Research article

Received: 14 June 2012 Accepted: 25 January 2013 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/xrs.2467

Multielemental analysis of powder samples by direct measurement with TXRF

C. Cantaluppi,* M. Natali, F. Ceccotto and A. Fasson
Total reection X-ray uorescence analysis was used to measure various powder samples directly put on an adhesive carbon tab placed on a quartz carrier. In this paper, the ability of the method to perform quantitative multielemental analysis without sample digestion was demonstrated. To assess the optimal measurement conditions, angular scans to nd the best glancing angle were carried out, different kinds of reference standard powders were measured, and matrix effects and detection limits were evaluated. The results show a good agreement of data obtained with certied values. This quick method can be applied to characterize powders without any chemical treatment, thus reducing time for analysis and minimizing the risk of sample contamination. As a consequence, a great advantage is that a large number of samples can be analyzed in a short time: This method can be very useful in environmental applications such as the analysis of many atmospheric particulate samples from a wide area and for repeated monitoring. Copyright 2013 John Wiley & Sons, Ltd.

Introduction
Total reection X-ray uorescence (TXRF) is an effective method to determine the multielemental composition of small amounts of samples. This technique is able to analyze both chemically treated samples (obtained by digestion) and as it is samples. In both cases, to determine the elemental concentration of samples, usually a reference element is used as an internal standard (dropped onto a quartz carrier)[1] or an external standard is required (a certied amount of element used for linear calibration).[2] Other techniques such as inductively coupled plasma [3] and atomic absorption spectrometry [4,5] are commonly used, but they always need digestion treatments. The latter may have some disadvantages such as the risk of sample contamination in handling and by reagent impurities and the possible loss and dilution of analytes.[6,7]The traditional XRF is a nondestructive analysis,[8,9] but it needs appropriate calibrations to correct for matrix effects, and moreover, hundreds of milligrams of sample are needed. The nuclear techniques such as particle-induced X-ray emission[10] and instrumental neutron activation analysis[11] are nondestructive and have high-accuracy and multielemental analysis capability, but are not widely used in research laboratories, because they require accelerator facilities. TXRF was used to measure powder samples, as a direct analytical method without any chemical pretreatment, avoiding the aforementioned risks. Moreover, the capability to analyze minute amounts of sample[12] makes TXRF a good tool for different applications in environmental studies. Several investigations demonstrate the feasibility to measure airborne particulate matter, collected on TXRF quartz carriers used as impaction plates[1316] or through ltration systems on lters analyzed as thin lms.[17,18] Environmental and mineral powders, sediments, soils, pigments, and others can be measured as slurries deposited onto a quartz carrier.[1921] The aim of this work was to set up an alternative TXRF method for quantitative, direct multielemental determination of different kinds of powder samples using a double-sided adhesive disk (carbon adhesive tab used for scanning electron microscope

(SEM) analysis) placed on TXRF quartz carrier. Jacques Renault and Chris McKee[22] proposed traditional XRF analysis of household dust collected on an adhesive, but the analysis was performed only for one element (lead), and some limits of the technique were highlighted (not less than 1020 mg of sample, several weighting steps, and long counting times). The method proposed in the present paper implies a very fast sample preparation/collection and requires only minute amounts of sample (~0.5 mg). Thus, it is possible to collect many samples that are immediately measurable without any treatments. Also, the use of conductive carbon adhesive tabs (quite inexpensive and commercially available) permits immediate SEM microanalysis and reliable preservation for other subsequent measurements.

Experimental
Instrumentation The TXRF spectrometer is a TX2000 (Ital Structures) 3-kW dual anode (Mo/W), with maximum tube voltage 50 kV, and maximum current 40 mA. The operating conditions were tube voltage 40 kV, tube current 30 mA, and Mo anode. The detector is a Si(Li) type, active depth 5 mm, and resolution < 140 eV for Mn Ka. Laser granulometry measurements were performed with a Malvern Mastersizer 2000 instrument. SEM pictures were taken with a Sigma Zeiss Field Emission SEM equipped with an Oxford X-max EDS system and an 800  C heating module.

* Correspondence to: C. Cantaluppi, Institute of Inorganic Chemistry and Surfaces, National Research Council (ICIS-CNR), C.so Stati Uniti 4, 35127 Padova, Italy. E-mail: chiara.cantaluppi@icis.cnr.it Institute of Inorganic Chemistry and Surfaces, National Research Council (ICIS-CNR), C.so Stati Uniti 4, 35127 Padova Italy

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C. Cantaluppi et al. Sample preparation and analysis As sample carrier, a double-sided adhesive carbon tab of 12 mm diameter and 100 mm thickness (sulfur-free conductive carbon disk C272 for SEM analysis), was placed on the quartz carrier (diameter 30 mm) used for TXRF analysis. The samples in powder form were put for the analysis on the tab using TeonW tools, distributing homogeneously the sample in a 5-mm spot at the center of the adhesive tab and accurately weighed with analytical grade balance. Prior to placing the carbon adhesive tab, the quartz disks were washed with detergent in ultrasonic bath, rinsed with ultrapure water, submerged in 10% nitric acid solution at 60  C for 2 h, rinsed with ultrapure water, dried in N2 ux, and analyzed by TXRF for purity. Several reference samples, with known elemental concentrations, were used for method setup: NIST SRM 1648 (National Institute of Standards Standard Reference Material, urban particulate matter), BCR CRM 277 (Community Bureau of Reference, Belgium, certied reference material estuarine sediment), NIST SRM 1575 (pine needles), and NIST SRM 1566 (oyster tissue). An amount of about 0.50.6 mg of sample was used, and measurement times were 2000 s. To evaluate the homogeneity of the sample layer on the carbon tab, three spectra were recorded at different azimuth angles of the sample, rotating the quartz disk by 120 . To evaluate the linearity of the method, a portion of the adhesive tab of 5 mm diameter (smaller than the detector aperture width of 7 mm) was cut out from the original tab to guarantee complete detection of the weighted amount of sample. Different sample aliquots of the reference standard NIST SRM 1648 were dispensed on the adhesive tab and weighed with analytical grade balance. For spectral analysis, the WinEDXRF32 software by Ital Structures/GNR was used, applying least-square tting of the spectrum and extracting element concentrations in TXRF analysis mode, assuming absence of matrix effects. For determining element concentrations when measuring reference standard materials, a chosen element was taken as an internal standard, and its known concentration was used. In case of unknown samples, the most abundant element was normalized to a concentration of 100%, thus obtaining element concentration ratios as the result, rather than element concentrations. Because the carbon adhesives contained residual impurities of Fe, Ni, and Br, for the determination of these elements in the powder samples, the additional measurement of a blank carbon adhesive tab was necessary. The latter was measured at the same grazing incidence angle as the sample. Peak areas for the relevant sample elements were then corrected by subtracting the peak areas of the blank. reference sample (NIST SRM 1648) distributed on the top of the adhesive tab (Fig. 1). From such angular scans, it turned out for all samples that the peak of the sample uorescence (e.g. Fe in the present case) is located at an angle where the scattering Mo signal decreases. Measuring spectra at an angle where the sample element uorescence/Mo scattering ratio is maximized, maximum signal/noise ratio can be achieved. In practice, because the location and shape of the uorescence peak also slightly depend on the sample (probably due to an unavoidably inhomogeneous distribution of the powder on the adhesive), a xed angle (arrow in Fig. 1), suitable for all investigated samples, was chosen at which the Mo scattering is low, whereas the sample uorescence is still high. The typical uorescence spectrum of the particulate matter standard sample recorded at this angle is shown in Fig. 2, together with the spectrum of a blank adhesive tab. The Fe, Ni, and Br impurities of the adhesive tab are evident. Another way to evaluate the background contribution of the adhesive tab in principle is to compare the spectrum of a powder sample placed on the adhesive tab with the same amount of sample placed directly on the quartz carrier. However, placing an amount of dry powder sample in the weight range 0.50.6 mg, as used for our tab method, directly on the sample carrier is not practical without preparing the powder sample into a slurry. We want to stress that the aim of our method is just to avoid the need for preparing a slurry because this is not practical in many cases of interest, such as rapid sampling of tiny amounts

Figure 1. Typical angular scans of Mo scattering signal and the Fe sample uorescence.

Results and discussion

Usually, for TXRF analysis, solid samples are digested to obtain a solution. On the contrary, in the proposed approach, the sample is in powder form and typically has a heterogeneous and rather wide grain size distribution (from few microns to tens or hundreds of micron). Moreover, the particulates were put on top of the 100-mm-thick and rather rough carbon adhesive lm, placed on the TXRF quartz carrier disk. It is therefore clear that the rigorous conditions of total reection are not achieved, and it is not a priori evident if there is a suitable TXRF measurement condition for such a sample. To investigate this aspect, the primary beam incidence angle (tube shield angle) was varied, performing angular scans of both the Mo diffuse scattering signal and the Fe uorescence of a

Figure 2. Comparison of the uorescence spectra of a blank adhesive tab and a sample (NIST SRM 1648 urban particulate matter).

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Multielement analysis of powder samples with TXRF of ambient dust deposited on small surfaces, e.g. for analysis of household dust or gunshot residues. The tab method permits to collect such samples by simply tapping the adhesive-coated quartz carrier onto the dusty surface of interest. In this way, the range of possible applications of TXRF is extended. Moreover, the powder collected on the carbon adhesive tabs can be directly analyzed also by SEM and permits prolonged storage for later analysis. Finally, this method, avoiding any sample handling and preparation, prevents any risk of sample contamination. That said, it is nevertheless instructive to compare the spectra of NIST SRM 1648 sample placed on the adhesive tab and the same amount of sample prepared as a slurry and dropped onto a siliconized quartz disk. To this purpose, the slurry was prepared by sonicating the particulate matter sample in ultrapure water, homogenizing it by shaking and dispensing 20 ml of the slurry both on the carbon adhesive tab and on the quartz disk. After drying under a lamp in both cases, a dry sample spot of about 34 mm diameter is obtained. The spectra of the two samples are compared in Fig. 3. First of all, the good overlap of all sample peaks can be noticed. The intensity of sample peaks is higher when measuring the sample as a slurry under standard TXRF conditions. By normalizing the intensity of the spectra to achieve comparable sample peak intensities, a higher relative background signal of the tab method is evident. This is not surprising giving the presence of the carbon matrix of the adhesive and does not invalidate our method. Indeed, as stressed earlier, the main aim of our method is to widen the range of applications of TXRF by extending the sampling methods beyond those presently available. Evaluation of the role of sample inhomogeneity and weight on concentration values Two principal sources of error affect the element concentrations: (1) statistical and (2) sampling. Statistical errors decrease with increasing peak areas (counts). However, because peak areas are determined by a peak-tting routine to deconvolve overlapping peaks and to subtract the background, the effective errors on peak areas can be larger than the pure counting statistics error.[23,24] Sampling errors are due to sample inhomogeneity. In the present conditions, they manifest themselves in differences in peak area ratios among the spectra recorded at the three different azimuth angles. A systematic evaluation of statistical and sampling errors was carried out by measuring NIST 1648 urban particulate matter samples at three different rotations and for different sample weights by recording spectra for 300 s at each rotation. The grain size distributions of the NIST 1648 sample as well as the other standard reference materials investigated are shown in Fig. 4. In Fig. 5, the average peak area and the sampling and statistical errors of the element concentrations are compared for ve different sample weights and ve selected elements: Cr (404 12 mg kg1), Mn (860 mg kg1), Cu (609 27 mg kg1), Zn (4760 140 mg kg1), and As (115 10 mg kg1). Figure 5 shows that peak areas increase with increasing sample weight, whereas statistical errors typically decrease. Nevertheless, as mentioned earlier, contributions from the peak-tting/deconvolution and background subtraction in some cases cause a deviation from this rule. The sampling error largely dominates the overall error, being generally much larger than the statistical errors, except for peaks with very low areas (e.g. for Cr in the 0.19 and 0.39-mg samples and As in the 0.19-mg sample). Sampling errors on element concentrations are typically in the 1020% range, except for some elements with relatively strong peaks (e.g. Zn in Fig. 5) that can have lower

Figure 4. Grain size distribution of standard reference materials used as determined by laser granulometry.

Figure 3. Comparison of total reection X-ray uorescence measurements of the NIST1648 urban particulate matter sample carried out with the tab method and by depositing the powder directly onto a quartz disk, after preparing a slurry using ultrapure water. The same amount of sample was used in both cases.

Figure 5. Evaluation of peak area and statistical and sampling errors for different elements and sample weights.

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C. Cantaluppi et al. sampling errors (below 10%). Moreover, because of the relatively random behavior of sampling errors, increasing sample weight does not necessarily improve the accuracy of the element concentrations, while it could possibly lead to systematic errors due to matrix effects. Finally, for a given sample and a given azimuth rotation, increasing counting time will reduce the statistical error. The counting time should be chosen such that the counts N of the weakest peak of interest give a statistical relative error N = 1/(N)1/2 that is negligible compared with the typical sampling errors.
Table 1. Calculated attenuation lengths Attenuation length (mm) Energy (keV) 1.487 3.691 5.412 6.399 8.631 10.540 13.370 17.480 Element Urban particulate matter 3.84E + 00 2.38E + 01 6.73E + 01 1.08E + 02 1.89E + 02 2.31E + 02 4.26E + 02 8.55E + 02 Estuarine sediment 3.55E + 00 1.37E + 01 3.80E + 01 6.10E + 01 1.16E + 02 2.05E + 02 4.04E + 02 8.68E + 02 Dry organic tissue 4.54E + 01 6.27E + 02 1.97E + 03 3.27E + 03 8.05E + 03 1.45E + 04 2.85E + 04 5.70E + 04

Evaluation of matrix effects To experimentally evaluate the relevance of matrix effects, the linearity of the uorescence intensity versus sample weight was checked, measuring different amounts of the reference sample SRM 1648: 0.19, 0.39, 0.56, 0.77, 1.08, 1.47, and 2.25 mg on the 5 mm diameter adhesive tab. In Fig. 6, the results for Cu and Mn are shown. Similar results were obtained for the other elements. Although the relatively large errors do not allow for a very precise verication of linearity, it appears reasonably clear that saturation of the uorescence intensity only occurs for relatively large sample weights, i.e. above about 1.5 mg. Absorption of X-rays in TXRF can be divided into absorption along the incoming radiation path that is nearly parallel to the sample layer and absorption along the outgoing uorescence radiation path perpendicular to the sample layer. As a rough estimate, considering the known elemental composition of the different standard reference materials and their densities ( = 1.6 g cm3 for the particulate matter sample, 2.2 g cm3 for an estuarine sediment, and 0.2 g cm3 for the dry organic tissue), the attenuation length (1/m) was calculated for the incoming Mo radiation and for emitted uorescence X-rays at different energies (Table 1).[25] From these data, it can be expected that the incident Mo radiation is absorbed only weakly by the carbon adhesive tab and by the organic dry tissues, whereas attenuation along the incident X-ray path is expected to be quite substantial by the particulate matter and sediment samples, so that illumination of the samples at the grazing incidence will be not very uniform for these samples. The latter circumstance contributes to the sampling errors when rotating the sample azimuthally, because different portions of the sample will be illuminated more intensely at each rotation. From these values, it also results that it is important especially for dense samples to distribute the sample in the central ~5 mm wide region seen by the detector.

Al Ka1 Ca Ka1 Cr Ka1 Fe Ka1 Zn Ka1 Pb La1 Rb Ka1 Mo Ka1

Using smaller adhesives or cutting out a 5-mm area from the 12 mm diameter adhesives simplies this task. Concerning the attenuation of the sample uorescence radiation, the size to compare with is the sample layer thickness. To gain an order of magnitude estimate, let us consider a hypothetical uniform and compact sample layer. In this case, for instance, a particulate matter sample with a weight of 0.5 mg and a density of about 1.6 g cm3 uniformly distributed over a circular area with 5 mm diameter would give an average sample layer thickness of about 7 mm. Because the sample distribution however is neither compact nor uniform and the typical grain size is larger than this

Figure 6. Fluorescence intensity versus sample weight for Cu and Mn peaks of NIST 1648 urban particulate matter sample.

Figure 7. (a) Histogram of selected measured and tabulated composition values and (b) plot of relative difference of composition values for NIST 1648 urban particulate matter (0.76-mg sample).

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Multielement analysis of powder samples with TXRF (typically 1020 mm for the particulate matter sample as can be seen from Fig. 5) in practice in most cases, it is the grain size distribution that determines the relevant path length for uorescent radiation absorption, rather than a hypothetical layer thickness. Taking 20 mm as a typical grain size for the NIST 1648 sample and comparing with the attenuation lengths in Table 1, we can notice that the uorescence radiation will be considerably absorbed by the lighter elements (e.g. Al and Ca), whereas absorption of uorescent radiation and thus matrix effects will be relatively negligible for elements with uorescent lines at or above those of the Cr Ka1 line (1/m = 67 mm). For the estuarine sediment (BCR 277) that has a similar grain size distribution as the particulate matter sample, given the higher density absorption effects, the attenuation may be considered sufciently small only for elements with uorescent lines at or above that of Fe Ka1 line (1/m = 61 mm). For the organic standard reference material samples, the attenuation lengths are smaller, but their grain size distribution extends to much larger grain sizes (Fig. 5). For the NIST 1566 oyster tissue samples, typical grain sizes are in the range 20200 mm so that absorption of uorescence radiation can be considered negligible for elements with uorescent energy above Ca (1/m = 627 mm). For the NIST 1575 pine needle sample, typical grain sizes are in the range 100600 mm, which makes the absorption of uorescent radiation for this sample particularly severe for elements below, e.g. Cr (1/m = 1970 mm). A more practical evaluation of matrix effects can be carried out by comparing composition values of different reference standard materials with the experimentally determined values. Composition measurements of certied reference standard materials The measured concentration values of different certied reference standard materials, analyzed with the tab method, are compared with the certied and tabulated values in Figs 710 for NIST 1648 urban particulate matter, BCR 277 estuarine sediment, NIST 1566 oyster tissue, and NIST 1575 pine needle. From the inspection of the histograms, a good qualitative overall agreement can be evinced in all analyzed samples for the reported elements. A more quantitative evaluation of the degree of agreement can be judged from the graphs of relative difference of the element concentrations. For the particulate matter sample (Fig. 7), the agreement with reference values within experimental errors is better than 20% for Ba, Ti, Mn, (Fe normalization element), Cu, Zn, Pb, As, and Br, whereas for Cr, Se, and Rb, the agreement is within 30%. For BCR 277 estuarine sediment sample (Fig. 8), Cr,Ni,Cu,Zn are in agreement with the certied values within 20%. For As as well as Ni in this case, quite large errors are obtained. Whereas the grain size distribution of this sample is similar to that of the particulate matter sample, the reason for the higher sampling errors can be attributed in the rst place to the lower concentration of corresponding elements and then to the overlap of a weak As contribution with the Pb peak. For the NIST 1566 oyster tissue sample (Fig. 9), again a good agreement within 10% is obtained for Mn, Fe, and Cu (Zn normalization element), except for Br, which is more difcult to determine because it also could be affected by possible errors in the peak area subtraction. Noteworthy is the good agreement for

Figure 8. (a) Histogram of measured and tabulated composition values and (b) relative differences of composition values for BCR 277 estuarine sediment (0.47-mg sample).

Figure 9. (a) Histogram of selected measured and tabulated composition values and (b) relative differences of composition values for NIST 1566 oyster tissue (0.42-mg sample).

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C. Cantaluppi et al.

Figure 12. Scanning electron microscopy picture of the atmospheric particulate sample.

Figure 10. (a) Histogram of selected measured and tabulated composition values and (b) relative differences of composition values for NIST 1575 pine needles (0.44-mg sample).

reported in Fig. 11. The grain size and shape distribution of the sample is visible on a picture of the same tab taken with SEM (Fig. 12): The composition of the dust sample in terms of size and dimensions is very heterogeneous, from less than 1 mm to tens of microns. Element areas were normalized with respect to the most abundant one (Fe). It can be seen that trace elements of interest in environmental monitoring such as As, Br, Rb, Cr, V, Ni, Zn, and Pb present with low relative abundance with respect to Fe (0.010.1%) can be quantitatively determined.

Conclusions
the relatively low element concentrations of As and Mn (below 20 mg kg1) giving an idea of the detection limit of the proposed method. Even lower element concentrations are present in the NIST 1575 pine needle standard, down to few mg kg1 for Ni and Cu and around 10 mg kg1 for Pb, Br, and Rb. In this case, a larger error and discrepancy up to 4050% of the element concentration is observed for all elements, clearly indicating that this sample represents a limiting case. At such low element concentrations, errors are excessively large, and the proposed method becomes qualitative. As an example, the analysis with this method of a sample of total atmospheric deposition collected with the adhesive tab is The main advantages of the method are that only very minute quantities are necessary (about 0.5 mg) that can be rapidly collected on the carbon adhesive tab and that samples are measured without any chemical treatment with relatively low counting times. Moreover, it is a nondestructive technique, and the same sample can be easily stored and directly analyzed by SEM. The comparison with standard materials having different matrices shows that the method is quantitative except for the lighter elements. The determined compositions are relative values with respect to one known element of the sample. Trace elements of environmental relevance (such as Cr, Cu, Ni, Zn, As, and Pb) can be quantitatively detected typically within 20% error down to 10 mg kg1. This fast analysis method is sufciently good for screening purposes, permitting many environmental applications such as 1. the analysis of tens or hundreds of airborne particle samples collected on a wide territory to identify the sources of pollution from the multielemental quantitative determination, 2. the quick mapping of fallout dusts in the case of plumes from industrial accidents involving the release of inorganic pollutants, 3. the determination of the elemental composition of the main classes of particles present in aerosol (collected by use of an impactor) after separation in size fractions, 4. the simultaneous measurements of many elements on the same sample makes the obtained data suitable for correlation and principal component analysis.

Figure 11. Histogram of composition values of an atmospheric particulate sample.

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Multielement analysis of powder samples with TXRF Acknowledgements The authors are very grateful to Prof. Sandro Degetto and Dr Aldo Cianchi for fruitful discussion, to Mr Loris Paganotto and Mr Luca Cecconello from Veneta Mineraria S.p.A. for granulometry analysis, and to Dr Simona Barison and Dr Simone Battiston (IENI-CNR) for SEM analysis.
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