Np(V) Retention at the Illite du Puy Surface.

In this study, Np(V) retention on Illite du Puy (IdP) was investigated since it is essential for understanding the migration behavior of Np in argillaceous environments. The presence of structural Fe(III) and Fe(II) in IdP was confirmed by Fe K-edge X-ray absorption near-edge structure (XANES) and 57Fe Mössbauer spectroscopy. In batch sorption experiments, a higher Np sorption affinity to IdP was found than to Wyoming smectite or iron-free synthetic montmorillonite. An increase of the relative Np(IV) ratio sorbed onto IdP with decreasing pH was observed by solvent extraction (up to (24 ± 2)% at pH 5, c0(Np) = 10-6 mol/L). Furthermore, up to (33 ± 5)% Np(IV) could be detected in IdP diffusion samples at pH 5. Respective Np M5-edge high-energy resolution (HR-) XANES spectra suggested the presence of Np(IV/V) mixtures and weakened axial bond covalency of the NpO2+ species sorbed onto IdP. Np L3-edge extended X-ray absorption fine structure (EXAFS) analysis showed that significant fractions of Np were coordinated to Fe─O entities at pH 9. This highlights the potential role of Fe(II/III) clay edge sites as a strong Np(V) surface complex partner and points to the partial reduction of sorbed Np(V) to Np(IV) via structural Fe(II).

Multicolor single-analyzer high-energy-resolution XES spectrometer for simultaneous examination of different elements.

The present work demonstrates the performance of a von Hámos high-energy-resolution X-ray spectrometer based on a non-conventional conical Si single-crystal analyzer. The analyzer is tested with different primary and secondary X-ray sources as well as a hard X-ray sensitive CCD camera. The spectrometer setup is also characterized with ray-tracing simulations. Both experimental and simulated results affirm that the conical spectrometer can efficiently detect and resolve the two pairs of two elements (Ni and Cu) Kα X-ray emission spectroscopy (XES) peaks simultaneously, requiring a less than 2 cm-wide array on a single position-sensitive detector. The possible applications of this simple yet broad-energy-spectrum crystal spectrometer range from quickly adapting it as another probe for complex experiments at synchrotron beamlines to analyzing X-ray emission from plasma generated by ultrashort laser pulses at modern laser facilities.

Site-Selective Real-Time Observation of Bimolecular Electron Transfer in a Photocatalytic System Using L-Edge X-Ray Absorption Spectroscopy*.

Time-resolved X-ray absorption spectroscopy has been utilized to monitor the bimolecular electron transfer in a photocatalytic water splitting system. This has been possible by uniting the local probe and element specific character of X-ray transitions with insights from high-level ab initio calculations. The specific target has been a heteroleptic [IrIII (ppy)2 (bpy)]+ photosensitizer, in combination with triethylamine as a sacrificial reductant and Fe3(CO)12 as a water reduction catalyst. The relevant molecular transitions have been characterized via high-resolution Ir L-edge X-ray absorption spectroscopy on the picosecond time scale and restricted active space self-consistent field calculations. The presented methods and results will enhance our understanding of functionally relevant bimolecular electron transfer reactions and thus will pave the road to rational optimization of photocatalytic performance.

Performance of the BL03U beamline at SSRF.

The vacuum ultraviolet beamline BL03U with a photon energy range from 7 eV upwards has been constructed at the 3.5 GeV Shanghai Synchrotron Radiation Facility. Equipped with an APPLE-Knot undulator, this beamline is dedicated to angle-resolved photoemission spectroscopy. An energy-resolving power of higher than 4.6 × 104 has been achieved in the photon energy range 21.6-48 eV, which is almost the same as the theoretical estimation.

Study on the reflectivity properties of spherically bent analyser crystals. Corrigendum.

Corrections to the paper by Honkanen et al. (2014). [J. Synchrotron Rad. 21, 104-110] are made.

High-Energy-Resolution X-ray Absorption Spectroscopy for Identification of Reactive Surface Species on Supported Single-Site Iridium Catalysts.

We report high-energy-resolution X-ray absorption spectroscopy detection of ethylene and CO ligands adsorbed on catalytically active iridium centers isolated on zeolite HY and on MgO supports. The data are supported by density functional theory and FEFF X-ray absorption near-edge modelling, together with infrared (IR) spectra. The results demonstrate that high-energy-resolution X-ray absorption spectra near the iridium LIII (2p3/2 ) edge provide clearly ascribable, distinctive signatures of the ethylene and CO ligands and illustrate effects of supports and other ligands. This X-ray absorption technique is markedly more sensitive than conventional IR spectroscopy for characterizing surface intermediates, and it is applicable to samples having low metal loadings and in reactive atmospheres and is expected to have an increasing role in catalysis research by facilitating the determination of mechanisms of solid-catalyzed reactions through identification of reaction intermediates in working catalysts.

A Low-Noise X-ray Astronomical Silicon-On-Insulator Pixel Detector Using a Pinned Depleted Diode Structure.

This paper presents a novel full-depletion Si X-ray detector based on silicon-on-insulator pixel (SOIPIX) technology using a pinned depleted diode structure, named the SOIPIX-PDD. The SOIPIX-PDD greatly reduces stray capacitance at the charge sensing node, the dark current of the detector, and capacitive coupling between the sensing node and SOI circuits. These features of the SOIPIX-PDD lead to low read noise, resulting high X-ray energy resolution and stable operation of the pixel. The back-gate surface pinning structure using neutralized p-well at the back-gate surface and depleted n-well underneath the p-well for all the pixel area other than the charge sensing node is also essential for preventing hole injection from the p-well by making the potential barrier to hole, reducing dark current from the Si-SiO2 interface and creating lateral drift field to gather signal electrons in the pixel area into the small charge sensing node. A prototype chip using 0.2 µm SOI technology shows very low readout noise of 11.0 e-rms, low dark current density of 56 pA/cm² at -35 °C and the energy resolution of 200 eV(FWHM) at 5.9 keV and 280 eV (FWHM) at 13.95 keV.

Ultra-stable sub-meV monochromator for hard X-rays.

A high-resolution silicon monochromator suitable for 21.541 keV synchrotron radiation is presented that produces a bandwidth of 0.27 meV. The operating energy corresponds to a nuclear transition in (151)Eu. The first-of-its-kind, fully cryogenic design achieves an energy-alignment stability of 0.017 meV r.m.s. per day, or a 100-fold improvement over other meV-monochromators, and can tolerate higher X-ray power loads than room-temperature designs of comparable resolution. This offers the potential for significantly more accurate measurements of lattice excitation energies using nuclear resonant vibrational spectroscopy if combined with accurate energy calibration using, for example, high-speed Doppler shifting. The design of the monochromator along with its performance and impact on transmitted beam properties are presented.

Resonant inelastic X-ray scattering spectrometer with 25 meV resolution at the Cu K-edge.

An unparalleled resolution is reported with an inelastic X-ray scattering instrument at the Cu K-edge. Based on a segmented concave analyzer, featuring single-crystal quartz (SiO2) pixels, the spectrometer delivers a resolution near 25 meV (FWHM) at 8981 eV. Besides the quartz analyzer, the performance of the spectrometer relies on a four-bounce Si(553) high-resolution monochromator and focusing Kirkpatrick-Baez optics. The measured resolution agrees with the ray-tracing simulation of an ideal spectrometer. The performance of the spectrometer is demonstrated by reproducing the phonon dispersion curve of a beryllium single-crystal.

Catalysis seen in action.

Synchrotron radiation techniques are widely applied in materials research and heterogeneous catalysis. In homogeneous catalysis, its use so far is rather limited despite its high potential. Here, insights in the strengths and limitations of X-ray spectroscopy technique in the field of homogeneous catalysis are given, including new technique developments. A relevant homogeneous catalyst, used in the industrially important selective oligomerization of ethene, is taken as a worked-out example. Emphasis is placed on time-resolved operando X-ray absorption spectroscopy with outlooks to novel high energy resolution and emission techniques. All experiments described have been or can be done at the Diamond Light Source Ltd (Didcot, UK).

Study on the reflectivity properties of spherically bent analyser crystals.

Theoretical and experimental studies are presented on properties of spherically bent analyser crystals for high-resolution X-ray spectrometry. A correction to the bent-crystal strain field owing to its finite surface area is derived. The results are used to explain the reflectivity curves and anisotropic properties of Si(660) and Si(553) analysers in near-backscattering geometry. The results from the calculation agree very well with experimental results obtained using an inelastic X-ray scattering synchrotron beamline.

New soft X-ray beamline BL07LSU at SPring-8.

A new soft X-ray beamline, BL07LSU, has been constructed at SPring-8 to perform advanced soft X-ray spectroscopy for materials science. The beamline is designed to achieve high energy resolution (E/ΔE> 10000) and high photon flux [>10(12) photons s(-1) (0.01% bandwidth)(-1)] in the photon energy range 250-2000 eV with controllable polarization. To realise this state-of-the-art performance, a novel segmented cross undulator was developed and adopted as a light source. The details of the undulator light source and beamline monochromator design are described. The achieved performance of the beamline, such as the photon flux, energy resolution and the state of polarization, is reported.

Synchrotron speciation of umbilical cord mercury and selenium after environmental exposure in Niigata.

The insidious and deadly nature of mercury's organometallic compounds is informed by two large scale poisonings due to industrial mercury pollution that occurred decades ago in Minamata and Niigata, Japan. The present study examined chemical speciation for both mercury and selenium in a historic umbilical cord sample from a child born to a mother who lived near the Agano River in Niigata. The mother had experienced mercury exposure leading to more than 50 ppm mercury measured in her hair and was symptomatic 9 years prior to the birth. We sought to determine the mercury and selenium speciation in the child's cord using Hg Lα1 and Se Kα1 high-energy resolution fluorescence detected X-ray absorption spectroscopy, the chemical speciation of mercury was found to be predominantly organometallic and coordinated to a thiolate. The selenium was found to be primarily in an organic form and at levels higher than those of mercury, with no evidence of mercury-selenium chemical species. Our results are consistent with mercury exposure at Niigata being due to exposure to organometallic mercury species.

High-accuracy measurement, advanced theory and analysis of the evolution of satellite transitions in manganese Kα using XR-HERFD.

Here, the novel technique of extended-range high-energy-resolution fluorescence detection (XR-HERFD) has successfully observed the n = 2 satellite in manganese to a high accuracy. The significance of the satellite signature presented is many hundreds of standard errors and well beyond typical discovery levels of three to six standard errors. This satellite is a sensitive indicator for all manganese-containing materials in condensed matter. The uncertainty in the measurements has been defined, which clearly observes multiple peaks and structure indicative of complex physical quantum-mechanical processes. Theoretical calculations of energy eigenvalues, shake-off probability and Auger rates are also presented, which explain the origin of the satellite from physical n = 2 shake-off processes. The evolution in the intensity of this satellite is measured relative to the full Kα spectrum of manganese to investigate satellite structure, and therefore many-body processes, as a function of incident energy. Results demonstrate that the many-body reduction factor S02 should not be modelled with a constant value as is currently done. This work makes a significant contribution to the challenge of understanding many-body processes and interpreting HERFD or resonant inelastic X-ray scattering spectra in a quantitative manner.

Development of a high energy resolution and wide dose rate range portable gamma-ray spectrometer.

In this paper, a portable gamma-ray spectrometer for real-time and in-situ gamma-ray detection applications is presented. By combining a quasi-hemispherical CdZnTe (CZT) semiconductor detector and a Geiger-Muller (GM) counter together, a wide dose rate range is achieved, ranging from 0.1 µSv/h to 100 mSv/h with a relative error of less than 10%. The GM counter is used to measure dose rate from 1 mSv/h to 100 mSv/h. With CZT, the spectrometer can provide a high energy resolution spectrum for nuclide identification and a high precision dose rate at low dose rates. The full width half maximum (FWHM) resolution is 2.2% at 662 keV below 70 µSv/h and is better than 3.3% at 3.8 mSv/h. The weight of the spectrometer is 3.2 kg for handheld and the runtime is up to 12 h without charging. For preliminary applications, the spectrometer was used to measure the gamma radiation around the Back-n white neutron beam line at China Spallation Neutron Source and around the steam generator in the nuclear power plant at Daya Bay Nuclear Power Station.

Paving the way for examination of coupled redox/solid-liquid interface reactions: 1 ppm Np adsorbed on clay studied by Np M5-edge HR-XANES spectroscopy.

The recently emerged actinide (An) M4,5-edge high-energy resolution X-ray absorption near-edge structure (HR-XANES) technique has proven to be very powerful for oxidation state studies of actinides. In this work, for the first time, Np M5-edge HR-XANES was applied to study Np sorption on illite. By improving the experimental conditions, notably by operation of the spectrometer under He atmosphere, it was possible to measure Np M5-edge HR-XANES spectra of a sample with ≈ 1 µg Np/g illite (1 ppm). This is 30-2000 times lower than Np loadings on mineral surfaces usually investigated by X-ray absorption spectroscopy. A newly designed cryogenic configuration enabled sample temperatures of 141.2 ± 1.5 K and successfully prevented beam-induced changes of the Np oxidation state. The described approach paves the way for the examination of coupled redox/solid-liquid interface reactions of actinide ions via An M4,5-edge HR-XANES spectroscopy at low metal ion concentrations, which are of specific relevance for contaminated sites and nuclear waste disposal studies.

Photon-in/photon-out spectroscopy at the I20-scanning beamline at diamond light source.

A scanning multi-crystal x-ray emission spectrometer to perform photon-in/photon-out spectroscopy at the I20-Scanning beamline at Diamond Light Source is described. The instrument, equipped with three analyzer crystals, is based on a 1 m Rowland circle spectrometer operating in the vertical plane. The energy resolution of the spectrometer is of the order of 1 eV, having sufficient resolving power to overcome the core-hole lifetime broadening of most of the transition metalsK-edges. Examples showing the capability of the beamline for performing high energy resolution fluorescence detection x-ray absorption spectroscopy (HERFD-XAS), non-resonant x-ray emission spectroscopy (XES) and resonant x-ray emission spectroscopy are presented. The comparison of the Zn and MnK-edge HERFD-XANES of ZnO and MnO withab initiocalculations shows that the technique provides enhanced validation of the models by making subtle spectral features more visible.

A new gamma spectroscopy methodology based on probabilistic uncertainty estimation and conservative approach.

The gamma spectroscopy technique is commonly used in many applications to evaluate the activity of gamma emitters in a given sample. This assessment of activity is of particular interest for the disposal of radioactive waste or for clearance purposes. However, for these specific applications, one needs to show that the evaluated activities are reasonably conservative. This paper shows an application of a methodology developed to quantify the efficiency calibration curve uncertainties originating from a test case sample and its associated geometry modelling. Therefore, the effects of enclosing geometries on the activity measurement results are discussed. The purpose is to provide an example of uncertainty analysis for an approach that could be applied to other studies in which a conservative estimation of the activity is required.

Low-dose low-scattering X-ray computed tomography with high-spatial-energy resolutions using a cooled cadmium telluride detector.

To improve the image quality of photon-counting energy-dispersive X-ray computed tomography (CT) and to reduce the incident dose for the object, we have developed a low-dose low-scattering CT scanner with high-spatial and -energy resolutions using a cooled cadmium telluride (CdTe) detector. X-ray photons are absorbed by the CdTe crystal, and the event pulses from the shaping amplifier are input to a high-speed triple-energy (TE) counter. In the TE-CT, four 3.0-mm-thick lead (Pb) pinholes are used. The line-beam diameter is roughly reduced using the first 2.0-mm-diam pinhole. Using the second 0.5-mm-diam pinhole, the line-beam diameter is reduced again, and the 0.5-mm-diam line beam is exposed to the object. The scattering photon count was reduced using the third 0.5-mm-diam pinhole, and the only penetrating photons are absorbed by the cooled CdTe crystal through the fourth 0.3-mm-diam pinhole for improving the spatial resolution. K-edge tomograms using iodine (I) and gadolinium (Gd) media were obtained simultaneously at two energy ranges of 33-50 and 50-100 keV, respectively. Utilizing I-K-edge CT, coronary arteries filled with I medium were visible. Next, blood vessels filled with Gd medium were observed at high contrasts using Gd-K-edge CT. The maximum count rate was 30 kilocounts per second (kcps) at a tube current of 0.33 mA, and the minimum count rate after penetrating objects was approximately 2 kcps. The maximum incident dose for the object was approximately 0.3 mGy, and the exposure time for TE-CT was 19.6 min at a total rotation angle of 360°. The energy resolution of the detector was 1.1% at 59.5 keV, and the spatial resolutions had values of 0.3 × 0.3 mm2.

Advanced X-ray Spectroscopic Methods for Studying Iron-Sulfur-Containing Proteins and Model Complexes.

In this chapter, a brief overview of X-ray spectroscopic methods that may be utilized to obtain insight into the geometric and electronic structure of iron-sulfur proteins is provided. These methods include conventional methods, such as metal and ligand K-edge X-ray absorption, as well as more advanced methods including nonresonant and resonant X-ray emission. In each section, the basic information content of the spectra is highlighted and important experimental considerations are discussed. Throughout the chapter, recent applications to iron-sulfur-containing models and proteins are highlighted.