X‐ray fluorescence determination of the manganese valence state and speciation in manganese ores

This work concerns determination of the manganese valence state and speciation by wavelength‐dispersive X‐ray fluorescence analysis. The authors investigated the effect of the manganese valence state and speciation on the intensity of some К‐series lines of the X‐ray emission spectrum for the samples of manganese compounds. The intensities of MnKβ₅ line and MnKβ′ satellite are least influenced by speciation, and they may be used for evaluating the manganese valence state for the samples containing low iron. The intensities of MnKβ″ and MnKβ^x satellites may be employed for assessing the manganese speciation. The results of X‐ray fluorescence determination of the manganese valence state and speciation in the manganese ores of the South Ural deposits agree with the X‐ray diffraction data. The X‐ray fluorescence method is definitely advantageous, because it does not require a complicated process of sample preparation and allows to receive fast information on the manganese valence state and speciation with the purpose to assess the quality of manganese ores. Copyright © 2015 John Wiley & Sons, Ltd.     

Distinction and quantification of inorganic sulfur species including thiosulfate by X‐ray fluorescence (WD‐XRF)

Sulfur occurs in a variety of inorganic and organic compounds with oxidation states from ?II up to +VI. Differentiation of these species in solid geochemical samples can be challenging because of oxidation processes during sample preparation by acidic digestion. Applying pressed powder pellets and an analysis by wavelength‐dispersive X‐ray fluorescence minimises reactions with oxidants and water. Main subjects of this work were five inorganic sulfur species, sulfide ?II, elemental sulfur 0, thiosulfate +II, sulfite +IV, and sulfate +VI, and the determination of their fluorescence energies in the sulfur X‐ray spectra. S Kα_1,2 and S Kβ₁ can be observed for all species, S Kβ′ satellites only for species with coordinated oxygen. The results are in good agreement with previously published data. Yet none of the 38 investigated papers from the past 90 years reported S Kα_1,2 of thiosulfate, which was determined as E = 2,309.12 eV in this work apparently for the first time. Binary mixtures of sulfur species are strongly differing in their ability of being quantitatively differentiated, as a reliable quantification requires a sufficient difference of the respective fluorescence energies. Regression equations for each mixture can be used to calculate the ratio of mass fractions of the investigated species from the evaluated fluorescence energy. If boundary conditions are considered, the presented approaches can be applied for analyses of geochemical samples or quality control of technical products. The main advantage of the described methods is the option of implementation to everyday X‐ray fluorescence lab routine without substantial additional effort.     

Instrumental detection limit and sensitivity of K and L shell X‐ray emission lines of 17Cl, 37Rb,and 38Sr elements using PC‐WDXRF spectrometer

This work was aimed to improve the instrumental detection limit and sensitivity of ₁₇Cl, ₃₇Rb, and ₃₈Sr elements present in solid samples by using the advanced polychromatic wavelength dispersive X‐ray fluorescence spectrometry method. Instrumental measuring parameters, as well as study of calibration curves of K and L shell spectral lines, were evaluated to select the best conditions for ₁₇Cl, ₃₇Rb, and ₃₈Sr quantification. From the results, it was observed that the detection limits of the Rb Kα and Sr Kα spectral lines were lower than those of the Kβ_1,3 and Lα spectral lines. From the calibration curves, it was concluded that Kα spectral lines are more suitable than Kβ_1,3 and Lα lines to identify the traces of ₁₇Cl, ₃₇Rb, and ₃₈Sr elements in different types of solid samples.     

The investigation of K‐shell fluorescence parameters of Zn–Fe alloys with different grain size and microstrain values

It is known that zinc alloys with iron group metals have better corrosion resistance than pure zinc. Owing to the corrosion resistance of these alloys, Zn–Fe coatings are widely used in automotive industry and have excellent mechanical performance. In this work, we investigated the relationship between the changes in the measured X‐ray fluorescence parameters (K_β/K_α, σ_Kα and σ_Kβ) and the changes in the structural parameters such as microstrain or grain size values for Zn–Fe alloys that were prepared with different pH values. To explain these changes, the K_α and K_βX‐ray production cross sections, and the K_β/K_αX‐ray intensity ratio values were calculated by three different ways for the elemental forms of Zn and Fe. The structural parameters, such as microstrain and grain size, were also calculated. We expect that the outer shell electronic distribution affects the structural parameters of the produced Zn–Fe alloys, changing the measured K_α and K_βX‐ray production cross sections, and the K_β/K_αX‐ray intensity ratio values. We also show that Zn–Fe alloy mi nimum microstrain value corresponds to the maximum changes in K_βX‐ray production cross‐section values of Fe and Zn. Copyright © 2017 John Wiley & Sons, Ltd.     

L x‐ray fluorescence cross‐sections of heavy elements in the atomic region 57 ≤ Z ≤ 71 excited by 17.78 keV photons

L x‐ray fluorescence cross‐sections (σ_Lα, σ_Lβ, and σ_Lγ) were measured with an accuracy of 6% (except for the Lγ x‐ray line around 8%) for La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Tm, Yb and Lu at an excitation energy of 17.78 keV. Relative intensities I_Kβ/I_Kα and I_Lγ/I_Lα were also measured for the same elements. The measured cross‐sections were compared with experimental and theoretical values. Measurements of the emitted x‐rays were performed using an Si(Li) detector. Copyright © 2004 John Wiley & Sons, Ltd.     

Energies and relative intensities of Kα3 and Kα4 x‐ray satellites of sulfur and sulfides by photon excitation

Energies and relative intensities of the K x‐ray satellites K_α4 and K_α3 of sulfur and two sulfides K₂S and FeS are measured by a wavelength dispersive spectrometer. The energy shifts of these satellites relative to the diagram line are compared with Dirac–Fock theoretical values. The energy shifts and relative intensities are examined for chemical effects. Supplementing the present data to the available data, Z dependence of K_α4/K_α3 intensity ratio is studied in the low Z region. Copyright © 2007 John Wiley & Sons, Ltd.     

Chemical speciation via X‐ray emission spectra

Since the early days of X‐ray spectrometry, X‐ray emission and fluorescence spectra have been used to investigate chemical speciation, e.g. the dependence on the formal oxidation state. Laboratory wavelength‐dispersive spectrometers have adequate resolution for these measurements. However, almost all studies have employed empirical methods to interpret the spectra. We aim to place such methods on a quantitative basis by means of efficient ab initio calculations of the X‐ray emission line shapes based on a self‐consistent, real‐space Green's function approach, as implemented in the X‐ray spectroscopy code FEFF8.2. Calculations are presented for the phosphorus K‐M_{2, 3}, and the chromium L‐series emission lines for a selection of simple compounds. These lines exhibit changes depending on the oxidation state and on the neighboring atoms in the compounds that can be observed with instruments available in many XRF laboratories. The calculated spectra, as modified by convolution with a model monochromator response function, are compared with measured spectra. Simulated and measured spectra are found to be in reasonable agreement, and show that the approach has the potential to yield quantitative information about the chemical state. Copyright © 2006 John Wiley & Sons, Ltd.     

Investigation of cadmium accumulation mechanism in hepatopancreas of Patinopecten yessoensis by synchrotron radiation X‐ray absorption fine structure and synchrotron radiation X‐ray fluorescence analyses

Chemical state of cadmium in a hepatopancreas of a scallop (Patinopecten yessoensis) was studied by means of synchrotron radiation‐based X‐ray analytical techniques. X‐ray absorption fine structure (XAFS) and X‐ray fluorescence (XRF) imaging were used to identify the chemical state and the distribution of cadmium in the hepatopancreas, respectively. The results of in vivo Cd K‐edge XAFS suggested that the neighboring atoms of the cadmium in the hepatopancreas are of sulfur. Therefore, we propose that cadmium was accumulated by a metalloprotein with sulfur. Micro XRF imaging of thin sections of the hepatopancreas showed that cadmium is distributed on the surface of intestinal epithelia and concentrated in the internal tissue of the hepatopancreas. These results indicated that scallops accumulate cadmium inside the hepatopancreas through the intestinal epithelium.     

Semi-empirical determination of Kα1,2, Kβ1,3, and Kβ2,4 X-ray natural line widths for various elements between 29 ≤ Z ≤ 74 at 123.6 keV

Abstract

In this study, K_α1,2, K_β1,3, and K_β2,4 X-ray natural line widths for various elements were determined semi-empirically at 123.6?keV by using K shell fluorescence yields obtained from energy dispersive X-ray fluorescence measurements. The obtained results contribute to a database for the development of new theoretical models of atomic structure, radiation shielding materials, and designing new technological devices related to the structural analysis of materials. The obtained results were compared with the literature, while new fitting polynomials for the studied parameters were acquired. The results showed that the natural linewidths of K X-ray lines fit fourth-order polynomials except for K_β2,4.     

Multivariate curve resolution alternating least squares in the quantitative determination of sulfur using overlapped S(Kα)–Mo(Lα) emission peaks by wavelength dispersive X‐ray fluorescence spectrometry

Spectral line overlap is a serious problem in quantitative X‐ray fluorescence analysis. In this study multivariate curve resolution alternating least squares (MCR‐ALS) approach was used to resolve the effect of overlapping S(K_α)–Mo(L_α) emission lines generated by standard‐less software of a wavelength dispersive X‐ray fluorescence spectrometer (WDXRF) for the quantitative monitoring of sulfur in mineral samples. Scan channel set contained Ge crystal, 550‐µm collimator, flow detector (Ar + CH₃) and rhodium (Rh) tube. The 18 calibration and 10 validation samples contain 0.00%–10.98% sulfate (SO₃) and 0.00%–92.40% MoO₃. The digitized spectral data were extracted in the range between 109° and 113.9° (2θ) at every 0.1 degree. Lack of fit percentage (LOF%) for experimental data and the variance explained at the optimum condition () were 2.32 and 99.94, respectively. The values of the root mean square error of prediction (RMSEP) for analyzing of sulfur were 0.23. MCR‐ALS was also compared with partial least squares (PLS) method for determination of sulfur in the presence of molybdenum. To evaluate the resolution and quantification performance of MCR‐ALS procedure, the method was used to determine sulfur in presence of molybdenum in two synthetic soil samples. Copyright © 2015 John Wiley & Sons, Ltd.     

Chemical shifts of Cr Kα and Kβ1, 3 lines by WDXRF spectrometry

Chemical shift and full widths at half maximum (FWHM) intensity of chromium Kα and Kβ_{1, 3} lines were examined for 12 kinds of materials containing chromium (CH₃CO₂)₇Cr₃(OH)₂, CrK(SO₄)₂.12H₂O, Cr(NO3)₃.9H₂O, Cr₂O₃, CrF₂, CrF₃.4H₂O, CrCl₂, CrCl₃, CrCl₃.6H₂O, [CrCl₂(H₂O)₄]Cl.2H₂O, Cr₂(SO₄)₃.15H₂O, CrO and Cr metal by wavelength‐dispersive X‐ray fluorescence (WDXRF) spectrometry. The chemical shifts, asymmetry index and the half‐widths of both the X‐ray emission lines show interesting trends with the oxidation state of chromium. It was observed that the chemical shifts for F compounds are higher than Cl compounds. It was also found larger chemical shifts and FWHM for Kβ_{1, 3} lines than Kα ones. It should be noted that the magnitude of chemical shifts increases with increase in the number of ligand atoms. Copyright © 2009 John Wiley & Sons, Ltd.     

Determination of gold and silver in dross using EDXRF technique

Gold and silver in dross were determined by energy‐dispersive X‐ray fluorescence technique. Sample was prepared by pressed pellet method using microcrystalline cellulose powder as binder, and a method of standard additions was used for quantification. L_β X‐ray of gold (11.4 keV) and K_β X‐ray of silver (24.9 keV) were used for analysis. The measured concentrations of gold and silver were 132 ± 8 and 1181 ± 84 mg kg^?1, respectively. The results were validated by instrumental neutron activation analysis technique. The t‐test indicated that there was no significant difference between results obtained by the two techniques. Energy‐dispersive X‐ray fluorescence is a simple, precise and accurate technique for the determination of gold and silver in dross. Copyright © 2014 John Wiley & Sons, Ltd.     

X‐ray fluorescence determination of Cs,Ba, La,Ce, Nd,and Ta concentrations in rocks of various composition

The technique has been developed for the quantification of small tantalum, cesium, barium, lanthanum, cerium, and neodymium concentration in rocks with X‐ray wavelength dispersive spectrometer S8 TIGER (Bruker AXS, Germany). The optimum conditions have been chosen for registration of the analyzed elements characteristic radiation and background positions. To determine the concentrations of analyzed elements accurately, the contribution of overlapping lines to the experimental intensities of the analytical lines has been taken into account. The sample of mass about 1.2 g has been pressed into pellet by the hydraulic press. Metrological studies showed that the accuracy in the determination of the concentration of analyzed elements for the developed technique meets the requirements for methods of III accuracy class. The Ta detection limits calculated for TaL_β1‐analytical and CsL_α1‐analytical lines were 2.6 and 3.4 ppm, respectively. The detection limit of Ba, La, Ce, and Nd was (in ppm), respectively, 4.3, 2.7, 5.8, and 4.7. The metrological characteristics of the previously developed and adapted techniques were compared. Ta concentration in granite pegmatite samples has been quantified. The samples of the highest tantalum content have been investigated additionally by powder diffraction and X‐ray microprobe analysis. The X‐ray diffraction method turned out to be insensitive to the detection of mineral phase of tantalum niobates, while micro‐XRF allowed detecting its presence in tourmaline grains. Copyright © 2017 John Wiley & Sons, Ltd.     

Quantitative analysis of sulphides and sulphates by WD‐XRF: Capability and constraints

In the course of geochemical characterisations, total sulphur analyses are common practice although a differentiated quantification of sulphur species could provide valuable additional information, particularly when samples from unclear or changing redox environments are investigated. Unfortunately, a likewise simple distinct determination of just sulphide and sulphate already requires considerable efforts as sample dissolution or extra equipment. Two comparatively convenient strategies based on extended routine wavelength dispersive X‐ray fluorescence spectrometry measurements were adapted and optimised for a reliable quantitative sulphur speciation whereupon the matrix influence can be neglected. About 100 synthetic samples with different concentration ratios of sulphides and sulphates have been prepared and analysed using a WD‐XRF spectrometer. The first approach to differentiate between oxidation states and their quantification takes advantage of the Kα_1,2 doublet shift. Sulphide lines are located at 2309 eV, sulphate lines at 2310 eV, and mixtures can be quantified by a regression curve of fluorescence energy versus sulphide amount. Secondly, the amount of sulphide can be calculated by a regression curve based on the quotient Kβ′/Kβ of the sulphur peak heights or areas. In contrast to sulphides, sulphates show sulphur Kβ′ satellite peaks, and the intensity of S Kβ′ increases with the increasing sulphate content. However, the applicability of this second method is limited by the lower detection limit of sulphide (10 g kg^?1 sulphide in the sample) and interferences with lead (Pb Mβ line). Both approaches are validated by an independent method, Electrothermal Vaporisation Inductively Coupled Plasma Optical Emission Spectrometry, and already employed in investigations of ore‐containing mining dumps in Saxony/Germany. Copyright © 2016 John Wiley & Sons, Ltd.     

The density and tube energy dependency of cobalt Kα/Kβ in x‐ray fluorescence spectrometryfor thick target measurements

The relative intensity of K_α/K_β for cobalt in thick targets with cobalt mass densities from 0.51 to 22.49% has been measured by the wavelength dispersive x‐ray fluorescence (XRF) spectrometer. The measuring conditions are: tube current ranging from 10 to 60 mA and voltages ranging from 20 to 60 kV. We plotted the K_α/K_β ratio vs Co densities for different tube voltages and currents. Our study shows that the K_α/K_β ratio is below the theoretical value for low Co densities and it increases with increasing Co density. For higher x‐ray energies, the K_α/K_β ratio shows a sharp growth at the special density and then reaches a nearly constant value. However, K_α/K_β ratio is theoretically constant and independent of energy in thin target measurements. The changes of this ratio according to the x‐ray energy and the element density have been studied in thick target measurements. The results provide experimental evidence to suggest that exciting energy and element density can indeed affect the K_α/K_β ratio. Copyright © 2008 John Wiley & Sons, Ltd.     

Chemical shift of the Ga and As Kα1,2 and Kβ1,3 X-ray emission lines

By means of a double crystal spectrometer and a computer the chemical shifts of the Ga Kα_1,2, As Kα_1,2 and Kβ_1,3 lines were determined with high accuracy. An interpretation of the results obtained with a free ion model and a calculation according to the Hartree method shows agreement of the values calculated for the effective atomic charges with those based on chemical experience, and also the presence of a charge transfer from the A atom to the B atom in A^IIIB^V compounds. The existence of binding charges is one of the reasons for the fact that |q_A| ≠ |q_B|. The interpretation of the Kβ_1,3 and Lα shifts shows the limitations of the free ion model.     

Experimental L x‐ray fluorescence cross‐sections for elements with 45 ≤ Z ≤ 50 at 7 keV by synchrotron radiation photoionization

L x‐ray fluorescence cross‐sections for elements with 45 ≤ Z ≤ 50 were measured at 7 keV using synchrotron radiation photoionization. The experimental set‐up provided a linearly polarized monoenergetic photon beam producing a low background and improving the signal‐to‐noise ratio. The data obtained for the L lines, Ll, Lα, Lβ_I, Lβ_II, Lγ_I and Lγ_II, were grouped considering the transition scheme, the energies of the emission lines and the detector resolution. Results for the experimental cross‐sections obtained were compared with theoretical values using two different data tables. In general, it was found that the experimental fluorescence cross‐sections are slightly higher (7–10%) than the theoretically calculated data and in some cases these differences are up to 40%. 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.     

A study of KαL1 X‐ray satellite spectrum of the elements 27 ≤ Z ≤ 31 by photon excitation

K _α X‐ray satellite spectra of Co, Ni, Cu, Zn, and Ga generated by photon excitation are analyzed using a wavelength dispersion spectrometer. Spectra of Ni, Cu, Zn, and Ga are studied for the first time using a LiF420 crystal. Spectrum of Co was studied with LiF200 crystal in second order. K_αL¹ X‐ray satellite energies and relative intensities are measured. The energy shifts relative to diagram line are computed and are compared with theoretical and semi‐empirical values. Dependence of energy shifts and relative intensities on Z and mode of excitation is analyzed.     

Three dimensional (Z‐dependence), collective and individual semi‐empirical formulae for L X‐ray production and ionization cross section by protons impact within corrected ECPSSR theory and updated experimental data: a review

In this paper we propose a new three dimensional semi‐empirical formulae for the deduction of L X‐ray production and ionization cross sections by introducing the dependence on the atomic number of the target, noted as ‘Z‐dependence’. The data are also fitted collectively and separately (for each element) by analytical functions to calculate semi‐empirical cross sections. For this purpose, the corrected ECPSSR model (noted as eCPSSR) and the published experimental data of L_α, L_β and L_γ X‐ray production and L₁, L₂ and L₃ ionization cross sections in the period (1950–2014) are combined to calculate the semi‐empirical ones for a wide range of elements by proton impact. The semi‐empirical cross sections (for the three x‐rays lines L_α, L_β, L_γ and the three sub‐shells L₁, L₂, L₃) are then deduced by fitting the available experimental data normalized to their corresponding theoretical values (using the eCPSSR model) giving a better representation of the experimental data for the individual interpolation. At last, a comparison is made between the three semi‐empirical formulae reported in this work. Copyright © 2016 John Wiley & Sons, Ltd.