Silicon K-edge XANES spectra of silicate minerals

Silicon K-edge x-ray absorption near-edge structure (XANES) spectra of a selection of silicate and aluminosilicate minerals have been measured using synchrotron radiation (SR). The spectra are qualitatively interpreted based on MO calculation of the tetrahedral SiO ₄ ^4? cluster. The Si K-edge generally shifts to higher energy with increased polymerization of silicates by about 1.3 eV, but with considerable overlap for silicates of different polymerization types. The substitution of Al for Si shifts the Si K-edge to lower energy. The chemical shift of Si K-edge is also sensitive to cations in more distant atom shells; for example, the Si K-edge shifts to lower energy with the substitution of Al for Mg in octahedral sites. The shifts of the Si K-edge show weak correlation with average Si-O bond distance (d_Si-O), Si-O bond valence (s_Si-O) and distortion of SiO₄ tetrahedra, due to the crystal structure complexity of silicate minerals and multiple factors effecting the x-ray absorption processes.     

Probing the local environment of substitutional Al$$^{}$$ in goethite using X-ray absorption spectroscopy and first-principles calculations

We present experimental and calculated Al K-edge X-ray absorption near-edge structure (XANES) spectra of aluminous goethite with 10–33 mol% of AlOOH and diaspore. Significant changes are observed experimentally in the near- and pre-edge regions with increasing Al concentration in goethite. First-principles calculations based on density functional theory (DFT) reproduce successfully the experimental trends. This permits to identify the electronic and structural parameters controlling the spectral features and to improve our knowledge of the local environment of \(\hbox {Al}^{3+}\) in the goethite–diaspore partial solid solution. In the near-edge region, the larger peak spacing in diaspore compared to Al-bearing goethite is related to the nature (Fe or Al) of the first cation neighbours around the absorbing Al atom (Al*). The intensity ratio of the two near-edge peaks, which decreases with Al concentration, is correlated with the average distance of the first cations around Al* and the distortion of the \(\hbox {AlO}_6\) octahedron. Finally, the decrease in intensity of the pre-edge features with increasing Al concentration is due to the smaller number of Fe atoms in the local environment of Al since Al atoms tend to cluster. In addition, it is found that the pre-edge features of the Al K-edge XANES spectra enable to probe indirectly empty 3d states of Fe. Energetic, structural and spectroscopic results suggest that for Al concentrations around 10 mol%, Al atoms can be considered as isolated, whereas above 25 mol%, Al clusters are more likely to occur.     

The local structure of Ca-Na pyroxenes. I. XANES study at the Na K-edge

 X-ray absorption Na K-edge spectra have been recorded on synthetic endmember jadeite and on a series of natural Ca-Na pyroxenes compositionally straddling the Jd-Di join. The C2/c members of the series are systematically different from the P2/n members. Differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra. These have been calculated by the multiple-scattering formalism from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. In the full multiple scattering region of the spectra (1075 to 1090 eV) C-pyroxenes exhibit three features which reflect the 6-2 configuration of the O back-scattering atoms around the Na absorber located at the center of the cluster (site M2 of the jadeite structure). P-pyroxenes show more complicated spectra in which at least four (possibly five) features can be recognized; they reflect the two types of configuration (6-2 and 4-2-2) of O around Na in the two independent M2 and M21 eight-fold coordinated sites of the omphacite structure. A weak, sometimes poorly resolved peak at 1079 eV is diagnostic and discriminates C- from P-pyroxenes. The Garnet Ridge C2/c impure jadeite exhibits a spectrum which is intermediate between those of jadeite and omphacite. The Hedin-Lundqvist potential proves best for these insulating materials and allows multiple-scattering calculations agreeing well with experiments. Received: July 11, 1996/Revised, accepted: October 21, 1996     

The site of Fe in Fe-bearing MgSiO3 enstatite and perovskite. a theoretical-, x-ray multiple-scattering study at Fe K-edge

Two polycrystalline-, Fe-bearing MgSiO₃ enstatite and perovskite have been probed by x-ray absorption near edge structure (XANES) spectroscopy at the Fe K-edge under ambient conditions. The perovskite sample was synthesized at 260 kbar and 1973 K in a multianvil apparatus. The experimental XANES spectrum has been compared to ab-initio-, x-ray multiple-scattering calculations (Feff 6 code). Calculations confirm that the Fe K-edge arises mainly from multiple scattering involving the first shell of oxygen neighbors around Fe. In Fe-enstatite, these calculations are consistent with Fe²⁺ as substituted in the M2 site of this orthopyroxene, in good agreement with crystal structure refinements and previous XANES studies. In perovskite, Feff 6 suggests that Fe is likely to be substituted to Mg within the (8+4)-coordinated sites of that perovskite. No evidences for 6-coordinated Fe were found. These results are consistent with a previous anharmonic analysis of the extended x-ray absorption fine structure (EXAFS) study that evidenced the presence of 8-coordinated Fe in the same perovskite sample.     

Crystal chemistry of iron in natural grandidierites: an X-ray absorption fine-structure spectroscopy study

 Fe–K edge XAFS spectra (pre-edge, XANES and EXAFS) were collected for eight grandidierites from Madagascar and Zimbabwe, as well as for Fe(II) and Fe(III) model compounds (staurolite, siderite, enstatite, berlinite, yoderite, acmite, and andradite). The pre-edge spectra for these samples are consistent with dominantly 5-coordinated ferrous iron. The analysis of the XANES and EXAFS spectra confirms that Fe(II) substitutes for Mg(II) in grandidierite, with a slight expansion of the local structure around Mg by ∼2%. In addition, ferric iron was also detected in some samples [5–10 mol% of the total Fe or 500–1100 ppm Fe(III)]. Based on theoretical calculations of the EXAFS region, Fe(III) appears to be located in the 5-coordinated sites of Mg(II) or in the most distorted 6-coordinated sites of Al (depending on the sample studied). Special attention is therefore required when using grandidierite as a model for ferrous iron in C_3v geometry, because of the possible presence of an extra contribution related to Fe(III). This additional contribution enhances significantly the Fe–K pre-edge integrated area [+40% for 1000 ppm Fe(III)]. Therefore, only a few grandidierite samples can be used as a robust structural model for the study of the Fe(II) coordination in glasses and melts. Received: 26 June 2000 / Accepted: 19 February 2001     

Unraveling the atomic structure of biogenic silica: evidence of the structural association of Al and Si in diatom frustules

We used X-ray absorption spectroscopy at the Al K-edge to investigate the atomic structure of biogenic silica and to assess the effect of Al on its crystal chemistry. Our study provides the first direct evidence for a structural association of Al and Si in biogenic silica. In samples of cultured diatoms, Al is present exclusively in fourfold coordination. The location and relative intensity of X-ray absorption near-edge structure (XANES) features suggests the structural insertion of tetrahedral Al inside the silica framework synthesized by the organism. In diatom samples collected in the marine environment, Al is present in mixed six- and fourfold coordination. The relative intensity of XANES structures indicates the coexistence of structural Al with a clay component, which most likely reflects sample contamination by adhering mineral particles. Extended X-ray absorption fine structure spectroscopy has been used to get Al-O distances in biogenic silica of cultured diatoms, confirming a tetrahedral coordination. Because of its effect on solubility and reaction kinetics of biogenic silica, the structural association between Al and biogenic silica at the stage of biosynthesis has consequences for the use of sedimentary biogenic silica as an indicator of past environmental conditions.     

Crystal-chemistry and cation ordering in the system diopside-jadeite: A detailed study by crystal structure refinement

The Nybö eclogite pod in Norway is characterized by a great variety of clinopyroxene compositions with Jd contents ranging from less than 5% up to nearly 80%, whilst Ac+Hd contents remain almost constant (mostly within 10±5%).Unconstrained X-ray structure refinement has been carried out on 16 pyroxene crystals (8 with C2/c and 8 with P2/n space group) from the Nybö eclogite, and also on one omphacite crystal (from Lago Mucrone in the Sesia-Lanzo Zone, Western Alps) which displays the highest degree of cation ordering yet described. The final discrepancy factors range from 0.014 to 0.029. The population of the sites has been determined on the basis of bond length considerations and of the results of the site occupancy refinement. Six of these crystals were subsequently analysed by electron microprobe.The tetrahedral sites are occupied by Si with negligible amounts of Al. Al, Mg, Fe³⁺ and Fe²⁺ occur at the octahedral sites; in the ordered P2/n crystals Al and Fe³⁺ are concentrated at the M11 site, whilst Mg and Fe²⁺ are concentrated and the M1 site. The eight-coordinated sites contain Ca and Na with negligible amounts of Fe and/or Mg. Ordering of Ca and Na takes place in the P2/n samples in such a way that in the most ordered crystal the M2 site contains almost exactly 0.75 Na+0.25 Ca and the M21 site 0.25 Na+0.75 Ca.Some geometrical features of the tetrahedra as well as of the octahedra (e.g. tetrahedral quadratic elongation and TILT angle) are not a simple linear function of composition, even when no change in space group occurs. The crystals evidently do not behave like a binary system of the two components, Di and Jd, but behave rather as if the composition Di_0.50 Jd_0.50 was a distinct end member.The boundaries between disordered and ordered phases in the Nybö pyroxenes fall at about 0.35 and 0.65 Jd/(Di+ Jd), in close agreement with the previous TEM investigations.The degree of order varies with composition following a bell-shaped curve: different coaxial bell-shaped curves can be drawn for crystals which have similar compositions but come from different metamorphic environments. The order vs composition diagrams may be useful for the interpretation of the P-T-t histories of the host rocks.     

Coordination nature of aluminum (oxy)hydroxides formed under the influence of tannic acid studied by X-ray absorption spectroscopy

The effect of biomolecules on the mechanisms of the formation and nature of the transformation products of Al (oxy)hydroxides at the atomic and molecular levels and the impact on their nano-scale surface chemistry remain to be uncovered. In this article, the coordination structure of Al in Al (oxy)hydroxides formed under the influence of tannic acid was studied with X-ray absorption near edge structure (XANES) spectroscopy. Al K-edge and L-edge spectra show that as the tannate/Al molar ratio (MR) was increased from 0, 0.001, 0.01 to 0.1, the coordination number of Al changed from the sixfold coordination to mixed six-, five-, and/or fourfold coordination in the structural network of the Al (oxy)hydroxides formed under the increasing perturbation of tannic acid. In O K-edge spectra, the intensity of the peak assigned to the π^∗ at 532.1 eV increased as the tannate/Al MR increased, with the spectrum of the Al precipitate formed at a tannate/Al MR of 0.1 being almost identical to that of tannic acid. These results indicate that tannate ligands are incorporated into the structural network of short-range ordered Al (oxy)hydroxides to perturb their structural configuration during the formation of Al precipitates under the influence of tannic acid. With increasing tannate/Al MR, the Al (oxy)hydroxides decreased in amount and developed structural defects and the Al-tannate precipitates increased in amount. The decrease in the coordination number of Al in the Al (oxy)hydroxides is attributed to steric and electronic factors which cause the change in Al-O bonding, because Al is complexed with tannate which has different functional groups and is much larger in size compared with OH and H₂O ligands. The surface reactivity of a metal-O bond is related to its covalency and coordination geometry. The findings obtained in the present study are, thus, of fundamental significance in understanding the structural and surface chemistry of Al (oxy)hydroxides and their impact on the transformation, transport, and fate of nutrients and pollutions in the environment.     

Sulfur K-edge XANES study of local electronic structure in ternary monosulfide solid solution [(Fe, Co, Ni)0.923S]

 Synchrotron radiation S K-edge XANES spectra and unit-cell parameters are used to investigate the local electronic structure of non-stoichiometric binary and ternary Fe-Co-Ni monosulfide solid solution (mss; M_0.923S, M = Fe, Co, Ni) quenched from 800 °C and low pressure. The prominent absorption edge feature of the XANES spectra represents transition of S 1s core level electrons to unoccupied S 3p σ* antibonding orbitals hybridized with empty metal 3d(e_g) orbitals. There is a progressive increase in area of the edge peak from Fe_0.923S to Ni_0.923S and Co_0.923S, which correlates with progressive decrease in c and a parameters for the NiAs-type subcell and increase in metallic character, and reflects increase in the number and availability of empty e_g ^β orbitals and covalence of metal-S bonds. More generally, the area of the edge peak exhibits an inverse linear correlation with a, c and unit-cell volume of binary and ternary mss. This inverse linear correlation is attributed to progressive increase in covalence and M-S-M bonding interaction in the c-axis direction, through metal-S [M 3d(e_g) - S 3p (or 3d)] π bonding. However, the area of the edge peak does not correlate very well with the average number of 3d electrons per metal atom in these solid solutions, showing that the absorption of synchrotron radiation reflects the local electronic structure of individual absorber atoms (i.e. the SM₆ cluster), and is not a group (crystal energy band) effect. Received: 21 March 2000 / Accepted: 14 July 2000     

A Fe K-edge XAS study of amethyst

An X-ray absorption spectroscopy (XAS) study of the Fe local environment in natural amethyst (a variety of α-quartz, SiO₂) has been carried out. Room temperature measurements were performed at the Fe K-edge (7,112 eV), at both the X-ray absorption near-edge structure (XANES) and extended X-ray absorption fine structure (EXAFS) regions. Experimental results were then compared with DFT calculations. XANES experimental spectra suggest Fe to occur mainly in the trivalent state, although a fraction of Fe²⁺ is identified. EXAFS spectra, on the other hand, reveal an unusual short distance for the first coordination shell:  = 1.78(2) Å, the coordination number being 2.7(5). These results allow to establish that Fe replaces Si in its tetrahedral site, and that numerous local distortions are occurring as a consequence of the presence of Fe³⁺ variably compensated by protons and/or alkaline ions, or uncompensated. The formal valence of Fe, on the basis of both experimental and DFT structural features, can be either 4+ or 3+. Taking into account the XANES evidences, we suggest that Fe mainly occurs in the trivalent state, compensated by protons, and that a minor fraction of Fe⁴⁺ is stabilised by the favourable local structural arrangement.     

X-ray K-edge absorption spectra of Fe minerals and model compounds: Near-edge structure

Synchrotron radiation has been used to collect high-resolution Fe K absorption near-edge spectra of a suite of Fe minerals and compounds having a range of Fe environments. These spectra, along with those of previous workers, indicate that the number, position, and intensity of near-edge features are characteristic of Fe valence and general site geometry. For example, the crest of the K-edge for Fe²⁺ in a six-coordinated site in the oxides studied is about 3 eV lower in energy than that for Fe³⁺ in a similar site. The K-edge crest for Fe³⁺ in a four-coordinated site is 1 to 2 eV lower than for Fe³⁺ in a regular site. The shape of the edge crest is sensitive to the details of first-neighbor bonding distances, tending to be broader in species with irregular Fe sites and varying in energy according to the average bond length. Comparison with Ca²⁺ and Zn²⁺ spectra from the literature is made and the applicability and utility of edge measurements discussed.     

Local structural environment of calcium in garnets: A combined structure-refinement and XANES investigation

Comparative crystal-chemical analysis of natural garnets allowed the compositional gap at Gr 45÷70% in the (Py, Alm)-Gr join to be related to the presence of two different structural arrangements around the X site in pyralspitic and ugranditic composition, respectively. A combined investigation (single-crystal X-ray structure-refinement (SREF), Ca K-edge XANES spectroscopy and multiple-scattering calculation of XANES spectra) carried out on a series of natural garnets in the (Py, Alm)-Gr join, allowed the structural modifications of the Ca local environment at increasing grossular content to be followed. The differences in the experimental XANES spectra as a function of the Ca content were shown to depend only on the configuration of the ligand shells surrounding the absorbing atom, and not on the nature of adjacent dodecahedral cations. Both experimental XANES spectra and their theoretical simulations confirm that Ca at the X site, when less abundant than (Fe+Mg), is not in the same structural configuration as in grossular, but adapts itself to that imposed by the dominant (Fe, Mg) cations. In the same way, (Fe, Mg) adapt themselves to the X-site configuration observed in grossular when Ca is the dominant cation. The deformation of the X site due to progressive Ca → (Fe, Mg) substitution is gradual but not linear along the solid solution; it shows different slopes on the two sides of the observed (Py, Alm)-Gr compositional gap. Best performances in reproducing the XANES spectra were obtained in the framework of the one-electron fullmultiple-scattering theory, using the real Hedin-Lundqvist exchange-correlation potential and clusters of 83 atoms (i.e. for a coordination sphere with 7 Å radius from the central Ca absorber); smaller clusters resulted inadequate in simulating some XANES features, indicating that a high number of single and multiple scatteringpaths contribute in garnets to the first part of the absorption spectrum.     

Aluminium X-ray absorption Near Edge Structure in model compounds and Earth’s surface minerals

Aluminium K-edge X-ray absorption near edge spectra (XANES) of a suite of silicate and oxides minerals consist of electronic excitations occurring in the edge region, and multiple scattering resonances at higher energies. The main XANES feature for four-fold Al is at around 2 eV lower energy than the main XANES feature for six-fold Al. This provides a useful probe for coordination numbers in clay minerals, gels, glasses or material with unknown Al-coordination number. Six-fold aluminium yields a large variety of XANES features which can be correlated with octahedral point symmetry, number of aluminium sites and distribution of Al-O distances. These three parameters may act together, and the quantitative interpretation of XANES spectra is difficult. For a low point symmetry (1), variations are mainly related to the number of Al sites and distribution of Al-O distances: pyrophyllite, one Al site, is clearly distinguished from kaolinite and gibbsite presenting two Al sites. For a given number of Al-site (1), variations are controlled by changes in point symmetry, the number of XANES features being increased as point symmetry decreases. For a given point symmetry (1) and a given number of Al site (1), variations are related to second nearest neighbours (gibbsite versus kaolinite). The amplitude of the XANES feature at about 1566 eV is a useful probe for the assessment of Al^IV/Al^total ratios in 2/1 phyllosilicates. Al-K XANES has been performed on synthetic Al-bearing goethites which cannot be studied by ²⁷Al NMR. At low Al content, Al-K XANES is very different from that of α-AlOOH but at the highest level, XANES spectrum tends to that of diaspore. Al-K XAS is thus a promising tool for the structural study of poorly ordered materials such as clay minerals and natural alumino-silicate gels together with Al-subsituted Fe-oxyhydroxides. Received: 18 December 1996 / Revised, accepted: 2 June 1997     

XAFS characterization of the structural site of Yb in synthetic pyrope and grossular garnets. II: XANES full multiple scattering calculations at the Yb LI- and LIII-edges

We present an X-ray absorption near-edge structure study performed at the Yb L_I- and L_III-edges on synthetic pyrope (Mg₃Al₂Si₃O₁₂) and grossular (Ca₃Al₂Si₃O₁₂) garnets containing about 1% wt of Yb. For the first time Yb L-edge XANES spectra are analyzed by full multiple scattering theory using clusters of different sizes and different final-state potentials. A comparison between experimental spectra and model calculations indicates that Yb³⁺ enters the dodecahedral X-site in both pyrope and grossular, in agreement with the results of an EXAFS study. Based on the present results, the charge balancing substitution mechanism required by the replacement of divalent Mg and Ca cations with trivalent Yb³⁺ is discussed in terms of vacancies in dodecahedral sites surrounding the central Yb³⁺ absorber. Received: 7 December 1998 / Revised, accepted: 7 May 1999     

Electronic and optical properties of Fe, Zn and Pb sulfides

Ab initio quantum-chemical calculations of the spatial and electronic structures of sphalerite (ZnS), pyrite (FeS₂) and galena (PbS), using the density functional theory (DFT) local density approximation (LDA) and generalized gradient approximation (GGA), the Hartree–Fock (HF) method and the hybrid functional B3LYP, have been carried out. For galena, the DFT LDA and GGA functionals provided the best estimate of the band gap, from within –0.1 eV to +0.4 eV of the measured value. B3LYP and RHF gave rise to errors of +1.3 and +5.4 eV, respectively. The unit cell parameter error varied from between –1.1% and +2.3% for all the functionals examined. For sphalerite the B3LYP functional provided the best estimate of the band gap (error +0.3 eV). The unit cell parameter error varied between –2.1% and +2.0% for the various DFT functionals and B3LYP. RHF gave rise to an error of +3.8%. For FeS₂, the DFT-GGA approach provides the best results for both the unit cell and the band gap. This may be due to mutual cancellation of the crystal field splitting and band separation force, which are of equal but opposite magnitudes. The calculated density of states (DOS) for the conduction band is used to interpret the experimental features of the S 1s XANES (X-ray absorption near-edge structure) spectra obtained using synchrotron radiation. Because of the l = ±1 selection rule for electron excitation, the S K-edge XANES spectra represent a transition of the S 1s electron to conduction band S p-like orbitals. The near-edge region, up to 15 eV past the edge is approximated well by the DOS. Individual peaks in the DOS correlate with peaks in the XANES spectra. In addition, the imaginary part of the dielectric function, which reflects the transitions from occupied to unoccupied levels, is used to model the near-edge region of the XANES, using the DFT-GGA formalism. Individual peaks in the XANES spectrum are moderately well resolved using the dielectric function, especially for ZnS and FeS₂, while the DOS for the conduction band is more successful in predicting the shape of the XANES spectra for all three minerals.     

砷在石膏中固定机制:掺杂态和表面吸附沉淀态以及其在砷污染控制中的作用

石膏是矿山开采及冶炼等工业过程产生的大宗固体废弃物。工业活动产生的废液普遍有高含量的砷等有毒元素,这导致所产生的石膏也含有较高浓度的砷等有毒元素。研究砷在石膏中地球化学行为和归趋对含砷石膏的砷污染控制具有重要的理论和实际意义。然而目前对含砷石膏中不同形态的砷的定量测定和分析尚存在问题。本文在不同pH值的条件下共沉淀砷和石膏,利用电感耦合等离子体质谱(ICP-MS)、同步辐射X-射线吸收近边光谱(XANES)和电子顺磁共振(EPR)对石膏中掺杂态和表面吸附沉淀态的砷进行定量分析。ICP-MS的结果表明随着pH从2升高到12 和14,石膏中砷的含量由57×10^-6 增加到 67 470×10^-6和63 980×10^-6。同步辐射X-射线吸收近边光谱和电子顺磁共振光谱分析表明石膏样品中主要含有五价砷。在2≤pH≤7.5时,固体样品中同步辐射吸收边后的峰形状和掺杂态砷的形状类似,而在pH≥8时,其边后峰的形状发生明显的变化;粉末电子顺磁共振(EPR)定量分析表明在2≤pH≤7.5时砷在石膏中的含量和ICP-MS的分析结果一致,而在pH≥8时其含量明显小于ICP-MS的分析结果。这些结果揭示了在2≤pH≤7.5时,砷在石膏中主要以掺杂态的形式存在,而在pH≥8时大部分砷是以吸附态或表面沉淀的形式存在。五价砷在石膏中的含量和固定机制随着pH值的变化而变化,其研究对了解尾矿中石膏对砷污染的控制作用具有重要作用。此外,研究石膏中由辐射导致的g约为2.33的[AsO₃]^2-自由基电子顺磁共振特征峰,有助于补充和完善石膏的电子顺磁共振特征谱在地质测年及辐射剂量学中的应用。     

富氯造岩矿物中溴的分子结构

卤族元素诸如氯和溴作为地球化学示踪剂,常用于指示岩浆、变质岩和热液的来源和演化过程。而认清溴在造岩矿物中的形态和结构有助于丰富和完善其在地质环境演变中的示踪作用。但是,溴在造岩矿物中的含量极低导致大多数结构分析方法都无法使用,因此造岩矿物中微量溴的结构研究极具挑战性。本文采用 ⁸¹Br魔角旋转核磁共振(MAS NMR)光谱和同步辐射吸收光谱(XAS)技术,首次对富氯造岩矿物中的微量溴进行了结构分析。结果表明溴离子在方硼石中的微区结构不同于该矿物中三配位Cl原子的结构环境,而与Mg₃B₇O₁₃Br中八面体配位的溴离子相似,表明即使在微量条件下也存在域偏析。而对其他富氯造岩矿物的Br K边X光吸收近边结构(XANES)光谱白线峰的位置和扩展X射线吸收精细结构(EXAFS)分析表明微量溴离子替代了这些矿物中氯的位置,导致局部结构扭曲膨胀。溴离子在造岩矿物中的这一微观结构研究结果可为探索氯和溴在地质演变过程的指示作用提供新的科学依据。     

Molecular environment of iodine in naturally iodinated humic substances: Insight from X-ray absorption spectroscopy

The molecular environment of iodine in reference inorganic and organic compounds, and in dry humic and fulvic acids (HAs and FAs) extracted from subsurface and deep aquifers was probed by iodine L₃-edge X-ray absorption spectroscopy. The X-ray absorption near-edge structure (XANES) of iodine spectra from HAs and FAs resembled those of organic references and displayed structural features consistent with iodine forming covalent bonds with organic molecules. Simulation of XANES spectra by linear combination of reference spectra suggested the predominance of iodine forming covalent bonds to aromatic rings (aromatic-bound iodine). Comparison of extended X-ray absorption fine structure (EXAFS) spectra of reference and samples further showed that iodine was surrounded by carbon shells at distances comparables to those for references containing aromatic-bound iodine. Quantitative analysis of EXAFS spectra indicated that iodine was bound to about one carbon at a distance d (I-C) of 2.01(4)-2.04(9) Å, which was comparable to the distances observed for aromatic-bound iodine in references (1.99(1)-2.07(6) Å), and significantly shorter than that observed for aliphatic-bound iodine (2.15(2)-2.16(2) Å). These results are in agreement with previous conclusions from X-ray photoelectron spectroscopy and from electrospray ionization mass spectrometry. These results collectively suggest that the aromatic-bound iodine is stable in the various aquifers of this study.     

The crystal and melt structure of spinel and alumina at high temperature: An in-situ XANES study at the Al and Mg K-edge

We present structural information obtained on spinel and alumina at high temperature (298-2400 K) using in-situ XANES at the Mg and Al K-edges. For spinel, ^[4](Al_x,Mg_1−x)^[6](Al_2−x,Mg_x)O_4, with increasing temperature, a substitution of Mg by Al and Al by Mg in their respective sites is observed. This substitution corresponds to an inversion of the Mg and Al sites. There is a significant change in the Al K-edge spectra between crystal and liquid, which can be attributed to a change of the ^[6]Al normally observed in corundum at room temperature, to a mixture of ^[6]Al-^[4]Al in the liquid state. This conclusion is in good agreement with previous ²⁷Al NMR experiments. Furthermore, both experiments at the Al and Mg K-edges are in good agreement with XANES calculation made using FDMNES code.     

Sulfur K- and L-edge X-ray absorption spectroscopy of sphalerite,chalcopyrite and stannite

Sulfur K-edge x-ray absorption spectra (XANES and EXAFS) and L-edge XANES of sphalerite (ZnS), chalcopyrite (CuFeS₂) and stannite (Cu₂FeSnS₄) have been recorded using synchrotron radiation. The K- and L-edge XANES features are interpreted using a qualitative MO/energy band structure model. The densities of unoccupied states at the conduction bands of sphalerite, chalcopyrite and stannite are determined using S K- and L-edge XANES features (up to 15 eV above the edge), combined with published metal K-edge XANES. The SK- and L-edge XANES also indicate that, for sphalerite, the Fe²⁺ 3d band at the fundamental gap has little or no bonding hybridization with S 3p and S 3s orbitals; for chalcopyrite, the Cu⁺ 3d and Fe³⁺ 3d bands have strong mixing with S 3p and S 3s states, while for stannite the Cu⁺ 3d band strongly hybridizes with S 3p and S 3s orbitals, but the Fe²⁺ 3d band does not. The post-edge XANES features (15–50 eV above the edge) of sphalerite, chalcopyrite and stannite are similar. These features are related to the tetrahedral coordination of sulfur in all these structures, and interpreted by a multiple scattering model. The resonance energies from both the K-edge and L-edge XANES for these minerals are well correlated with reciprocal interatomic distances and lattice spaces. Sulfur K-edge EXAFS analyses using Fourier transform and curve fitting procedures are presented. Comparison of the structural parameters from EXAFS with x-ray structure data shows that the first shell bond distances (BD) from EXAFS are usually accurate to ±0.02 Å, and that coordination numbers (CN) are generally accurate to ±20 percent. For sphalerite, EXAFS analysis yields the structure parameters for the first three neighbour shells around a sulfur atom; the BD and CN even for the third shell are in close agreement with the x-ray structure, and the Debye-Waller term decreases from the first shell to the third shell. It is shown that sphalerite (ZnS) is a good model compound for EXAFS analysis of sulfur in chalcogenide glasses and metalloproteins.