A structural model for the geometry of Fe(III) octahedra near the surface of finely divided ferrihydrite was elaborated based on the bond-valence theory and by considering the interaction of water molecules in the 2 nearest hydration spheres. In contrast to bulk Fe atoms, which are bonded to bridging oxo (O) and hydroxo (OH) ligands, surface Fe atoms are also octahedrally coordinated to H2O ligands forming the 1st hydration shell ((H2O)I). In the wet state, external water molecules of the 2nd hydration shell ((H2O)II) are singly H-bonded to (H2O)I, while they are doubly coordinated in the dry state. Accordingly, wet ferrihydrite contains twice as many sorbed water molecules as dry ferrihydrite, and the structural difference due to the 2nd hydration shell accounts quantatively for the 15% increase of ferrihydrite weight experimentally measured in moist atmosphere. The interaction of surface Fe atoms with their 2 nearest hydration spheres modifies the geometry of surface Fe octahedra as compared to bulk octahedra, and idealized Fe-OH and Fe-H2O bond lengths in the wet and dry state were evaluated by the bond-valence theory. Our structural model provides a sound crystal-chemical basis to describe many apparent incongruities of Fe X-ray absorption near edge structure (K-XANES) and extended X-ray absorption fine structure (EXAFS) spectroscopic data that have led to differing interpretations of the coordination environment of Fe in ferrihydrite by various investigators.

The substitution in layered double hydroxide-like phases (LDH) of composition $\begin{array}{cc}{\left({\text{Co}}_{1-y}^{2+}{\text{Cu}}_y^{2+}\right)}_2{\text{Al}}^{3+}{\left(\text{OH}\right)}_6{\text{Cl}}^{-}\cdot n{\text{H}}_{\text{2}}\text{O}& \left(0⩽y⩽1\right)\end{array}$ was studied by X-ray diffraction and X-ray absorption spectroscopy. It was found that the lamellar character is maintained over the entire range of the substitution. The local order for the composition {Co2Al} is typical of brucite-like sheets, whereas segregation into small domains may explain the results obtained when the percentage of Cu atoms is increased. The {Cu2Al} end-member material presents a local order around the Cu atoms closely related to the botallackite structure as present in basic layered Cu salts, with the presence of two distinct Cu-Cu distances.

Pyrrhotite Fe1–xS is the main sulfide component of platinum-group element (PGE) ores and commonly contains from a few tenths to a few dozen ppm of disseminated Pt. Here we report an X-ray absorption spectroscopy investigation into the state of Pt in synthetic pyrrhotite in combination with theoretical spectra modelling. The pyrrhotite crystals were obtained by means of the salt flux technique, using a eutectic mixture of alkali metal halides as the transport media. Analysis of the chemical composition of synthesised crystals showed that an increase of the temperature and sulfur fugacity yields higher concentrations of Pt in pyrrhotite. The Pt content reached 0.6 wt.% at the maximum temperature and sulfur fugacity (t = 720°C, log $f_{{\rm S}_ 2}$ = –0.1) achieved in a Pt-saturated system. X-ray absorption near-edge structure (XANES) analysis of Pt L3-edge spectra revealed that Pt is present in pyrrhotite in the 4+ and 2+ ‘formal’ oxidation states. Theoretical modelling of XANES and interpretation of extended X-ray absorption fine structure (EXAFS) spectra showed that Pt4+ substitutes for Fe in the crystal lattice of pyrrhotite, whereas Pt2+ forms PtS-like clusters disseminated in the pyrrhotite matrix. Atoms of isomorphous Pt4+ are surrounded by 6 S atoms at a distance of 2.39 ± 0.02 Å. According to theoretical simulations using the FDMNES program, the second coordination sphere of the solid-solution Pt contains one vacancy in the Fe sublattice within the Fe-layer. The Pt2+S-like clusters can be considered as a quench product. High sulfur fugacity stabilises the solid-solution Pt and prevents the formation of the PtS-like clusters during cooling. The maximum content of the solid-solution Pt in pyrrhotite is ca. 50 times lower than in pyrite and can be approximated by a straight line in the log C(Pt) vs. 1/T plot, it increases from 1 ppm at 350°C to 3 wt.% at 900°C.

The crystal structure of trimethylarsine oxide dihydrate, (CH3)3AsO⋅2H2O, (TMAO dihydrate) has been solved using parallel tempering with the FOX software package and refined using synchrotron powder diffraction data obtained from beamline 08B1-1 at the Canadian Light Source. Rietveld refinement, performed with the software package GSASII, yielded orthorhombic lattice parameters of a = 13.3937(4) Å, b = 9.53025(30) Å, and c = 11.5951(3) Å (Z = 8, space group Pbca). The Rietveld refined structure was compared with density functional theory calculations performed with VASP and shows reasonable agreement. Arsenic K-edge X-ray absorption spectroscopy analysis also revealed additional information on the electronic structure of the arsenic atom within the TMAO dihydrate structure.

Eudialyte-group minerals (EGM) attract global interest as potential resources for high-field-strength elements (e.g. Zr, Nb, Ta, and rare-earth elements), i.e. critical materials for modern technologies. They are particularly valued for their relative enrichment in the most critical lanthanides, i.e. Nd and heavy rare earth elements (Gd–Lu). However, rare earth element (REE) substitution mechanisms into the EGM structure are still poorly understood. Light and heavy REE may occupy different sites and there may be ordering and/or defect clustering in the structure. This study uses X-ray absorption spectroscopy to determine the structural state of REE in EGM from prospective eudialyte-bearing complexes. Yttrium K-edge and Nd L3-edge spectra were collected as proxies for heavy and light REE, respectively, and compared to natural and synthetic REE-bearing standards. Extended X-ray absorption fine structure data yield best fits for Y in six-fold coordination with Y–O distances of 2.24–2.32 Å, and a second coordination sphere comprising Fe, Na, Ca, Si and O at radial distances of 3.6–3.8 Å. These findings are consistent with dominant Y3+ substitution for Ca2+ on the octahedral M1 site in all the samples studied, and exclude preferential substitution of Y3+ onto the smaller octahedral Z site or the large low-symmetry N4 site.

Using lattice strain theory, we constructed relative partitioning models to predict site preferences of lanthanides we have not measured directly. The models predict that all REE are favoured on the Ca-dominant M1 site and that preferential partitioning of heavy over light REE increases in EGM containing significant Mn in the M1-octahedral rings (oneillite subgroup). Thus, the flat REE profiles that make EGM such attractive exploration targets are not due to preferential partitioning of light and heavy REE onto different sites. Instead, local ordering of Mn- and Ca-occupied M1 sites may influence the capacity of EGM to accommodate heavy REE.

Sphalerite is the main source of In – a ‘critical’ metal widely used in high-tech electronics. In this mineral the concentration of In is commonly correlated directly with Cu content. Here we use X-ray absorption spectroscopy of synthetic compounds and natural crystals in order to investigate the substitution mechanisms in sphalerites where In is present, together with the group 11 metals. All the admixtures (Au, Cu, In) are distributed homogeneously within the sphalerite matrix, but their structural and chemical states are different. In all the samples investigated In3+ replaces Zn in the structure of sphalerite. The In ligand distance increases by 0.12 Å and 0.09–0.10 Å for the 1st and 2nd coordination shells, respectively, in comparison with pure sphalerite. The In–S distance in the 3rd coordination shell is close to the one of pure sphalerite. Gold in synthetic sphalerites is coordinated with sulfur (NS = 2.4–2.5, RAu–S = 2.35 ± 0.01 Å). Our data suggest that at high Au concentrations (0.03–0.5 wt.%) the Au2S clusters predominate, with a small admixture of the Au+ solid solution with an Au–S distance of 2.5 Å. Therefore, the homogeneous character of a trace-element distribution, which is commonly observed in natural sulfides, does not confirm formation of a solid solution. In contrast to Au, the presence of Cu+ with In exists only in the solid-solution state, where it is tetrahedrally coordinated with S atoms at a distance of 2.30 ± 0.03 Å. The distant coordination shells of Cu are disordered. These results demonstrate that the group 11 metals (Cu, Ag and Au) can exist in sphalerite in the metastable solid-solution state. The solid solution forms at high temperature via the charge compensation scheme 2Zn2+↔Me++Me3+. The final state of the trace elements at ambient temperature is governed by the difference in ionic radii with the main component (Zn), and concentration of admixtures.

The Fe 2p X-ray absorption spectra of single crystal gillespite, BaFeSi4O10, show a strong linear dichroism, i.e. a large difference in the absorption when measured with the polarization of the X-rays either parallel or perpendicular to the plane of the FeO4 group. The isotropic spectrum, obtained from measurement at the ‘magic angle’, and the polarization dependent spectra have been compared to atomic multiplet calculations and show an excellent agreement with theory. Analysis of the branching ratio, the linear dichroism, and the detailed peak structure confirms that the 5A1 level is the ground state at room temperature and pressure. The 5B2 level is sufficiently low in energy that a distortion of the electronic charge density, induced by increased pressure, may result in a 5B2 ground state.

Despite the growing geological evidence that fluid boiling and vapour-liquid separation affect the distribution of metals in magmatic-hydrothermal systems significantly, there are few experimental data on the chemical status and partitioning of metals in the vapour and liquid phases. Here we report on an in situ measurement, using X-ray absorption fine structure (XAFS) spectroscopy, of antimony speciation and partitioning in the system Sb2O3-H2O-NaCl-HCl at 400°C and pressures 270—300 bar corresponding to the vapour-liquid equilibrium. Experiments were performed using a spectroscopic cell which allows simultaneous determination of the total concentration and atomic environment of the absorbing element (Sb) in each phase. Results show that quantitative vapour-brine separation of a supercritical aqueous salt fluid can be achieved by a controlled decompression and monitoring the X-ray absorbance of the fluid phase. Antimony concentrations in equilibrium with Sb2O3 (cubic, senarmontite) in the coexisting vapour and liquid phases and corresponding SbIII vapour-liquid partitioning coefficients are in agreement with recent data obtained using batch-reactor solubility techniques. The XAFS spectra analysis shows that hydroxy-chloride complexes, probably Sb(OH)2Cl0, are dominant both in the vapour and liquid phase in a salt-water system at acidic conditions. This first in situ XAFS study of element fractionation between coexisting volatile and dense phases opens new possibilities for systematic investigations of vapour-brine and fluid-melt immiscibility phenomena, avoiding many experimental artifacts common in less direct techniques.

Oxidative dissolution of a primary Mn-silicate phase (rhodonite) was studied via synchrotron X-ray techniques. The study was designed to combine the element-specific chemical technique of Glancing Incidence X-ray Absorption Spectroscopy (GIXAS) with the surface structural technique of X-ray scattering in order to produce the first depth resolved study of Mn-silicate low-temperature reactivity. A chemo-mechanically polished polycrystalline rhodonite sample was characterized and then reacted with pH 3.5 nitric acid. The surface originally had a mosaic structure and 15.5 (±1) Å r.m.s. roughness. Surface composition was not measurably different from bulk rhodonite before reaction, indicating that the surface preparation regimen had not produced an altered surface. After 1 h of reaction, the roughness of the mineral surface decreased and reflectivity oscillations developed, resulting from the formation of a leached layer. This layer was 74.7 (±2) Å thick with an electron density equal to 72% of that of bulk rhodonite (equal to the loss of ~1 in 2 Mn atoms). Both the primary and the buried interfaces had similar roughnesses; 4.9 and 4.5 (±1.0) Å , respectively. Diffuse scatter indicated that the correlation length between surface features also decreased. The GIXAS analysis showed that the Mn remaining in the surface had become oxidized, with the degree of oxidation decreasing as a function of depth. Oxidation penetrated at least 140 Å into the structure. A further 2.5 h of reaction at pH 3.5 caused dissolution of the leached layer and reduced the thickness of this altered region to 16.0 (±2) Å , while surface roughness increased slightly to 6.2 (±1.0) Å . Depletion of Mn in this region increased only slightly relative to the first reaction step; the electron density was 67% that of bulk rhodonite, equivalent to the loss of 2 in 3 Mn atoms. The thickness of the oxidized region however, persisted. Analysis by XPS on the same specimen corroborates the X-ray results.

Geological disposal facilities (GDF) are intended to isolate and contain radioactive waste within multiple protective barriers, deep underground, to ensure that no harmful quantities of radioactivity reach the surface environment. The last line of defense in a multi-barrier GDF is the geosphere, where iron is present in the host rock mineralogy as either Fe(II) or Fe(III), and in groundwater as Fe(II) under reducing conditions. The mobility of risk-driving radionuclides, including uranium and technetium, in the environment is affected significantly by their valence state. Due to its low redox potential, Fe(II) can mediate reduction of these radionuclides from their oxidized, highly mobile, soluble state to their reduced, insoluble state, preventing them from reaching the biosphere. Here a study of five types of potential host rocks, two granitoids, an andesite, a mudstone and a clay-rich carbonate, is reported. The bulk rocks and their minerals were analysed for iron content, Fe(II/III) ratio, and for the speciation and fine-grained nature of alteration product minerals that might have important controls on groundwater interaction. Total iron content varies between 0.9% in clays to 5.6% in the andesite. X-ray absorption spectroscopy reveals that Fe in the granitoids and andesite is predominantly Fe(II), and in mudstones, argillaceous limestone and terrestrial sandstone is predominantly Fe(III). The redox reactivity of the potential host rocks both in the presence and absence of Fe(II)-containing 'model' groundwater was investigated using an azo dye as a probe molecule. Reduction rates as determined by reactivity with the azo dye were correlated with the ability of the rocks to uptake Fe(II) from groundwater rather than with initial Fe(II) content. Potential GDF host rocks must be characterized in terms of mineralogy, texture, grain size and bulk geochemistry to assess how they might interact with groundwater. This study highlights the importance of redox reactivity, not just total iron and Fe(II)/(III) ratio, when considering the host rock performance as a barrier material to limit transport of radionuclides from the GDF.

Synthesis of Ni and Zn substituted nano-greigite, Fe3S4, is achieved from single source diethyldithiocarbamato precursor compounds, producing particles typically 50–100 nm in diameter with plate-like pseudohexagonal morphologies. Up to 12 wt.% Ni is incorporated into the greigite structure, and there is evidence that Zn is also incorporated but Co is not substituted into the lattice. The Fe L3 X-ray absorption spectra for these materials have a narrow single peak at 707.7 eV and the resulting main X-ray magnetic circular dichroism (XMCD) has the same sign at 708.75 eV. All XMCD spectra also have a broad positive feature at 711 eV, a characteristic of covalent mixing. The greigite XMCD spectra contrast with the three clearly defined XMCD site specific peaks found in the ferrite spinel, magnetite. The Fe L2,3X-ray absorption spectra and XMCD spectra of the greigite reflect and reveal the high conductivity of greigite and the very strong covalency of the Fe–S bonding. The electron hopping between Fe3+ and Fe2+ on octahedral sites results in an intermediate oxidation state of the Fe in the Oh site of Fe2.5+ producing an effective formula of [Fe3+ ↑]A-site[2Fe2.5+ ↓]B-siteS42–]. The Ni L2,3 X-ray absorption spectra and XMCD reveal substitution on the Oh site with a strongly covalent character and an oxidation state <Ni1.5+ in a representative formula [Fe3+ ↑]A[[(2 – x)Fe2.5+ ↓][Nix1.5+]]BS42–.

X-ray absorption spectroscopy (XAS) is a widely used characterization technique to explore the local geometric and electronic structures of materials with element specificity. XAS measurements are performed at synchrotron radiation sources that provide brilliant, tunable, and monochromatic energy photons. The advantages of XAS include good elemental, chemical, and orbital sensitivities, which all stem from inherent electron excitation and transition processes. XAS is categorized into soft (<2000 eV) and hard (>5000 eV) x-ray regimes, based on the incident photon energy. Soft x-rays can probe the K-edges of low-Z (atomic number) elements, including Li, C, N, O, and F, and the L-edges of 3d transition metals, whose K-edge is within the hard x-ray regime. All of these elements are essential components of energy materials. This article introduces the principle of XAS and reviews some recent applications in energy storage and energy conversion, illustrating the capabilities of XAS to investigate the fundamental properties of materials from the points of view of atomic and electronic structures, which play crucial roles in understanding the reaction mechanisms in high-performance devices.

Synchrotron powder X-ray diffraction, X-ray absorption spectroscopy (XAS), and proton nuclear magnetic resonance (1H-NMR) data have been used to examine the structure of hypoxanthine, 1,7-dihydro-6H-purin-6-one (C5H4N4O), a purine base that participates in numerous metabolic processes. XAS and 1H-NMR spectroscopy were used to determine that hypoxanthine was present in its keto form (both in solid state and dissolved in an organic solvent). Rigid body refinement was performed with the Rietveld software package GSAS yielding triclinic lattice parameters of a = 7.1179 (2) Å, b = 9.7830 (3) Å, c = 10.4009 (3) Å, α = 58.876 (1)°, β = 67.609 (1)°, and γ = 71.937 (2)° (C5H4N4O, Z = 4, space group P $\bar 1$ ).

Recent efforts to characterize the nanoscale structural and chemical modifications induced by energetic ion irradiation in nuclear materials have greatly benefited from the application of synchrotron-based x-ray diffraction (XRD) and x-ray absorption spectroscopy (XAS) techniques. Key to the study of actinide-bearing materials has been the use of small sample volumes, which are particularly advantageous, as the small quantities minimize the level of radiation exposure at the ion-beam and synchrotron user facility. This approach utilizes energetic heavy ions (energy range: 100 MeV–3 GeV) that pass completely through the sample thickness and deposit an almost constant energy per unit length along their trajectory. High energy x-rays (25–65 keV) from intense synchrotron light sources are then used in transmission geometry to analyze ion-induced structural and chemical modifications throughout the ion tracks. We describe in detail the experimental approach for utilizing synchrotron radiation (SR) to study the radiation response of a range of nuclear materials (e.g., ThO2 and Gd2TixZr2−xO7). Also addressed is the use of high-pressure techniques, such as the heatable diamond anvil cell, as a new means to expose irradiated materials to well-controlled high-temperature (up to 1000 °C) and/or high-pressure (up to 50 GPa) conditions. This is particularly useful for characterizing the annealing kinetics of irradiation-induced material modifications.

The structures of anhydrous nickel, niobium, and tantalum chlorides have been investigated in situ in acidic and basic ionic liquids (ILs) of 1-methyl-3-ethylimidazolium chloride (EMIC)/AlCl3 with X-ray absorption spectroscopy (XAS). The coordination of NiCl2 changes from tetrahedral in basic solution to octahedral in acidic solution. The NiCl2 is a strong Lewis acid in that it can induce the AlCl3 to share its chlorides in the highly acidic IL, forming a structure with six near Cl− ions and eight further distant Al ions which share the chloride ions surrounding the Ni2+. When Nb2Cl10, a dimer, is added to the acidic or basic solution, the dimer breaks apart and forms two species. In the acid solution, two trigonal bipyramids are formed with five equal chloride distances, while in the basic solution, a square pyramid with four chlorides forming a square base and one shorter axial chloride bond. Ta2Cl10 is also a dimer and divides into half in the acidic solution and forms two trigonal bipyramids. In the basic solution, the dimer breaks apart but the species formed is sufficiently acidic that it attracts two additional chloride ions and forms a seven coordinated tantalum species.

X-ray absorption spectroscopy has been applied to probe the local structure of FeSc nanostructured amorphous solids around Sc atoms. At the Sc K-edge, the Fe90Sc10 nanoglass is characterized by a very short range order (EXAFS oscillations are only present up to k = 8 Å-1). A drastic difference in the phase and the amplitude of the nanoglass EXAFS signal compared to the amorphous ribbon indicating a different local structure around Sc atoms in both structures is observed. In addition, the changes in the local structure around Sc atoms are more significant than around Fe atoms.

Sodium-covered silica films formed on silicon substrates have been examined by X-ray photoemission spectroscopy (XPS) and X-ray absorption spectroscopy (EXAFS) in ultra-high vacuumconditions at 300K. The results show that sodium diffuses into the silica layer on a reversible manner and that it modifies the silica network in order to create its own site. Sodium atoms are surrounded by oxygen atoms at an average distance of 2.3 Å and by a second shell which is assigned to silicon atoms located at 3.8 Å. At high Na concentrations, sodium atoms are also present in the close environment of one sodium atom.