A setup for synchrotron‐radiation‐induced total reflection X‐ray fluorescence and X‐ray absorption near‐edge structure recently commissioned at BESSY II BAMline

An automatic sample changer chamber for total reflection X‐ray fluorescence (TXRF) and X‐ray absorption near‐edge structure (XANES) analysis in TXRF geometry was successfully set up at the BAMline at BESSY II. TXRF and TXRF‐XANES are valuable tools for elemental determination and speciation, especially where sample amounts are limited (<1 mg) and concentrations are low (ng ml^?1 to µg ml^?1). TXRF requires a well defined geometry regarding the reflecting surface of a sample carrier and the synchrotron beam. The newly installed chamber allows for reliable sample positioning, remote sample changing and evacuation of the fluorescence beam path. The chamber was successfully used showing accurate determination of elemental amounts in the certified reference material NIST water 1640. Low limits of detection of less than 100 fg absolute (10 pg ml^?1) for Ni were found. TXRF‐XANES on different Re species was applied. An unknown species of Re was found to be Re in the +7 oxidation state.     

SUT‐NANOTEC‐SLRI beamline for X‐ray absorption spectroscopy

The SUT‐NANOTEC‐SLRI beamline was constructed in 2012 as the flagship of the SUT‐NANOTEC‐SLRI Joint Research Facility for Synchrotron Utilization, co‐established by Suranaree University of Technology (SUT), National Nanotechnology Center (NANOTEC) and Synchrotron Light Research Institute (SLRI). It is an intermediate‐energy X‐ray absorption spectroscopy (XAS) beamline at SLRI. The beamline delivers an unfocused monochromatic X‐ray beam of tunable photon energy (1.25–10 keV). The maximum normal incident beam size is 13 mm (width) × 1 mm (height) with a photon flux of 3 × 10⁸ to 2 × 10¹⁰ photons s^?1 (100 mA)^?1 varying across photon energies. Details of the beamline and XAS instrumentation are described. To demonstrate the beamline performance, K‐edge XANES spectra of MgO, Al₂O₃, S₈, FeS, FeSO₄, Cu, Cu₂O and CuO, and EXAFS spectra of Cu and CuO are presented.     

X‐ray reflectivity from curved liquid interfaces

X‐ray reflectivity studies of the structure of liquid–vapour and liquid–liquid interfaces at modern sources, such as free‐electron lasers, are currently impeded by the lack of dedicated liquid surface diffractometers. It is shown that this obstacle can be overcome by an alternative experimental approach that uses the natural curvature of a liquid drop for variation of the angle of incidence. Two modes of operation are shown: (i) sequential reflectivity measurements by a nanometre beam and (ii) parallel acquisition of large ranges of a reflectivity curve by micrometre beams. The feasibility of the two methods is demonstrated by studies of the Hg/vapour, H₂O/vapour and Hg/0.1 M NaF interface. The obtained reflectivity curves match the data obtained by conventional techniques up to 5α_c in micro‐beam mode and up to 35α_c in nano‐beam mode, allowing observation of the Hg layering peak.     

Investigation of nanoparticulate silicon as printed layers using scanning electron microscopy,transmission electron microscopy,X‐ray absorption spectroscopy and X‐ray photoelectron spectroscopy

The presence of native oxide on the surface of silicon nanoparticles is known to inhibit charge transport on the surfaces. Scanning electron microscopy (SEM) studies reveal that the particles in the printed silicon network have a wide range of sizes and shapes. High‐resolution transmission electron microscopy reveals that the particle surfaces have mainly the (111)‐ and (100)‐oriented planes which stabilizes against further oxidation of the particles. X‐ray absorption spectroscopy (XANES) and X‐ray photoelectron spectroscopy (XPS) measurements at the O 1s‐edge have been utilized to study the oxidation and local atomic structure of printed layers of silicon nanoparticles which were milled for different times. XANES results reveal the presence of the +4 (SiO₂) oxidation state which tends towards the +2 (SiO) state for higher milling times. Si 2p XPS results indicate that the surfaces of the silicon nanoparticles in the printed layers are only partially oxidized and that all three sub‐oxide, +1 (Si₂O), +2 (SiO) and +3 (Si₂O₃), states are present. The analysis of the change in the sub‐oxide peaks of the silicon nanoparticles shows the dominance of the +4 state only for lower milling times.     

X‐ray absorption near‐edge structure anomalous behaviour in structures with buried layers containing silicon nanocrystals

Substructure and phase composition of silicon suboxide films containing silicon nanocrystals and implanted with carbon have been investigated by means of the X‐ray absorption near‐edge structure technique with the use of synchrotron radiation. It is shown that formation of silicon nanocrystals in the films' depth (more than 60 nm) and their following transformation into silicon carbide nanocrystals leads to abnormal behaviour of the X‐ray absorption spectra in the elementary silicon absorption‐edge energy region (100–104 eV) or in the silicon oxide absorption‐edge energy region (104–110 eV). This abnormal behaviour is connected to X‐ray elastic backscattering on silicon or silicon carbide nanocrystals located in the silicon oxide films depth.     

Effects of organic ligands on Pb absorption and speciation changes in Arabidopsis as determined by micro X‐ray fluorescence and X‐ray absorption near‐edge structure analysis

Pb can pass through the food chain via plants and threaten human health, which has attracted widespread attention. Changes in Pb speciation affect its bioavailability in soils and water. However, whether organic ligands can change the uptake and mobility of Pb in plants and increase or decrease Pb bioavailability remains uncertain. To reveal the roles of organic and inorganic Pb in Pb metabolism in plants, the localization and speciation changes of Pb in Arabidopsis thaliana plants grown in organic and inorganic Pb were characterized by synchrotron radiation micro X‐ray fluorescence and X‐ray absorption near‐edge structure, respectively. These results demonstrated that Arabidopsis absorbed more Pb from Pb(NO₃)₂ than Pb(CH₃COO)₂ at the same exposure concentration. A higher percentage of Pb‐citrate was found in Arabidopsis exposed to inorganic Pb solution, which suggested that Pb‐citrate was the main complex for root‐to‐shoot transportation in Arabidopsis exposed to inorganic Pb solutions. Pb complexed with the organic ligand CH₃COO^? significantly inhibited primary root growth and lateral root development, while, at the same time, Pb was blocked by root hairs, which represented another way to reduce Pb absorption and protect the plant from biotoxicity.     

Titanium local structure in tektite probed by X‐ray absorption fine structure spectroscopy

The local structure of titanium in tektites from six strewn fields was studied by Ti K‐edge X‐ray absorption near edge structure (XANES) and extended X‐ray absorption fine structure (EXAFS) in order to provide quantitative data on Ti—O distance and Ti coordination number. The titanium in tektites possessed different coordination environment types. XANES spectra patterns revealed resemblance to high‐temperature TiO₂–SiO₂ glass and TiO₂ anatase. All samples showed that the valence of Ti is 4+. Based on the Ti—O distances, coordination numbers and radial distribution function determined by EXAFS analyses, the tektites were classified into three types: type I, Ti occupies a four‐coordinated tetrahedral site with Ti—O distances of 1.84–1.79 Å; type II, Ti occupies a five‐coordinated trigonal bipyramidal or tetragonal pyramidal site with Ti—O distances of 1.92–1.89 Å; type III, Ti occupies a six‐coordinated octahedral site with Ti—O distances of 2.00–1.96 Å. Although Ti occupies the TiO₆ octahedral site in most titanium minerals under ambient conditions, some tektites have four‐ and five‐coordinated Ti. This study indicated that the local structure of Ti might change in impact events and the following stages.     

A novel X‐ray diffractometer for studies of liquid–liquid interfaces

The study of liquid–liquid interfaces with X‐ray scattering methods requires special instrumental considerations. A dedicated liquid surface diffractometer employing a tilting double‐crystal monochromator in Bragg geometry has been designed. This diffractometer allows reflectivity and grazing‐incidence scattering measurements of an immobile mechanically completely decoupled liquid sample, providing high mechanical stability. The available energy range is from 6.4 to 29.4 keV, covering many important absorption edges. The instrument provides access in momentum space out to 2.54 Å^?1 in the surface normal and out to 14.8 Å^?1 in the in‐plane direction at 29.4 keV. Owing to its modular design the diffractometer is also suitable for heavy apparatus such as vacuum chambers. The instrument performance is described and examples of X‐ray reflectivity studies performed under in situ electrochemical control and on biochemical model systems are given.     

In situ X‐ray absorption spectroscopic studies of copper in a copper‐rich sludge during electrokinetic treatments

Speciation of copper in a copper‐rich chemical‐mechanical polishing sludge during electrokinetic treatment has been studied by in situ extended X‐ray absorption fine structure (EXAFS) and X‐ray absorption near‐edge structure (XANES) spectroscopy. The least‐squares‐fitted XANES spectra indicate that the main copper species in the sludge are Cu(OH)₂ (74%), nanosize CuO (20–60 nm) (13%) and CuO (>100 nm) (13%). The average bond distance and coordination number (CN) of Cu—O are 1.96 Å and 3.5, respectively. Under electrokinetic treatment (5 V cm^?1) for 120 min, about 85% of the copper is dissolved in the electrolyte, 13% of which is migrated and enriched on the cathode. Notably the copper nanoparticles in the sludge can also migrate to the cathode under the electric field. By in situ EXAFS, it is found that during the electrokinetic treatment the bond distance and CN of Cu—O are increased by 0.1 Å and 0.9, respectively.     

X‐ray powder diffraction at the XRD1 beamline at LNLS

Various upgrades have been completed at the XRD1 beamline at the Brazilian synchrotron light source (LNLS). The upgrades are comprehensive, with changes to both hardware and software, now allowing users of the beamline to conduct X‐ray powder diffraction experiments with faster data acquisition times and improved quality. The main beamline parameters and the results obtained for different standards are presented, showing the beamline ability of performing high‐quality experiments in transmission geometry. XRD1 operates in the 5.5–14 keV range and has a photon flux of 7.8 × 10⁹ photons s^?1 (with 100 mA) at 12 keV, which is one of the typical working energies. At 8 keV (the other typical working energy) the photon flux at the sample position is 3.4 × 10¹⁰ photons s^?1 and the energy resolution ΔE/E = 3 × 10^?4.     

An attempt to analyze the bark disease in Havea brasiliensis using X‐ray absorption near‐edge spectroscopy

The X‐ray absorption near‐edge spectroscopy (XANES) technique has been used to determine the chemical change of elements induced by bark diseases in Havea brasiliensis (rubber latex tree). The results show the good sensitivity of in situ XANES for characterizing the chemical structure of phosphorus, sulfur, potassium and calcium in healthy and diseased Havea brasiliensis. Important information for understanding the bark disease involved in the sulfur metabolism of plants was also obtained from XANES.     

A large‐volume gas cell for high‐energy X‐ray reflectivity investigations of interfaces under pressure

A cell for the investigation of interfaces under pressure is presented. Given the pressure and temperature specifications of the cell, P≤ 100 bar and 253 K ≤T≤ 323 K, respectively, high‐energy X‐rays are required to penetrate the thick Al₂O₃ windows. The CH₄(gas)/H₂O(liquid) interface has been chosen to test the performance of the new device. The measured dynamic range of the high‐energy X‐ray reflectivity data exceeds 10^?8, thereby demonstrating the validity of the entire experimental set‐up.     

Protective radiolucent aluminium oxide coatings for beryllium X‐ray optics

Beryllium, being one of the most transparent materials to X‐ray radiation, has become the material of choice for X‐ray optics instrumentation at synchrotron radiation sources and free‐electron laser facilities. However, there are concerns due to its high toxicity and, consequently, there is a need for special safety regulations. The authors propose to apply protective coatings in order to seal off beryllium from the ambient atmosphere, thus preventing degradation processes providing additional protection for users and prolonging the service time of the optical elements. This paper presents durability test results for Be windows coated with atomic‐layer‐deposition alumina layers run at the European Synchrotron Radiation Facility. Expositions were performed under monochromatic, pink and white beams, establishing conditions that the samples could tolerate without radiation damage. X‐ray treatment was implemented in various environments, i.e. vacuum, helium, nitrogen, argon and dry air at different pressures. Post‐process analysis revealed their efficiency for monochromatic and pink beams.     

Hard X‐ray nanotomography beamline 7C XNI at PLS‐II

The synchrotron‐based hard X‐ray nanotomography beamline, named 7C X‐ray Nano Imaging (XNI), was recently established at Pohang Light Source II. This beamline was constructed primarily for full‐field imaging of the inner structures of biological and material samples. The beamline normally provides 46 nm resolution for still images and 100 nm resolution for tomographic images, with a 40 µm field of view. Additionally, for large‐scale application, it is capable of a 110 µm field of view with an intermediate resolution.     

In situ X‐ray diffraction study on the growth kinetics of NiO nanoparticles

The growth kinetics of NiO nanoparticles have been studied by in situ X‐ray diffraction using two detection systems (conventional and imaging plate). NiO nanoparticles were formed by thermal decomposition after heating of an amorphous compound formed by the coprecipitation method. It was found that the detection method using an imaging plate is more efficient than the conventional detection mode for observing changes in the crystallite growth of nanocrystalline materials. Studies have been carried out to investigate the effects of the heating rates on the particles growth. The results suggest that the growth process of the particles is accelerated when the samples are treated at low heating rates. The evolution of particles size and the diffusion coefficient obtained from X‐ray powder diffraction patterns are discussed in terms of the thermal conditions for the two types of detection.     

XAS spectroelectrochemistry: reliable measurement of X‐ray absorption spectra from redox manipulated solutions at room temperature

The design and operation of a low‐volume spectroelectrochemical cell for X‐ray absorption spectroscopy (XAS) of solutions at room temperature is described. Fluorescence XAS measurements are obtained from samples contained in the void space of a 50 µL reticulated vitreous carbon (sponge) working electrode. Both rapid electrosynthesis and control of the effects of photoreduction are achieved by control over the flow properties of the solution through the working electrode, where a good balance between the rate of consumption of sample and the minimization of decomposition was obtained by pulsing the flow of the solution by 1–2 µL with duty cycle of ～3 s while maintaining a small net flow rate (26–100 µL h^?1). The performance of the cell in terms of control of the redox state of the sample and minimization of the effects of photoreduction was demonstrated by XAS measurements of aqueous solutions of the photosensitive Fe^III species, [Fe(C₂O₄)₃]^3?, together with that of the electrogenerated [Fe(C₂O₄)₃]^4? product. The current response from the cell during the collection of XAS spectra provides an independent measure of the stability of the sample of the measurement. The suitability of the approach for the study of small volumes of mM concentrations of protein samples was demonstrated by the measurement of the oxidized and electrochemically reduced forms of cytochrome c.     

Analysis of engine motor oils by X‐ray absorption and X‐ray fluorescence spectroscopies

The molecular structure of lubricating motor oils is investigated by X‐ray absorption fine structure spectroscopy measurements. Both fresh and used oils are studied. Although the Zn K‐edge spectra gave information about the degradation of the antiwear/antioxidant zinc dialkyl dithiophosphate (ZDDP) additives within the oil, Fe K‐edge spectra are representatives for iron species dispersed in the oil during operation at elevated temperatures and pressures in the engine. The detailed analysis of the measured data shows that substantial differences are detectable in the spectra of the fresh and used oil. Our results show that the Zn–S bonds of the ZDDP are decomposed during the operation, resulting in Zn–O bonds instead. Furthermore, sixfold Fe–O bonds similar to those in Fe₂O₃ are found within the used oil, suggesting the presence of debris from the antiwear film of lubricated motor parts in the used oil. Copyright © 2014 John Wiley & Sons, Ltd.     

Biological soft X‐ray tomography on beamline 2.1 at the Advanced Light Source

Beamline 2.1 (XM‐2) is a transmission soft X‐ray microscope in sector 2 of the Advanced Light Source at Lawrence Berkeley National Laboratory. XM‐2 was designed, built and is now operated by the National Center for X‐ray Tomography as a National Institutes of Health Biomedical Technology Research Resource. XM‐2 is equipped with a cryogenic rotation stage to enable tomographic data collection from cryo‐preserved cells, including large mammalian cells. During data collection the specimen is illuminated with `water window' X‐rays (284–543 eV). Illuminating photons are attenuated an order of magnitude more strongly by biomolecules than by water. Consequently, differences in molecular composition generate quantitative contrast in images of the specimen. Soft X‐ray tomography is an information‐rich three‐dimensional imaging method that can be applied either as a standalone technique or as a component modality in correlative imaging studies.