0.049F0.001 0.532F0.014 0.81F0.01
micro-XRF-p 40.01F0.52 6.26F0.04 3.13F0.08 0.186F0.004 0.535F0.013 1.03F0.01
A14 ICP-AES 53.96F0.66 4.97F0.14 2.05F0.06 0.032F0.001 0.636F0.025 1.80F0.04
micro-XRF-s 46.85F0.52 5.74F0.03 2.70F0.12 0.076F0.002 0.525F0.012 3.13F0.02
micro-XRF-p 41.06F0.48 5.96F0.03 2.60F0.06 0.080F0.001 0.535F0.009 1.64F0.01
a
Determined by FAES.

sample A14 mean concentrations of CaO presented statisti-
cally not significant differences. Finally, Fe2O3 mean
concentration did not differ significantly between ICP-
AES and micro-XRF on pellets for sample A2. These
differences are justified by the fact that in ICP-AES the
bulk volume of the sample is used in the sample
preparation procedure, while, in micro-XRF applied on
pellets, the grain size was restricted to a certain fraction,
and, in micro-XRF applied directly on sherds, the external
layer is analyzed and heterogeneity greatly affects the final
analytical result.
4. Conclusions
A good agreement was observed between elemental
mean values that were determined by the current micro-XRF
instrument and certified or recommended values, for five
reference materials (SARM69, NCS DC 73332, SRM620,
AW-I and PR-I). Multielement and nondestructive analysis
constitutes an objective of increasing interest in the
archaeometry research field. Six different ceramic samples
from ancient Abdera, Northern Greece were analysed by
micro-XRF spectrometry (both as sherds and as pressed
pellets) and also by ICP-AES. Elemental mean concen-
trations show statistically significant differences (95% CL)
when comparisons are performed among the different
analytical procedures used. These differences could be
attributed to the different parameters that affect the
analytical results in each procedure. The choice between a
destructive (ICP-AES) or a non-destructive (micro-XRF)
method of analysis depends on the specific demands of each
investigation. Most importantly, sample preparation plays a
crucial role not only between different analytical methods,
(ICP-AES or micro-XRF), where the sample may be
analysed in the form of aliquot or solid but also in the
same analytical method (micro-XRF) where the sample may
be analysed in pellet form or as an untreated sherd.
Nevertheless, a strong correlation was noticed between the
mean elemental concentration obtained by micro-XRF
analysis applied on sherds and by micro-XRF applied on
pellets for three out of six elements and a moderate
correlation for one element. Micro-XRF applied directly
on ancient ceramics is beneficial with respect to time of
analysis and is nondestructive. However, heterogeneity
problems that affect the quantification procedure are more
prominent in this case. Consequently, the portable micro-
XRF spectrometer employed is a promising tool that may be
used for a quick screening analysis of ancient sherds,
without the need for time-consuming sample preparation
procedures.
Acknowledgments
The current project is part of Mrs D.N. Papadopoulou
PhD thesis. It was funded by the Greek General Secretariat
of Research and Technology and the EU, in terms of the
programme PENED 2001 (project 01ED240). The authors
wish to express their gratitude to Mrs K. Kallintzi, director
of the excavation in the cemetery of ancient Abdera, and
Mrs M. Chrisafi, archaeologist, for their assistance in the
sampling of the ancient ceramic sherds.
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