Elemental mapping of frozen‐hydrated cells with cryo‐scanning X‐ray fluorescence microscopy

Visualizing the elemental distributions of cells and tissues is of growing importance in biology and medical science because such data deepen our understanding of the behavior of metal‐binding proteins and ions. Elemental mapping by X‐ray fluorescence analysis with a hard X‐ray nanobeam is very well suited for this purpose owing to its high sensitivity and high resolution. Using this technique, samples must be prepared without artifacts that are caused by treatments such as chemical fixation and staining procedures. In many studies of elemental mapping, sample preparation is not explicitly considered. To overcome this deficiency, we developed a cryo‐scanning X‐ray fluorescence microscope and installed it in the second experimental hutch of BL29XUL of SPring‐8. We used it to observe frozen‐hydrated cells that had been fixed by a quick‐freezing technique to preserve elemental data of the living state at an X‐ray energy of 11.5 keV. The distributions of K, Ca, Fe, Cu and Zn were successfully visualized. The distributions of these elements (especially those of K, Ca and Fe) differed from those in cells fixed with paraformaldehyde. Copyright © 2010 John Wiley & Sons, Ltd.     

Combined X‐ray diffraction and alpha particle X‐ray spectrometer analysis of geologic materials

The shallow interrogation depth of the lightest elements (Na, Mg, Al, and Si) detected by the particle‐induced X‐ray emission branch of the Curiosity Rover's alpha particle X‐ray spectrometer suggests that the X‐rays of these elements very likely emerge from a single mineral grain. This reality violates the assumption of atomic homogeneity at the micron scale made in both existing spectrum‐reduction approaches for the alpha particle X‐ray spectrometer. Consequently, analytical results for these elements in igneous geochemical reference materials exhibit deviations from certified concentrations in a manner that can be related to the total alkali‐silica diagram. A computer code is introduced here to provide quantitative prediction of these deviations using the mineral abundances determined from X‐ray diffraction. The latter are converted to area coverage fractions to represent the sample surface, and a fundamental parameters computation predicts the elemental X‐ray yields from each mineral and sums these. In this process, the chemistry of each individual mineral has to be varied by an iterative simplex approach; X‐ray yields are computed and compared with the peak areas from the fit of the bulk sample. When the difference between mineral yields and peak areas for each element are minimized, the mineral formulae are set and elemental X‐ray yields provided. The ratio between the summed mineral X‐ray yields and the corresponding yields based on the homogeneity assumption may then be compared directly with the concentration deviations measured in our earlier work. For several rock types, good agreement is found, thereby consolidating our understanding of the effects of sample mineralogy on alpha particle X‐ray spectrometer results. Copyright © 2017 John Wiley & Sons, Ltd.     

Characteristics of a robust and portable large area X‐ray fluorescence imaging system

A low‐cost and portable Energy Disperse X‐Ray Fluorescence imaging system is presented. It is capable of scanning large areas (up to 10 × 10 cm²) in steps as small as 0.2 mm. It consists of a small X‐ray tube and a Silicon Drift Detector, both controlled by a homemade software. The spatial resolution is evaluated as a function of the step width and of the X‐ray collimator diameter. The time of acquisition per unit of scanned surface is studied as a function of the step width and of the time of acquisition per point. X‐ray fluorescence images showing the 2D distributions of some elements in biological samples are presented. Copyright © 2013 John Wiley & Sons, Ltd.     

The new PIXE‐alpha spectrometer for the analysis of Roman nummi surfaces

The particle‐induced X‐ray emission (PIXE)‐alpha portable spectrometer of the Laboratori Nazionali del Sud has been upgraded to improve X‐ray energy resolution and efficiency. A value of 124 eV at Mn Κα‐line and a factor of 3 were, respectively, achieved. These enhanced capabilities allowed the thin surface examination of 5 Roman nummi, in which previous near‐surface X‐ray fluorescence measurements revealed traces of mercury. In particular, the new version of the PIXE‐alpha spectrometer has allowed the distinction of the 2.19 keV Hg M‐line from the 2.30 keV S K‐line and the 2.34 keV Pb M‐line. Subsequent elemental association has demonstrated a correlation between surface mercury and silver. Copyright © 2012 John Wiley & Sons, Ltd.     

Intensity correction of WD‐XRF spectra from 2θ to energy

Generally, the energy‐dispersive X‐ray fluorescence spectra are plotted as an equi‐energy interval with the constant energy resolution. On the other hand, the wavelength‐dispersive X‐ray fluorescence spectra are usually measured with an equi‐angle interval supposed the constant angular resolution. When the wavelength axis of wavelength‐dispersive X‐ray fluorescence spectra is converted into energy, the intensity should be also corrected. This intensity correction is important even for a narrow scan range such as Pb Lα and Lβ peaks. The intensity ordering is Lβ > Lα for 2θ plot, but it becomes Lα > Lβ for energy plot. The detailed conversion equations for abscissa and ordinate axes are presented. Copyright © 2012 John Wiley & Sons, Ltd.     

Measurement of background components in wavelength dispersive X‐ray fluorescence spectrometry

Three components of the background have been investigated: first, characteristic radiation of the lamellas of the collimator excited by secondary x‐ray beam; second, secondary x‐ray beam scattered by the lamellas of the collimator; third, diffusive and incoherent scattering of the secondary x‐ray beam by the focusing crystal. The relationships between chemical content of the specimen and the intensity of the first and the second components were determined by a wavelength‐dispersive x‐ray spectrometer that has an energy‐dispersive x‐ray detector. The intensity of the third component was very low. It was not found in this experiment. Copyright © 2006 John Wiley & Sons, Ltd.     

A high‐resolution X‐ray fluorescence spectrometer and its application at SSRF

A high‐resolution X‐ray fluorescence spectrometer based on Rowland circle geometry was developed and installed at BL14W1 XAFS beamline of Shanghai Synchrotron Radiation Facility. The spectrometer mainly consists of three parts: a sample holder, a spherically curved Si crystal, and an avalanche photodiode detector. The simplicity of the spectrometer makes it easily assembled on the general purpose X‐ray absorption beamline. X‐ray emission spectroscopy and high‐resolution X‐ray absorption near edge spectroscopy can be carried out by using this spectrometer. X‐ray emission preliminary results with high‐resolution about 3 eV of Mn compounds were obtained, which confirmed the feasibility of the spectrometer. The application about Eu (III) retention on manganese dioxide was also studied using this spectrometer. Compared with conventional X‐ray absorption fine structure spectroscopy technique, the fluorescence peak of probed element [Eu (III) Lα] and matrix constituents (Mn Kα) were discriminated using this technique, indicating its superiority in fluorescence detection. Copyright © 2013 John Wiley & Sons, Ltd.     

A high‐energy‐resolution resonant inelastic X‐ray scattering spectrometer at ID20 of the European Synchrotron Radiation Facility

An end‐station for resonant inelastic X‐ray scattering and (resonant) X‐ray emission spectroscopy at beamline ID20 of ESRF – The European Synchrotron is presented. The spectrometer hosts five crystal analysers in Rowland geometry for large solid angle collection and is mounted on a rotatable arm for scattering in both the horizontal and vertical planes. The spectrometer is optimized for high‐energy‐resolution applications, including partial fluorescence yield or high‐energy‐resolution fluorescence detected X‐ray absorption spectroscopy and the study of elementary electronic excitations in solids. In addition, it can be used for non‐resonant inelastic X‐ray scattering measurements of valence electron excitations.     

ED‐XRF set‐up for size‐segregated aerosol samples analysis

The knowledge of size‐segregated elemental concentrations in atmospheric particulate matter (PM) gives a useful contribution to the complete chemical characterisation; this information can be obtained by sampling with multi‐stage cascade impactors. In this work, samples were collected using a low‐pressure 12‐stage Small Deposit Impactor and a 13‐stage rotating Micro Orifice Uniform Deposit Impactor^?. Both impactors collect the aerosol in an inhomogeneous geometry, which needs a special set‐up for X‐ray analysis. This work aims at setting up an energy dispersive X‐ray fluorescence (ED‐XRF) spectrometer to analyse quantitatively size‐segregated samples obtained by these impactors. The analysis of cascade impactor samples by ED‐XRF is not customary; therefore, as additional consistency test some samples were analysed also by particle‐induced X‐ray emission (PIXE), which is more frequently applied to size‐segregated samples characterised by small PM quantities. A very good agreement between ED‐XRF and PIXE results was obtained for all the detected elements in samples collected with both impactors. The good inter‐comparability proves that our methodology is reliable for analysing size‐segregated samples by ED‐XRF technique. The advantage of this approach is that ED‐XRF is cheaper, easier to use, and more widespread than PIXE, thus promoting an intensive use of multi‐stage impactors. Copyright © 2011 John Wiley & Sons, Ltd.     

Simultaneous X‐ray fluorescence and scanning X‐ray diffraction microscopy at the Australian Synchrotron XFM beamline

Owing to its extreme sensitivity, quantitative mapping of elemental distributions via X‐ray fluorescence microscopy (XFM) has become a key microanalytical technique. The recent realisation of scanning X‐ray diffraction microscopy (SXDM) meanwhile provides an avenue for quantitative super‐resolved ultra‐structural visualization. The similarity of their experimental geometries indicates excellent prospects for simultaneous acquisition. Here, in both step‐ and fly‐scanning modes, robust, simultaneous XFM‐SXDM is demonstrated.     

A three‐crystal spectrometer for high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy and X‐ray emission spectroscopy at SSRF

A Johann‐type spectrometer for the study of high‐energy resolution fluorescence‐detected X‐ray absorption spectroscopy, X‐ray emission spectroscopy and resonant inelastic X‐ray scattering has been developed at BL14W1 X‐ray absorption fine structure spectroscopy beamline of Shanghai Synchrotron Radiation Facility. The spectrometer consists of three crystal analyzers mounted on a vertical motion stage. The instrument is scanned vertically and covers the Bragg angle range of 71.5–88°. The energy resolution of the spectrometer ranges from sub‐eV to a few eV. The spectrometer has a solid angle of about 1.87 × 0^?3 of 4π sr, and the overall photons acquired by the detector could be 10⁵ counts per second for the standard sample. The performances of the spectrometer are illustrated by the three experiments that are difficult to perform with the conventional absorption or emission spectroscopy. Copyright © 2016 John Wiley & Sons, Ltd.     

Application of Synchrotron X‐Ray Microbeam Spectroscopy to the Determination of Metal Distribution and Speciation in Biological Tissues

Abstract

Resolving the distribution and speciation of metal(loid)s within biological environmental samples is essential for understanding bioavailability, trophic transfer, and environmental risk. We used synchrotron x‐ray microspectroscopy to analyze a range of samples that had been exposed to metal(loid) contamination. Microprobe x‐ray fluorescence elemental mapping (µSXRF) of decomposing rhizosphere microcosms consisting of Ni‐ and U‐contaminated soil planted with wheat (Triticum aestivum) showed the change in Ni and U distribution over a 27‐day period, with a progressive movement of U into decaying tissue. µSXRF maps showed the micrometer‐scale distribution of Ca, Mn, Fe, Ni, and U in roots of willow (Salix nigra L.) growing on a former radiological settling pond, with U located outside of the epidermis and Ni inside the cortex. X‐ray computed tomography (CMT) of woody tissue of this same affected willow showed that small points of high Ni fluorescence observed previously are actually a Ni‐rich substance contained within an individual xylem vessel. µSXRF and x‐ray absorption near‐edge spectroscopy (XANES) linked the elevated Se concentrations in sediments of a coal fly ash settling pond with oral deformities of bullfrog tadpoles (Rana catesbeiana). Se distribution was localized within the deformed mouthparts, and with an oxidation state of Se (?II) consistent with organo‐Se compounds, it suggests oral deformities are caused by incorporation of Se into proteins. The range of tissues analyzed in this study highlight the applicability of synchrotron X‐ray microspectroscopic techniques to biological tissues and the study of metal(loid) bioavailability.     

Elemental depth imaging of solutions for monitoring corrosion process of steel sheet by confocal micro X‐ray fluorescence

Non‐destructive and non‐contact analysis has been in demand on numerous occasions. Confocal micro X‐ray fluorescence analysis enables depth‐selective elemental analysis of solid samples in the laboratory. In this paper, we applied this technique for imaging elemental distributions in solutions. A low‐carbon steel sheet was placed in artificial seawater (NaCl: 3.5 mass%), and the corrosion process in the solution was observed. A depth image of Fe Kα intensity in the NaCl solution was obtained by using this technique. The Fe Kα intensity in the solution was measured with corrosion time by sequential line analysis at a fixed lateral position. The corrosion of Fe from the steel sheet, the migration of Fe ions in solution, and their condensation near a polymer window were successfully monitored. Copyright © 2014 John Wiley & Sons, Ltd.     

X‐ray tube spectral measurement method for quantitative analysis of X‐ray fluorescence analysis

Lα and Lβ X‐ray fluorescence spectra of a lead metallic sheet were measured using an energy dispersive X‐ray spectrometer by changing the X‐ray tube voltage and the material of the primary filter. The Lα to Lβ intensity ratio changed from Lα: Lβ = 3: 1 at 15 kV to Lα: Lβ = 1: 1 at 50 kV depending on the X‐ray tube voltage and the filter. The scattered X‐ray spectra of an acrylic slab instead of the sample in the sample holder were measured by changing the applied voltage and the material of the primary filter. The calculated values of the Pb Lα/Lβ intensity ratio of the metallic sheet using the Shiraiwa–Fujino formula by inserting the scattered X‐ray spectra of an acrylic plate as incident X‐ray spectra and the fundamental parameters taken from the Elam database were in good agreement with the experimental ones. We conclude that we can obtain an incident X‐ray spectrum approximately by measuring the scattered X‐ray spectrum without measuring the direct incident beam. Copyright © 2010 John Wiley & Sons, Ltd.     

Measurement of L subshell fluorescence yield ratios of some high Z elements by selective excitation method

The L₁, L₂ and L₃ subshells of Hf, Ta and Re atoms have been excited selectively by using microprobe XRF beam line, Indus‐2, RRCAT, India. The consequent characteristic L X‐ray photons, emitted from the targets due to creations of vacancies in L subshells, are measured using silicon drift detector (X‐123) spectrometer. As the energy of synchrotron radiation increases, the contribution of characteristic L X‐ray intensity increases. The advantage of the increase in the intensity of the characteristic L X‐ray photons with an increase in the energy of synchrotron radiation has been used to determine the L subshell fluorescence yield ratios of Hf, Ta and Re atoms by adopting the selective excitation method. The measured ratios of L subshell fluorescence yield have been compared with theoretical and other experimental values.     

Optimized energy dispersive X‐ray fluorescence analysis of atmospheric aerosols collected at pristine and perturbed Amazon Basin sites

Elemental composition of aerosols is important to source apportionment studies and to understand atmospheric processes that influence aerosol composition. Energy dispersive X‐ray fluorescence spectroscopy was applied for measuring the elemental composition of Amazonian atmospheric aerosols. The instrument used was a spectrometer Epsilon 5, PANalytical B.V., with tridimensional geometry that reduces the background signal with a polarized X‐ray detection. The measurement conditions were optimized for low‐Z elements, e.g. Mg, Al, Si, that are present at very low concentrations in the Amazon. From Na to K, our detection limits are about 50% to 75% lower than previously published results for similar instrument. Calibration was performed using Micromatter standards, except for P whose standard was produced by nebulization of an aqueous solution of KH₂PO₄ at our laboratory. The multi‐element reference material National Institute of Standards and Technology–2783 (air particulate filter) was used for evaluating the accuracy of the calibration procedure of the 22 elements in our standard analysis routine, and the uncertainty associated with calibration procedures was evaluated. The overall performance of the instrument and validation of our measurements were assessed by comparison with results obtained from parallel analysis using particle‐induced X‐ray emission and another Epsilon 5 spectrometer. The elemental composition in 660 samples collected at a pristine site in the Amazon Basin and of 1416 samples collected at a site perturbed by land use change was determined. Our measurements show trace elements associated with biogenic aerosols, soil dust, biomass burning, and sea‐salt, even for the very low concentrations as observed in Amazonia. Copyright © 2014 John Wiley & Sons, Ltd.     

Comparison of the detection limits in the analysis of some medium atomic number elements measured with a portable XRF and an external proton beam PIXE spectrometer system

A portable X‐ray fluorescence (XRF) spectrometer system was constructed using an Amptek Mini‐X X‐ray tube and an X‐123 compact spectrometer. The spectrometer is optimised for the best limits of detection. Its analytic properties are tested and compared with an analogous laboratory‐based instrument, an external beam proton‐induced X‐ray emission spectrometry (PIXE) setup. Depending on elements in question the thick target detection limits of this portable XRF device are comparable or even lower than the PIXE setup. Copyright © 2011 John Wiley & Sons, Ltd.     

Investigation of nanoscale element distributions at surfaces with grazing incidence X‐ray spectroscopy techniques – an instrumentation study

Grazing incidence X‐ray methods are well‐established in the characterization of nanostructures at interfaces and surfaces. The purpose of the experiments reviewed in this work is the comparative characterization of different instrumentation concepts for grazing incidence X‐ray fluorescence analyses. Fluorescence scans recorded with a total reflection X‐ray fluorescence spectrometer featuring a variable angle of incidence are compared with data obtained with synchrotron radiation. The conclusions to the element distribution profiles, which are drawn from fluorescence scans carried out with the respective instrument, are compared. This way, the suitability of the total reflection X‐ray fluorescence spectrometer to complement synchrotron radiation facilities and the possibility to transfer surface and interface analyses from the synchrotron to the laboratory are assessed. The structures investigated include an Au on Si surfaces in the form of layers and particles, submicrometer‐sized droplets, a liquid film, and ions implanted into a Si wafer. Copyright © 2014 John Wiley & Sons, Ltd.     

Combined X‐ray microanalytical study of the Nd uptake capability of argillaceous rocks

Argillaceous rocks are considered as suitable host rock formation to isolate the high‐level radioactive waste from the biosphere for thousands of years. Boda Claystone Formation, the possible host rock formation for the Hungarian high‐level radioactive waste repository, has geologically and mineralogically been studied in detail, but its physico‐chemical parameters describing the retention capability of the rock needed further examinations. Studies were performed on thin sections subjected to 72 h sorption experiments using inactive Nd(III). Nd(III) has been used as a chemical analogue for transuranium elements of the radioactive waste to examine the ion uptake capability of the micrometre size mineral phases occurring in the rock. The elemental mapping of synchrotron radiation‐based microscopic X‐ray fluorescence (micro‐XRF) combined with scanning electron microscopy energy dispersive X‐ray analysis (SEM/EDX) has sufficient sensitivity to study the uptake capability of the different mineral phases on the microscale without the necessity of applying radioactive substances. Elemental maps were recorded on several thousand pixels using micrometre magnitude spatial resolution. By interleaving micro‐XRF and SEM/EDX data sets from the same sample area and applying multivariate methods, calcite and clay minerals could be identified as the main mineral phases responsible for Nd(III) uptake without using additional microscopic X‐ray diffraction mapping. It should be highlighted that the ion uptake capability of dolomite containing calcium and magnesium could be distinguished from the characteristics of calcite only by the interleaving of micro‐XRF and SEM/EDX data sets. The presence of minerals was verified by applying microscopic X‐ray diffraction point measurements. Copyright © 2015 John Wiley & Sons, Ltd.