S K- and L-edge XANES and electronic structure of some copper sulfide minerals

The S K and L-edge x-ray absorption near-edge structures (XANES) of low bornite, cubanite, chalcocite, covellite, enargite and tetrahedrite have been measured with synchrotron radiation. The near-edge features are interpreted based on comparison with the S K- and L-edge spectra of chalcopyrite and a MO/energy band structure model. The XANES spectra of these sulfides reflect the DOS of unoccupied S s-, p- and d-like states near and above the Fermi level. In tetrahedral Cu-Fe sulfides, the Fe³⁺ 3d crystal field band has much more significant DOS of unoccupied S 3p-and 3s-like states than the Cu⁺ 3d crystal field band. For Cu sulfides, the Cu⁺ 3d crystal field band has the higher DOS of S 3p- and 3 s-like states in tetrahedral structure than in structures with the triangular CuS₃ cluster. The shifts in both S K- and L-edges correlate approximately linearly with the energy gap.     

Polarized X-ray absorption spectra and electronic structure of molybdenite (2H-MoS2)

Polarized S K- and L-edge, Mo L₃- and L₂-edge x-ray absorption near-edge structure (XANES) of natural molybdenite (2H-MoS₂) have been measured with synchrotron radiation. These results are qualitatively interpreted using the energy band model of molybdenite and provide important information on the unoccupied states of molybdenite. The valence band (VB) maximum of molybdenite is characterized by fully occupied Mo 4d_z ², and the conduction band (CB) minimum of molybdenite is characterized by unoccupied Mo 4d states. The unoccupied Mo 4d band is split into two sub-bands, designated as t _2g ^– /t _2g ⁺ and e _g ^– /e _g ⁺ sets. Although the relative energy of these two sets are difficult to be evaluated, probably the former has the lower energy than the latter, both two sets have the combination wave functions of the other unoccupied Mo 4d components, rather than the simple 4d_x ² — y₂ and 4d_xy states. The unoccupied Mo 4d sub-bands contain significant DOS of both S 3 p- and 3 s-like states, indicating strong hybridization with S 3s and 3 p states. In the lower energy sub-band, the DOS of the S p_z- and p_x,y-like states are very similar. However, in the higher energy sub-band, the DOS of the S 3 p_x,y-like state is lower than that of the S 3p_z state. Polarized S K-edge XANES also reveal the features of antibonding S p_z- and p_x,y-like states in molybdenite. The feature assigned to the S 3 p_z-like states is stronger and sharper, and shifts to lower energy by about 2 eV relative to that for the S 3 p_x,y-like states.     

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.     

Pristine and reacted surfaces of pyrrhotite and arsenopyrite as studied by X-ray absorption near-edge structure spectroscopy

Fe L-, S L-, and O K-edge X-ray absorption spectra of natural monoclinic and hexagonal pyrrhotites, Fe_1-xS, and arsenopyrite, FeAsS, have been measured and compared with the spectra of minerals oxidized in air and treated in aqueous acidic solutions, as well as with the previous XPS studies. The Fe L-edge X-ray absorption near-edge structure (XANES) of vacuum-cleaved pyrrhotites showed the presence of, aside from high-spin Fe²⁺, small quantity of Fe³⁺, which was higher for a monoclinic mineral. The spectra of the essentially metal-depleted surfaces produced by the non-oxidative and oxidative acidic leaching of pyrrhotites exhibit substantially enhanced contributions of Fe³⁺ and a form of high-spin Fe²⁺ with the energy of the 3d orbitals increased by 0.3–0.8 eV; low-spin Fe²⁺ was not confidently distinguished, owing probably to its rapid oxidation. The changes in the S L-edge spectra reflect the emergence of Fe³⁺ and reduced density of S s–Fe 4s antibonding states. The Fe L-edge XANES of arsenopyrite shows almost unsplit e_g band of singlet Fe²⁺ along with minor contributions attributable to high-spin Fe²⁺ and Fe³⁺. Iron retains the low-spin state in the sulphur-excessive layer formed by the oxidative leaching in 0.4 M ferric chloride and ferric sulphate acidic solutions. The S L-edge XANES of arsenopyrite leached in the ferric chloride, but not ferric sulphate, solution has considerably decreased pre-edge maxima, indicating the lesser admixture of S s states to Fe 3d orbitals in the reacted surface layer. The ferric nitrate treatment produces Fe³⁺ species and sulphur in oxidation state between +2 and +4.     

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.     

X-ray absorption near-edge spectra of transition metal disulfides FeS2 (pyrite and marcasite), CoS2, NiS2 and CuS2, and their isomorphs FeAsS and CoAsS

Metal K- and L₃-, sulfur K- and arsenic K- and L₃-edge X-ray absorption near-edge spectra of a series of metal disulfides, FeS₂ (both pyrite and marcasite), CoS₂, NiS₂, and CuS₂, and their isomorphs, FeAsS and CoAsS, are presented. The features in this region of these spectra are interpreted using band structure and molecular orbital calculations in terms of the transitions from the 1s or 2p_3/2 state to unoccupied states. The 3d transition metal L₃-edge spectra of these materials show dependence on the degree of multiplet splitting in the final state, and thus offer less information on the electronic ground state. There are substantial differences in the spectra of the isostructural materials, whereas the spectra of the isotopes pyrite and marcasite show several similarities, illustrating the dependence of near-edge region on electronic structure.     

The electronic structures of the pyrite-type disulphides (MS2, where M = Mn,Fe, Co,Ni, Cu,Zn) and the bulk properties of pyrite from local density approximation (LDA) band structure calculations

A local density approximation (LDA) band structure method, the Linear Muffin-Tin Orbital Atomic Sphere Approximation (LMTO-ASA) method has been used to calculate the electronic structures of the pyrite-type disulphides (MS₂, where M = Mn, Fe, Co, Ni, Cu, Zn). The total density of states has been calculated for 10 eV above and below the Fermi Level, along with the separate contributions from metal and sulphur and shows that the metal d band occurs above the sulphur p bands in MnS₂, FeS₂, CoS₂ and NiS₂, whereas in CuS₂, the d band passes through the sulphur p band and in ZnS₂, it lies below the sulphur p band. Substantial hybridization of the metal d states with the sulphur states occurs. FeS₂ is calculated to be a semiconductor with a direct band gap of 0.64 eV in good agreement with experiment. The calculated local densities of states have been used in turn to calculate X-ray photoelectron spectra and Bremsstrahlung Isochromat spectra for this series of compounds, and these also show reasonable agreement with experimental data. A particular strength of the LMTO-ASA method is the ability to calculate and predict certain bulk properties of solids of interest in mineral physics. This has enabled the first reasonably accurate calculations of the total energy of the valence electrons of the system for pyrite (FeS₂), given as — 345.885 rydbergs per unit cell, and the equilibrium unit cell volume which is within 3.3% of that determined experimentally. A theoretical pressure vs. volume curve for pyrite was also calculated along with values for the bulk modulus. However, our calculations predict a bulk modulus of 6.75 Mbar which is too high by a factor of 4.6 due to the simplifying assumption of a uniform scaling of interatomic distances on compression.     

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.     

Insights into oxygen-cation bonding in fresnoite-type structures from O <Emphasis Type="Italic">K</Emphasis>- and Ti <Emphasis Type="Italic">L</Emphasis><Subscript>23</Subscript>-electron energy-loss spectra and ab initio calculations of the electronic structure

O K- and Ti L₂₃-core-loss spectra of fresnoite Ba₂TiSi₂O₈ (BTS) and Sr₂TiSi₂O₈ (STS), which is isotypic to BTS, have been measured by electron energy-loss spectroscopy (EELS). The energy-loss near-edge structures (ELNES) of the O K edge have been identified on the basis of theoretical simulations and interpretations of the X-ray absorption near-edge structures (XANES), which have been modelled in the framework of self-consistent full multiple-scattering (FMS) theory using FEFF8. Herewith, the K-absorption spectra of oxygen (E) and the local partial electron density of states (DOS) of all atoms have been calculated. For BTS, the observed spectral features in the O K-edge spectra are interpreted in terms of mixing between the central O p and neighbouring Ba 5d and 4f, Si 3p and 3d, and Ti 3d orbitals. The observed differences in the O K-edge spectra for STS and BTS can mainly be attributed to three properties: (1) The lack of high local partial Sr unoccupied DOS with 4f symmetry near the Fermi level compared to the high Ba 4f unoccupied DOS results in differences of overlapping O 2p – cation orbitals. (2) The differences in the ionic radii of Sr and Ba result in a larger unit cell for BTS and, thus, in larger oxygen-cation bonding distances. (3) In comparison to STS, the strength of the incommensurate 2-D structural modulation is significantly weaker in BTS, i.e. distortions of coordination polyhedra occur to a much lesser extent. All these effects alter the oxygen-cation hybridization and, hence, result in a variation of the O 1s p transition and consequently of the O K-edge spectral shape. The observed peak broadening in Ti L₂₃ ELNES of STS compared to BTS is correlated with strong displacive modulations hosted in STS.     

Sulfur K-edge XANES analysis of natural and synthetic basaltic glasses: Implications for S speciation and S content as function of oxygen fugacity

XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO₂ conditions for the transition from sulfide (S²⁻) to sulfate (S⁶⁺) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S²⁻ and S⁶⁺ species, emphasizing the relevance of S⁶⁺ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO₂ ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S²⁻ and S⁶⁺ with changes in fO₂. No significant features related to sulfite (S⁴⁺) species were observed. These results were used to construct a function that allows estimates of S⁶⁺/ΣS from XANES data. Comparison of S⁶⁺/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S⁶⁺/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S⁶⁺/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S⁶⁺/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S⁶⁺/ΣS as a function of fO₂ indicates that the transition from S²⁻ to S⁶⁻ with increasing fO₂ occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO₂ above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.     

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.     

The local structure of Ca-Na pyroxenes. II. XANES studies at the Mg and Al K edges

X-ray absorption spectra at the Mg and Al K edges have been recorded using synchrotron radiation on synthetic end member diopside (Di) and jadeite (Jd) and on a series of natural Fe-poor Ca-Na clinopyroxenes compositionally straddling the Jd-Di join. The spectra of C2/c end members and intermediate members of the solid solution series (C-omphacites) are different from those of the intermediate members having P2/n symmetry (P-omphacites). Differences can be interpreted and explained by comparing the experimental spectra with theoretical spectra calculated via the full multiple-scattering formalism, starting from the atomic positional parameters determined by single-crystal X-ray diffraction structure refinement on the same samples. Atomic clusters with at least 89 atoms, extending to more than 0.60 nm away from the Mg or Al absorbers, are needed to reproduce the experimental spectra. This shows that in the clinopyroxene systems XANES detects medium- rather than short-range order-disorder relationships. Theoretical spectra match the experimental ones well for all features in the regions from 16 to 60 eV above threshold. Experimental near-edge features in the first 16 eV are also reproduced, albeit less accurately. Certain near-edge features of C-omphacites reflect the octahedral arrangement of the back-scattering six O atoms nearest neighbours of the probed atom (Mg or Al) located at site M1 of the crystal structure, thus being indicators of short-range order. Others arise again from medium-range order. P-omphacites show more complicated spectra than C-omphacites. Their additional features reflect the increased complexity of the structure and the greater local disorder around the probed atom induced by the two alternative M1, M11 configurations of the six O atoms forming the first coordination shells. Mg and Al are confirmed to be preferentially partitioned in the M1 and M11 site of the P-omphacite crystal structure, however with a certain degree of local disorder. The relative heights of certain prominent features are directly related to sample composition in terms of Di:Jd ratio in the Al K-edge spectra, whereas they show abrupt variations in the Mg K-edge spectra. They demonstrate that XANES is directly related to composition and may be used to distinguish C- from P-omphacites. Received: 24 November 1998 / Revised, accepted: 10 June 1999     

New approaches to studying heavy metals in soils by X-ray absorption spectroscopy (XANES)) and extractive fractionation

A comprehensive approach to studying the nature of interaction between heavy-metal ions and the organic–mineral matrix of soils involves application of modern physical analytical techniques and chemical methods of extractive fractionation. XANES was used to obtain the first data on the near-edge fine structure of X-ray spectra for a number of heavy-metal species in ordinary chernozem. Data on the structure of soil samples saturated with Zn²⁺ and Cu²⁺ obtained by XANES (X-ray absorption near-edge structure) make it possible to elucidate the interaction mechanisms of the metals and the types of chemical bonds formed thereby. As contamination doze of with Cu and Zn is increased (from 2000 to 10 000 mg/kg soil), particularly if the metals are introduced in the form of readily solubility salts, bonding between the metals and soil components weakens. Data of extractive fractionation of metal compounds from samples saturated with Cu and Zn compounds testify that the Cu²⁺ ion is preferably retained in the organic matter of the soil, whereas the Zn²⁺ ion is bound mostly to silicates, carbonates, and Fe and Mn (hydro)oxides.     

Determination of the oxidation state of radiogenic Pb in natural zircon using X-ray absorption near-edge structure

We examined the L_III-edge Pb X-ray absorption near-edge structure (XANES) of three natural zircon samples with different amounts of radiation doses (1.9 × 10¹⁵ to 6.8 × 10¹⁵ α-decay events/mg). The results suggest that the oxidation state of radiogenic Pb in the zircon sample with the highest radiation dose is divalent. The XANES spectra of the two other samples with lower radiation doses suggest that radiogenic Pb(II) is present, and further that some Pb may be tetravalent. This is the first work on the determination of the oxidation state of radiogenic Pb in natural zircon using XANES.     

The oxidation state of sulfur in synthetic and natural glasses determined by X-ray absorption spectroscopy

Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities (fO₂) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO₂ < −9) or oxidised (log fO₂ > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S²⁻. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV.The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO₄²⁻. Sulfite (SO₃²⁻) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S⁶⁺). S⁴⁺ does, however, occur unambiguously with S⁶⁺ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO₄ at 4-16 kbar, and when buffered with Re/ReO₂ at 10 kbar. Solubility of S⁴⁺ thus requires partial pressures of SO₂ considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO₂s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S²⁻ and S⁶⁺ were found to coexist in some samples that were not in equilibrium with the imposed fO₂.The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S²⁻, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S²⁻ + 8Fe³⁺ = S⁶⁺ + 8Fe²⁺, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S²⁻ and S⁶⁺ are frequently found together despite the very limited fO₂ range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.     

Correlation between local structure and molar ratio of Au (III) complexes in aqueous solution: An XAS investigation

The local and geometrical structure around gold (III) e.g., Au³⁺ ions in aqueous solution with different OH⁻/Cl⁻ molar ratios, has been investigated by X-ray absorption spectroscopy (XAS). X-ray absorption near-edge structure (XANES) spectra of [AuCl_n(OH)_4−n]⁻ solutions have been calculated and the multiple-scattering spectral features have been attributed to Cl d-states, axial water molecules and the replacement of Cl⁻ ligands by OH⁻ ligands. A square–planar geometry for [AuCl_n(OH)_4−n]⁻ with two axial water molecules has been identified. Moreover, a spectral correlation between XANES features and the type of planar atoms has been identified. By extended X-ray absorption fine structure spectra (EXAFS), the planar Au bond distances in the solutions have also been determined, e.g., 2.28 Å for Au–Cl and 1.98 Å for Au–O, respectively. The same EXAFS analysis provides evidence that the peak at about 4.0 Å in solutions with the lowest OH⁻/Cl⁻ molar ratio arises from collinear Cl–Au–Cl multiple-scattering contributions. For the first time, a complete detailed reconstruction of the hydration structure of an Au ion at different pH values has been achieved.     

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     

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.     

XANES evidence for sulphur speciation in Mn-, Ni- and W-bearing silicate melts

S K-edge XANES and Mn-, W- and Ni-XANES and EXAFS spectra of silicate glasses synthesised at 1400 °C and 1 bar with compositions in the CaO-MgO-Al₂O₃-SiO₂-S plus MnO, NiO, or WO₃ systems were used to investigate sulphur speciation in silicate glasses.S K-edge spectra comprised a composite peak with an edge between 2470 and 2471.4 eV, which was attributed to S²⁻, and a peak of variable height with an edge at 2480.2-2480.8 eV, which is consistent with the presence of S⁶⁺. The latter peak was attributed to sample oxidation during sample storage. W-rich samples produced an additional lower energy peak at 2469.8 eV that is tentatively attributed to the existence of S 3p orbitals hybridised with the W 5d states.Deconvolution of the composite peak reveals that the composite peak for Mn-bearing samples fits well to a model that combines three Lorentzians at 2473.1, 2474.9 and 2476.2 eV with an arctan edge step. The composite peak for W-bearing samples fits well to the same combination plus an additional Lorentzian at 2469.8 eV. The ratio of the proportions of the signal accounted for by peaks at 2473.1 and 2476.2 eV correlates with Mn:Ca molar ratios, but not with W:Ca ratios. Spectra from Ni-bearing samples were qualitatively similar but S levels were too low to allow robust quantification of peak components. Some part of the signal accounted for by the 2473.1 eV peak was therefore taken to record the formation of Mn-S melt species, while the 2469.8 peak is interpreted to record the formation of W-S melt species. The 2474.9 and 2476.2 eV peaks were taken to be dominated by Ca-S and Mg-S interactions. However, a 1:1 relationship between peak components and specific energy transitions is not proposed. This interpretation is consistent with known features of the lower parts of the conduction band in monosulphide minerals and indicates a similarity between sulphur species in the melts and the monosulphides. S-XANES spectra cannot be reproduced by a combination of the spectra of the component element monosulphides.Mn-, W- and Ni-XANES and EXAFS for synthetic glasses without sulphide exsolution did not show any sensitivity to the presence of sulphur, which is unsurprising as S:O ratios were sufficiently low that metals would be mostly co-ordinated by O. Mn EXAFS spectra were consistent with divalent Mn in 5 co-ordinated Mn-O melt species. W spectra were consistent with tetrahedrally co-ordinated hexavalent W, most likely in scheelite-like melt species, and Ni spectra were consistent with [4] co-ordinated divalent Ni. These results indicate lower co-ordinations for both W and Ni than those inferred by some previous workers. Cation co-ordination may reflect the proportion of non-bridging oxygens, which is lower in the Ca-rich and Al-poor samples investigated here than for previous studies.     

Iron environment in a montmorillonite from Gola del Furlo (Marche,Italy). A synchrotron radiation XANES and a Mössbauer study

Summary The iron environment and oxidation state has been determined by XANES spectroscopy in a montmorillonite sample from Gola del Furlo (Marche, Italy). A comparison with the XANES spectra of Fe^2– in a natural hematite from Elba (Italy) and of Fe 21 in a synthetic Fe[C0₃] (the fine structures in the spectra of which have also been clarified in detail on the basis of the known crystal structures) permits recognizing that in this sheet silicate Fe is mostly in the trivalent oxidation state and in a distorted octahedral coordination. Mössbauer spectroscopy confirms the XANES assignment, but it also shows that minor octahedral Fee+ is present besides the predominant octahedral Fe^3—.

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Zusammenfassung Synchroton Radiation XANES und Mössbauer-Studien zur Vertielung des Eisens im Montmorillonit aus Gola del Furlo(Marche, Italien) Die Verteilung und die Oxidationsstufe des Eisens eines Montmorillonites aus Gola del Furlo (Marche, Italien) wurden untersucht. Ein Vergleich der XANES Spektren dieses Schichtsilikates mit denen von FeFe³⁺ eines natürlichen Hämatites von Elba (Italien) und von Fe²⁺ eines synthetischen Fe[C0₃], wobei die Details der Spektren auf Grund der Kenntnis der bekannten Kristallstruktur geklärt werden konnten, zeigt, daß Eisen großteils in dreiwertiger Form und in verzerrter oktaedrischer Koordination vorliegt. Mössbauer-Studien bestätigen die Ergebnisse der XANES Untersuchungen, zeigen aber auch, daß untergeordnet Fe e+ an Stelle von Fe³⁺ in der oktaedrischen Position eingebaut wird.