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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.
[8], Cariati et al. [9] or Fernández-Ruiz et al. [10–12], were the foil, adjusting the intensity so that a count rate of about 5000 cps
departure point for this investigation. The best approach to the was achieved and an acquisition time of 1000 s. TXRF 8030C
ideal TXRF thin film criteria for a solid particle deposition is that spectrometer (Cameca, France) was also used with the objective
the following three fundamental requirements are fulfilled: (1) of undertaking studies of angular dependence of signal intensity
chemical homogeneity of the solid particles, (2) average particle for some elements. This spectrometer combines a 3 kW X-ray
sizes around 1 μm and lower than 10 μm [13], and (3) tube with a Mo/W alloy anode with a W/C double-multilayer
homogeneous spatial distribution of the deposited particles on monochromator and in addition allows the variation of the
the sample carrier. incidence angle by tilting the sample holder unit.
To provide the TXRF validation for this type of studies, a The QELS system used in this study was the AutoSizer IIc of
reference clay material analyzed routinely by INAA was Malvern Instruments Ltd., equipped with a He–Ne 5 mW laser,
employed as reference material, Ohio Red Clay from Resco a photo-multiplier and a processing electronic system controlled
Products, Inc, Oak Hill, OH, USA (Ohio Red Clay-2 hereafter). by the Malvern AutoSizer computer package. The SEM
This sample was habitually used as batch control by the team of equipment used was the Philips XL-30 equipped with a W
the University of Missouri-Columbia in their INAA analyses source, detectors of secondary and backscattering electrons and
[14]. This work presents the results obtained in the comparison a vacuum working lower than 4 × 10− 4 Pa.
of both techniques (INAA and TXRF) for the Ohio Red Clay-2
reference sample and also, the investigations carried out for the 2.2. Procedure of sedimentation
samples preparation and optimization for TXRF analysis. The
application of the final TXRF procedure developed was applied 2.2.1. Samples preparation
for evaluating a real archaeological case. Keeping in mind the three main requirements mentioned in
the Introduction section, and as a first approach to the problem,
2. Experimental section it is possible to obtain different clay size fractions by the
sedimentation method. Three sets of samples (5 samples each)
2.1. Instrumentation were prepared from the Ohio Red Clay-2 reference sample.
First, the sample was ground for 30 min in an agate mortar.
Three main techniques have been used in this work. TXRF Then 100 mg of the ground sample was poured into a test-tube
for the analysis of the samples; quasi-elastic light scattering and mixed with high-purity water (Milli-Q, 18.2 MΩ) up to
spectroscopy (QELS) for the determination of the distribution 10 ml. Next, the test-tube was placed in an ultrasonic bath for
of particle sizes in suspension of the analyzed samples and 30 min in order to disaggregate and homogenize the sample.
scanning electron microscopy (SEM) for the investigation of the Once this process was carried out, the sample was left to settle
final size, distribution and homogeneity of particles deposited for 12 h. Finally, aliquots of 1 ml were taken, measured from the
on the flat carrier. base, at three different depths (15 cm in Set-1; 10 cm in Set-2;
The analysis by TXRF was performed by using a Seifert and 5 cm in Set-3) in order to obtain an average distribution of
EXTRA-II spectrometer (Rich Seifert & Co, Ahrensburg, different particle sizes (always lower than 10 μm and with an
Germany), equipped with a molybdenum X-ray fine focus average size around 1 μm as postulated in the second main
lines, and a Si(Li) detector with an active area of 80 mm2 and a requirement). Thus, the following three particle size sets were
resolution of 157 eV at 5.9 keV (Mn Kα). The measurements obtained: Set-1, lower than 2 μm; Set-2, between 0.05 and
were performed working at 50 kV and filtered with a 50 μm Mo 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.
SFe Ax
mx ¼ mFe ð1Þ
Sx AFe
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) 2.3.2. SEM verification
in which the sedimentation problems were diminished. In order to verify the third main requirement, different kinds
of depositions were generated on quartz sample supports and
2.3.1. Sample preparation observed by SEM after gold metallization. The first one was a
First, the sample was ground by an agate mortar until it had a suspension in water, showing a distribution of concentric rings
particle size lower than 30 μm. Then it was ground again for 1 h in shape, probably associated with an edge effect in the liquid–
by using a vibration micro-pulverizer equipped with a ball and solid interface during the water evaporation process (Fig. 4-a,
base of agate. Afterwards, 1 ml of high-purity water was added. b). In order to obtain a distribution of particles that were isolated
Next, the mix was poured into a test-tube in which high-purity and homogeneous, we experimented with different agents of
water was added up to 10 ml. The sample was homogenized for different surface tensions, particularly with toluene and high-
1/2 h by ultrasonic disaggregation in order to disperse possible purity water. It was established that toluene provided the best
agglomeration of particles. Finally, the particle size distribution distribution (Fig. 4-c, d). Nevertheless, it was noticed that this
in suspension was checked by using QELS until it had the agent seriously distorted the analytical determinations. Probably
required distribution and, therefore, was in accordance with the the observed quantitative analytical distortion can be attributed
second main requirement. When the sample had this size to the mountain effect, at micro particle level, that can be
distribution, it was again homogenized and, maintaining the appreciated in Fig. 4-d. This effect produces the lost of the thin
agitation always constant, 5 μl of the suspension was placed on film geometry and the appearance of the energy dependent
the quartz flat carrier and dried on a ceramic hot plate. All matrix effect, which is in agreement with the experimental
manipulations were made in an A-100 class laminar flow observations. As a result, we finally decided to use high-purity
chamber. water, even though such a water did not strictly comply with the
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