Calculation of attenuation and x‐ray fluorescence intensities for non‐parallel x‐ray beams

With the nowadays widespreaded use of x‐ray optics in x‐ray fluorescence analysis, large convergence or divergence angles can occur. This experimental situation violates a basic assumption of the usual fundamental parameter quantification procedure. In order to take beam divergences in micro x‐ray fluorescence analysis into account, a way of calculating fluorescence intensities numerically by Monte Carlo integration is described. For three examples of typical micro‐XRF set‐ups the fluorescence intensities and their deviation from the parallel beam geometry are calculated. Furthermore, we propose a new approach with ‘equivalent angles’ which correct for the beam divergences in fundamental parameter methods. Copyright © 2003 John Wiley & Sons, Ltd.     

Analysis of Limoges painted enamels from the 16th to 19th centuries by using a portable micro x‐ray fluorescence spectrometer

Material analysis of Limoges painted enamels was undertaken by using an x‐ray fluorescence spectrometer equipped with a low‐power x‐ray tube, polycapillary x‐ray optics and a silicon drift chamber detector. The spectrometer, which includes helium purging for detecting elements down to sodium, can easily be assembled and dismantled within 1 h. A quantification method for enamel and glass objects was developed and verified using standard materials. The layer arrangement and possible influence on the XRF measurements were especially considered in theoretical calculations. Over 160 painted enamels from the late Renaissance and Revival periods in the 19th century in various collections were investigated. Comparison of the quantitative results from objects which are securely dated and attributed by art historians allowed a more reliable attribution of pieces with doubted authenticity. Copyright © 2004 John Wiley & Sons, Ltd.     

The capabilities of an electrically cooled energy‐dispersive x‐ray detector for quantitative x‐ray fluorescence analysis

The capabilities of the Si PIN diode x‐ray detector were determined and compared with those of a standard Si(Li) detector. The x‐ray fluorescence (XRF) analysis systems assembled with these two detectors included annular radioisotope excitation sources of Cd‐109 and Fe‐55. The systems were calibrated for sensitivity and quantification was performed with fundamental parameters software. Based on the analysis of the standard reference material NIST 2710 (Montana soil), the elemental sensitivities and the limits of detection of both systems were obtained. The elemental sensitivities of the Si PIN detector for fluorescence x‐rays in the energy range up to 10 keV were comparable to those of the Si(Li) detector. At higher fluorescence x‐ray energies the sensitivity of the Si PIN detector gradually decreased and was smaller by a factor of ～4 at 20 keV. The reason was mainly the small thickness of the sensitive volume of the Si PIN diode (0.2 mm) and therefore the smaller relative efficiency of this detector. The assessed limits of detection (LODs) were comparable for the two detectors, which was mainly due to the lower spectral background of the Si PIN detector in excitation with the Cd‐109 source as a result of its smaller sensitive thickness. The accuracy of elemental determinations for the two detectors was comparable and within the limits of the assessed uncertainties, which were calculated considering all the steps of the analysis, i.e. spectrum measurement and analysis, sensitivity calibration and quantification. Copyright © 2004 John Wiley & Sons, Ltd.     

Determination of trace elements in Mycobacterium fortuitum by x‐ray fluorescence spectrometry

Using energy‐dispersive x‐ray fluorescence analysis with an ¹²⁵I ring source, it was possible to determine the concentration of several elements, such as Mn, Fe, Cu, Zn, Br, Rb and Sr, at the µg g^?1 level in a microorganism (Mycobacterium fortuitum) and in nutrient medium. It was observed that the bacteria always incorporated a fixed amount of a given element even if the concentration in the nutrient medium was different. It was possible to contaminate the cells also with Zr. The sample preparation and irradiation process developed is a non‐destructive microorganism analytical method, as about 70% of the bacteria survived the measuring process. Copyright © 2003 John Wiley & Sons, Ltd.     

Application of selected fundamental parameters in x‐ray fluorescence analysis

The effectiveness of selected fundamental parameters in x‐ray fluorescence analysis previously proposed by the authors was examined with a few examples. Some synthetic fused binary disks were prepared and measured to obtain the measured binary coefficients. The theoretical influence coefficients were also calculated based on the synthetic specimens and measuring conditions using those selected fundamental parameters and compared with the measured values. It was found that the theoretical influence coefficients calculated with selected fundamental parameters agreed better with measured values than those calculated with original parameters. The synthetic fused disks, some Au–Ag–Cu alloys and some Chinese rock reference materials were measured and quantitatively calculated with the program NRLXRF, that uses original parameters, and with NRL301, that uses selected fundamental parameters, using only one calibration standard for fused disks and only pure elements for alloys. The relative errors of the results from NRL301 are much smaller than those from NRLXRF. Data for the example of pressed powders of cement published in an NBS Technical Note were also calculated with NRL301 with one calibration standard. The results are comparable to those from NBSGSC obtained with seven calibration standards. Copyright © 2003 John Wiley & Sons, Ltd.     

X‐ray absorption and x‐ray fluorescence for the characterization of titanium oxide‐modified HPLC silicas

Titanium oxide grafted on to the surfaces of chromatographic silica was investigated by x‐ray fluorescence (XRF) and x‐ray absorption (XAS) spectroscopy and the latter used before and after the extensive use of this material as a support for reversed‐phase high‐performance liquid chromatography (RP‐HPLC). XRF indicated the formation of a complete 2:1 monolayer whereas XAS suggested the presence of more than one titanium oxide structure. These structures show some slight modification after immobilization of PMOS and use in HPLC. Copyright © 2005 John Wiley & Sons, Ltd.     

Nanoresolution interface studies in thin films by synchrotron x‐ray diffraction and by using x‐ray waveguide structure

In the last years we performed several measurements with synchrotron radiation of several facilities to reveal interesting interface phenomena on the nanoscale. We used both x‐ray diffraction [1] , [2] (XRD) and spectrometry techniques. In this paper, we briefly summarize the results obtained from diffraction measurements, which lead us to our recent grazing incidence x‐ray fluorescence analysis (GIXRF) and extended x‐ray absorption fine structure (EXAFS) experiments. We show how a combination of experimental methods of GIXRF analysis and EXAFS spectroscopy in fluorescence detection with x‐ray standing waves (XSW) technique was applied for the depth profiling of a‐Si/Co/a‐Si layers with nanometer resolution to monitor the growth of CoSi intermetallic phase. The investigated layers were placed into the waveguide structure formed by two Ta films to increase sensitivity and accuracy of the measurements. Copyright © 2009 John Wiley & Sons, Ltd.     

Development of a K‐shell x‐ray fluorescence measurement of cadmium in bone

Cadmium is known to accumulate in the human body and chronic exposures have been clearly linked to adverse health effects, showing the kidney as the critical target organ. However, there is evidence of an association between extensive environmental exposure to cadmium and alterations in bone/calcium metabolism. Therefore, it is desirable to be able to measure bone cadmium non‐invasively in humans. Tibia was selected as a measurement site and source‐excited K‐shell x‐ray fluorescence was investigated both experimentally and computationally. Initially the 88 keV γ‐rays from ¹⁰⁹Cd were used to assess minimum detectable level (MDL) of cadmium in phantoms comprising plaster of Paris (bone) and wax (soft tissue). An MDL of 3–4µg g^?1 was achieved for overlying tissue thicknesses of up to 5 mm. Alternative sources were ¹²⁵I and ²⁴¹Am. Monte Carlo simulation showed that the spectral contrast for ¹²⁵I would be poor. The 60 keV γ‐rays from ²⁴¹Am were more promising, provided that the 26 keV γ‐rays were filtered out. Experiments with ²⁴¹Am confirmed that a lower MDL could be achieved. However, the product of MDL and square root of dose (a figure of merit) was not improved. Since effective doses for these source‐excited x‐ray fluorescence procedures are low (typically of the order of 0.1 µSv or less), it may be that lower MDL would be preferred over lower dose. Nevertheless, development continues as a further reduction in MDL is highly desirable. Copyright © 2005 John Wiley & Sons, Ltd.     

Chemical effects on x‐ray fluorescence yield of Ag+ compounds

X‐ray fluorescence measurements were carried out for silver metal and a number of silver compounds containing Ag⁺ ions such as Ag₂CO₃, Ag₂SO₄, AgNO₃, AgCl, AgBr and AgI using 59.6 keV γ‐rays, emitted from ²⁴¹Am, as the excitation source, to evaluate the value of Kβ/Kα x‐ray intensity ratio. For silver metal the value of this parameter is found to be 0.206 ± 0.003 and wide variations, 0.190 ≤ Kβ/Kα≤ 0.207, were observed for these compounds. The results are explained in terms of the charge transfer occurring between Ag⁺ and the coordinating anions. Copyright © 2005 John Wiley & Sons, Ltd.     

Raman analysis assessed by Fourier‐Transformed infrared and X‐ray fluorescence spectroscopies: a multi‐analytical approach of ancient chromolithographs from the 19th century

A set of chromolithographs from the 19th century were analysed to identify the fillers and pigments used for their elaboration. Because of the delicacy of the chromolithographs, the research involved the use of Raman, Fourier‐transform infrared and energy dispersive X‐ray fluorescence spectroscopies for a complete characterization of the works on paper without removing any microsamples. Despite the high fluorescence of the samples when analyzed by Raman spectroscopy, in this paper, we demonstrated that ink spectra can be successfully enhanced by subtracting the spectra of the supporting background paper. The results of the study showed that, apparently, the lithographer used a limited range of common inorganic pigments from the 19th century (carbon black, chrome yellow, Prussian blue, red ochre, red lead and vermilion) together with organic pigments (indigo blue, gamboge and a red organic pigment). The study also found that despite the fact that during the 19th and early 20th century the use of mixtures of several pigments was a common practice, unusual admixtures were used for the preparation of some colours of the studied chromolithographs. Copyright © 2011 John Wiley & Sons, Ltd.     

Empirical coefficients models for x‐ray fluorescence analysis of intermediate‐thickness samples

Empirical coefficients models for correction of matrix effects in intermediate‐thickness samples are presented. Two proposed mathematical models correct simultaneously matrix effects and various masses per unit area of the samples. In the first model, it is necessary to know the masses per unit area of the samples and in the second model masses are predicted from the scattered radiation. To calculate coefficients of the models, a series of multi‐element intermediate‐thickness standards with various compositions and various masses per unit area are required. The models were tested experimentally using synthetic samples pressed into pellets and geological certificate reference materials collected on a membrane filter. The calculated concentrations were in good agreement with the certificate values. Copyright © 2004 John Wiley & Sons, Ltd.     

Determination of Mg and Ti in Ziegler–Natta catalysts by x‐ray fluorescence spectrometry

The metal content in Ziegler–Natta catalysts based on Ti and Mg derivatives could not be determined directly by x‐ray fluorescence (XRF) spectrometry owing to the instability of the catalyst. The samples were then calcined and the resultant Mg and Ti oxides were characterized by x‐ray diffraction (XRD). A series of synthetic standards were prepared with high‐purity MgO and TiO₂, since there were no available certified standards for the catalysts. Samples and standards were compressed with high‐purity H₃BO₃ flux. This protocol was shown to be reproducible, having a correlation coefficient of 0.9999. The metal contents determined by XRF were in accordance with those obtained by a complexometric titration (Mg) and a UV–visible spectrophotometric method (Ti). Copyright © 2004 John Wiley & Sons, Ltd.     

Time‐resolved x‐ray fluorescence for monitoring the intake of mineral nutrients in living plants

We have applied a time‐resolved means of measurement for studying living plants. The intake of mineral nutrients in a living plant such as stevia has been observed by this measuring instrument. A solution containing K, Ca, Mn, Fe, Cu, and Zn compounds was used as the mineral nutrient solution. The concentrations of the standard solutions were specifically chosen to obtain optimal intensities of the x‐ray peaks. The time dependence of the x‐ray fluorescence (XRF) intensity showed specific intake processes depending on the type of element. In addition, the experimental results suggest differences in the translocation of each element in the stevia stem. We conclude that time‐resolved XRF is a powerful technique for studying living plants. Copyright © 2007 John Wiley & Sons, Ltd.     

The effects of absorption edge structure of atoms in x‐ray fluorescence analysis

The effects of the absorption edge structure in x‐ray fluorescence (XRF) manifest themselves as a very strong attenuation of the analytical line radiation when it is in the x‐ray absorption near edge structure (XANES) range. In this paper, this effect is exemplified by an ultra‐strong Ba‐caused attenuation of the Ce Lβ₁ line. This case was experimentally studied. Comparison of measured and calculated relative intensities has shown that the actual mass attenuation coefficient of the Ce Lβ₁ line in Ba is 1.6 times greater than known values. This is due to that the Ce Lβ₁ line is within the initial range of L3 Ba absorption edge, i. e. the XANES range. Such an effect of the absorption edge structure of atoms must be considered using the fundamental parameters method in quantitative XRF analysis. This paper also presents some other possible cases of this effect. Copyright © 2009 John Wiley & Sons, Ltd.     

Selective excitation and integral counting of x‐ray fluorescence (SEICXRF)

This paper proposes a spectrometric method for x‐ray fluorescence, based on selective excitation and integral counting of the emitted photons by the sample. It is named SEICXRF (Selective Excitation and Integral Counting of X‐Ray Fluorescence). The general characteristics of the method are shown: the spectrometer, the spectrum acquisition, the effects involved in the determination of the jump intensity and their respective algorithms (the primary and secondary intensities and other unexpected effects), its capacity to identify elements, its sensitivity, its limitations and scope. Copyright © 2003 John Wiley & Sons, Ltd.