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.     

Use of L-edge X-ray absorption spectroscopy to characterize multiple valence states of 3d transition metals; a new probe for mineralogical and geochemical research

2p (L _2,3) X-ray absorption spectra are presented for a range of minerals to demonstrate the usefulness of L-edge spectroscopy as a symmetry- and valenceselective probe. 2p XAS provides a sensitive fingerprint of the electronic states of 3 d transition metals and can be applied to phases containing mixtures of such elements. Calculated spectra for 3d ⁿ → 2p ⁵ 3d ⁿ⁺¹ transitions provide a basis for the interpretation of the measured spectra. Thus, in principle, multiple valence states of a particular 3 d metal can be precisely characterized from a single L-edge spectrum. Examples of vanadium L-edge spectra are presented for a range of minerals; these complex spectra hold information concerning the presence of vanadium in multiple valence states. The Cu L-edge spectrum of sulvanite (Cu₃ VS₄) indicates the presence of both Cu⁺ and Cu²⁺; the V L-edge spectrum of the same sample shows that both V²⁺ and V⁵⁺ are present. Spectral simulations representing mixtures of Fe d ⁵ and Fe d ⁶ states are used to quantify Fe³⁺/∑Fe in a spinel, a glass, and an amphibole, all of which contain Fe as a major component. To illustrate the sensitivity of 2p XAS in a dilute system, the Fe L-edge spectrum of amethyst (α-SiO₂: Fe) has been recorded; this spectrum shows that ～68% of the Fe in amethyst is Fe²⁺, and ～32% is Fe³⁺. Although previous studies on amethyst using other spectroscopic methods cite evidence for Fe⁴⁺, there is no indication in the L-edge spectrum for Fe⁴⁺ in amethyst. Comparison of theoretical and experimental spectra not only allows the valence states of 3 d ions to be recognised, but also provides site-symmetry information and crystal field parameters for each ion site.     

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.     

57Fe-Moessbauer spectra,electronic and crystal structure of members of the CuS2-FeS2 solid solution series

Members of the (Cu, Fe)S₂ solid solution crystallize in the pyrite structure type, space group Pa 3, Cu and Fe being statistically distributed on the metal sites. Within this series, a semiconductor to metal transition can be detected between 25 and 38 mole% CuS₂. Compositional dependent ⁵⁷Fe-Moessbauer spectra reveal Fe²⁺ in low-spin configuration. A minimum of the quadrupole splitting and the slope in the ⁵⁷Fe-isomer shift in the intermediate part of the system, near 30 mole% CuS₂, can be correlated with the onset of metallic conductivity, whereas the structural parameters are not influenced by this transition. The analysis of the compositional dependency of the quadrupole splitting, in comparison to the isotypic system (Co, Fe)S₂, leads to the conclusion that Cu in solid (Cu, Fe)S₂ compounds is Cu⁺ with an Ar -3 d¹⁰ electronic configuration.     

Luminescence excitation spectra of Mn2+ in synthetic forsterite

Detailed ligand-field spectra of Mn²⁺ in both microcrystalline and single-crystal synthetic forsterite are obtained using the technique of luminescence excitation spectroscopy. It is shown that Mn²⁺ has an almost exclusive preference for one particular cation site which is most probably the M2 site. Low temperature measurements reveal a no-phonon (purely electronic) transition at 16,260 cm^?1 (615 nm) which is the energy of the lowest split component of the ⁴ T ₁(G) state above the ground state. Phonon replicas of this transition are evident showing that a particular phonon mode (180 cm^?1) is dominantly involved. An analysis of the polarized spectra of Mn²⁺ in single-crystal forsterite shows the choice of C _2v (C ₂, σ _d ) pseudosymmetry for the M2 site yields the best agreement with the polarization dependence of the transitions between the ligand-field states of the Mn²⁺ ion in this site.     

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.     

The structural behavior of ferric and ferrous iron in aluminosilicate glass near meta-aluminosilicate joins

Iron-57 resonant absorption Mössbauer spectroscopy was used to describe the redox relations and structural roles of Fe³⁺ and Fe²⁺ in meta-aluminosilicate glasses. Melts were formed at 1500 °C in equilibrium with air and quenched to glass in liquid H₂O with quenching rates exceeding 200 °C/s. The aluminosilicate compositions were NaAlSi₂O₆, Ca_0.5AlSi₂O₆, and Mg_0.5AlSi₂O₆. Iron oxide was added in the form of Fe₂O₃, NaFeO₂, CaFe₂O₄, and MgFe₂O₄ with total iron oxide content in the range ∼0.9 to ∼5.6 mol% as Fe₂O₃. The Mössbauer spectra, which were deconvoluted by assuming Gaussian distributions of the hyperfine field, are consistent with one absorption doublet of Fe²⁺ and one of Fe³⁺. From the area ratios of the Fe²⁺ and Fe³⁺ absorption doublets, with corrections for differences in recoil-fractions of Fe³⁺ and Fe²⁺, the Fe³⁺/ΣFe is positively correlated with increasing total iron content and with decreasing ionization potential of the alkali and alkaline earth cation. There is a distribution of hyperfine parameters from the Mössbauer spectra of these glasses. The maximum in the isomer shift distribution function of Fe³⁺, δ_Fe³⁺, ranges from about 0.25 to 0.49 mm/s (at 298 K relative to Fe metal) with the quadrupole splitting maximum, Δ_Fe³⁺, ranging from ∼1.2 to ∼1.6 mm/s. Both δ_Fe³⁺ and δ_Fe²⁺ are negatively correlated with total iron oxide content and Fe³⁺/ΣFe. The dominant oxygen coordination number Fe³⁺ changes from 4 to 6 with decreasing Fe³⁺/ΣFe. The distortion of the Fe³⁺-O polyhedra of the quenched melts (glasses) decreases as the Fe³⁺/ΣFe increases. These polyhedra do, however, coexist with lesser proportions of polyhedra with different oxygen coordination numbers. The δ_Fe²⁺ and Δ_Fe²⁺ distribution maxima at 298 K range from ∼0.95 to 1.15 mm/s and 1.9 to 2.0 mm/s, respectively, and decrease with increasing Fe³⁺/ΣFe. We suggest that these hyperfine parameter values for the most part are more consistent with Fe²⁺ in a range of coordination states from 4- to 6-fold. The lower δ_Fe²⁺-values for the most oxidized melts are consistent with a larger proportion of Fe²⁺ in 4-fold coordination compared with more reduced glasses and melts.     

Distribution and bioavailability of Cr in central Euboea, Greece

Plants and soils from central Euboea, were analyzed for Cr_(totai), Cr(VI), Ni, Mn, Fe and Zn. The range of metal concentrations in soils is typical to those developed on Fe-Ni laterites and ultramafic rocks. Their bioavailability was expressed in terms of concentrations extractable with EDTA and 1 M HNO₃, with EDTA having a limited effect on metal recovery. Cr(VI) concentrations in soils evaluated by alkaline digestion solution were lower than phytotoxic levels. Chromium and Ni — and occasionally Zn — in the majority of plants were near or above toxicity levels. Cr(VI) concentrations in plants were extremely low compared to total chromium concentrations. Cr_(total) in ground waters ranged from <1 μg.L^?1 to 130 μg.L^?1, with almost all chromium present as Cr(VI). With the exception of Cr_(total) and in some cases Zn, all elements were below regulatory limits for drinking water. On the basis of Ca, Mg, Cr_(total) and Si ground waters were classified into three groups: Group(I) with Cr concentrations less than 1 μg.L^?1 from a karstic aquifer; Group(II) with average concentrations of 24 μg.L^?1 of Cr and relatively high Si associated with ophiolites; and Group(III) with Cr concentrations of up to 130 μg.L^?1, likely due to anthropogenic activity. Group(III) is comparable to ground waters from Assopos basin, characterized by high Cr(VI) concentrations, probably due to industrial actrivities.     

Mössbauer spectra and magnetic features of ilvaites

Ilvaite samples from six different localities in Japan are found to be members of a solid-solution series varying from Ca(Fe²⁺,Fe³⁺)₂Fe²⁺(OH)O Si₂O₇ to approaximately Ca(Fe²⁺,Fe³⁺)₂Fe _0.5 ²⁺ Mn _0.5 ²⁺ (OH)O Si₂O₇, and have been studied by Mössbauer spectrometry and magnetic measurements. The variation in intensity of Mössbauer doublets confirms that Mn substitutes for Fe²⁺ in the M(B) cation site. An temperatures decreasing from 300 K to 4K, an abrupt change in the reciprocal mass magnetic susceptibility, 1/x _g, occurs about 120 K; 1/x _g depends linearly upon temperature above 120 K. This change, which is characterized by an unusual mode of decrease in 1/x _g, has been interpreted based on Mössbauer spectra at 80 K: the spectra of Fe²⁺ and Fe³⁺ in the M(A) site show Zeeman splitting, whereas those of Fe²⁺ in the M(B) site do not show the effect. This Mössbauer evidence suggests that magnetic spins of Fe in M(A) are in an ordered state, very likely of antiparallel coupling, whereas those of Fe in M(B) are randomly oriented, showing that below 120 K ilvaite has two different magnetic states for Fe ions. As there is a line of evidence that the spins of Fe in M(B) would take an ordered state at extremely low temperatures, ilvaite magnetism may be regarded as basically antiferromagnetic. The magnetic spins of Fe in M(A) and M(B) undergo magnetic transitions at different specific temperatures, thus giving as a whole unusual features of magnetism.     

The Removal of Dissolved Metals by Hydroxysulphate Precipitates during Oxidation and Neutralization of Acid Mine Waters, Iberian Pyrite Belt

This study examines the removal of dissolved metals during the oxidation and neutralization of five acid mine drainage (AMD) waters from La Zarza, Lomero, Esperanza, Corta Atalaya and Poderosa mines (Iberian Pyrite Belt, Huelva, Spain). These waters were selected to cover the spectrum of pH (2.2–3.5) and chemical composition (e.g., 319–2,103 mg/L Fe; 2.85–33.3 g/L SO₄⁼) of the IPB mine waters. The experiments were conducted in the laboratory to simulate the geochemical evolution previously recognized in the field. This evolution includes two stages: (1) oxidation of dissolved Fe(II) followed by hydrolysis and precipitation of Fe(III), and (2) progressive pH increase during mixing with fresh waters. Fe(III) precipitates at pH < 3.5 (stages 1 and 2) in the form of schwertmannite, whereas Al precipitates during stage 2 at pH 5.0 in the form of several hydroxysulphates of variable composition (hydrobasaluminite, basaluminite, aluminite). During these stages, trace elements are totally or partially sorbed and/or coprecipitated at different rates depending basically on pH, as well as on the activity of the SO₄⁼ anion (which determines the speciation of metals). The general trend for the metals which are chiefly present as aqueous free cations (Pb²⁺, Zn²⁺, Cu²⁺, Cd²⁺, Mn²⁺, Co²⁺, Ni²⁺) is a progressive sorption at increasing pH. On the other hand, As and V (mainly present as anionic species) are completely scavenged during the oxidation stage at pH < 3.5. In waters with high activities (> 10⁻¹) of the SO ₄⁼ ion, some elements like Al, Zn, Cd, Pb and U can also form anionic bisulphate complexes and be significantly sorbed at pH < 5. The removal rates at pH 7.0 range from around 100% for As, V, Cu and U, and 60–80% for Pb, to less than 20% for Zn, Co, Ni and Mn. These processes of metal removal represent a significant mechanism of natural attenuation in the IPB.     

Multi-spectroscopic study of Fe(II) in silicate glasses: Implications for the coordination environment of Fe(II) in silicate melts

The coordination environment of Fe(II) has been examined in seven anhydrous ferrosilicate glasses at 298 K and 1 bar using ⁵⁷Fe Mössbauer, Fe K-edge X-ray near edge structure (XANES), and extended X-ray absorption fine structure (EXAFS), UV-Vis-NIR, and magnetic circular dichroism (MCD) spectroscopies. Glasses of the following compositions were synthesized from oxide melts (abbreviation and nonbridging oxygen:tetrahedral cation ratio (NBO/T) in parentheses): Li₂FeSi₃O₈ (LI2: 1.33), Rb₂FeSi₃O₈ (RB2: 1.33), Na_l.08Fe_l.l7Si_3.l3O₈ (NAl: 1.09), Na_l.46Ca_0.24Fe_l.08Si_2.97O₈ (NC6: 1.38), Na_l.09Ca_0.51Fe_0.72Si_3.10O₈ (NC2: 1.15), Na_0.99Ca_0.92Fe_0.24 Si_3.17O₈ (NCl: 1.04), and Na_0.29Mg_0.53Ca_0.52Fe_0.56Al_0.91Si_2.44O₈ (BAS: 1.05). Mössbauer, XANES, and EXAFS information suggests that iron is dominantly ferrous in all glasses (<10 atom% Fe(III)) with an average first-neighbor Fe(II) coordination varying from ∼ 4 to 5.2 (±0.2) oxygens. The UV-Vis-NIR spectrum of each sample exhibits intense absorption centered near 8100-9200 cm⁻¹ and weak absorption near 5000 cm^−l, which cannot be assigned unambiguously. The MCD spectrum of NC6 glass, which is the first such measurement on a silicate glass, shows three transitions at ∼8500 cm⁻¹, ∼6700 cm⁻¹, and ∼4500 cm⁻¹. The behavior of these MCD bands as a function of temperature (1.6 K to 300 K) and magnetic field strength (1 T to 7 T) indicates that they most likely arise from three distinct Fe(II) sites with different ground states, two of which are 5-coordinated and one of which is 4-coordinated by oxygens.The combined results suggest that Fe(II) predominantly occupies 5- and 4-coordinated sites in each glass, with the ratios differing for the different compositions. Small amounts of 6-coordinated Fe(II) are possible as well, but primarily in the more basic glass compositions such as BAS. The substitution of Li(I) for Rb(I) in the M₂FeSi₃O₈ base glass composition causes a weakening of the average Fe(II)-O bond, as indicated by the longer Fe(II)-O distance in the latter. The basalt composition glass was found to have the largest Fe(II) sites relative to those in the other glasses in this study. A bond valence model that helps predict the coordination number of Fe(II) in silicate glasses is proposed. The structural information extrapolated to Fe(II)-bearing melts is parameterized using bond valence theory, which helps to rationalize the melt-crystal partitioning behavior of ferrous iron in natural and synthetic melt-crystal systems.     

Iron (III)-silica interactions in aqueous solution: insights from X-ray absorption fine structure spectroscopy

The influence of aqueous silica on the hydrolysis of iron(III) nitrate and chloride salts in dilute aqueous solutions (m_Fe ∼ 0.01 mol/kg) was studied at ambient temperature using X-ray absorption fine structure (XAFS) spectroscopy at the Fe K-edge. Results show that in Si-free iron nitrate and chloride solutions at acid pH (pH < 2.5), Fe is hexa-coordinated with 6 oxygens of H₂O- and/or OH-groups in the first coordination sphere of the metal, at an Fe-O distance of 2.00 ± 0.01 Å. With increasing pH (2.7 < pH < 13), these groups are rapidly replaced by bridging hydroxyls (-OH-) or oxygens (-O-), and polymerized Fe hydroxide complexes form via Fe-(O/OH)-Fe bonds. In these polymers, the first atomic shell of iron represents a distorted octahedron with six O/OH groups and Fe-O distances ranging from 1.92 to 2.07 Å. The Fe octahedra are linked together by their edges (Fe-Fe distance 2.92-3.12 Å) and corners (Fe-Fe distance ∼3.47 ± 0.03 Å). The Fe-Fe coordination numbers (N_edge = 1-2; N_corner = 0.5-0.7) are consistent with the dominant presence of iron dimers, trimers and tetramers at pH 2.5 to 2.9, and of higher-polymerized species at pH > 3.At pH > 2.5 in the presence of aqueous silica, important changes in Fe(III) hydrolysis are detected. In 0.05-m Si solutions (pH ∼ 2.7-3.0), the corner linkages between Fe octahedra in the polymeric complexes disappear, and the Fe-Fe distances corresponding to the edge linkages slightly increase (Fe-Fe_edge ∼ 3.12-3.14 Å). The presence of 1 to 2 silicons at 3.18 ± 0.03 Å is detected in the second atomic shell around iron. At basic pH (∼12.7), similar structural changes are observed for the iron second shell. The Fe-Si and Fe-Fe distances and coordination numbers derived in this study are consistent with (1) Fe-Si complex stoichiometries Fe₂Si_1-2 and Fe₃Si_2-3 at pH < 3; (2) structures composed of Fe-Fe dimers and trimers sharing one or two edges of FeO₆-octahedra; and (3) silicon tetrahedra linked to two neighboring Fe octahedra via corners. At higher Si concentration (0.16 m, polymerized silica solution) and pH ∼ 3, the signal of the Fe second shell vanishes indicating the destruction of the Fe-Fe bonds and the formation of different Fe-Si linkages. Moreover, ∼20 mol.% of Fe is found to be tetrahedrally coordinated with oxygens in the first coordination shell (R_Fe-O = 1.84 Å). This new finding implies that Fe may partially substitute for Si in the tetrahedral network of the silica polymers in Si-rich solutions.The results of this study demonstrate that aqueous silica can significantly inhibit iron polymerization and solid-phase formation, and thus increase the stability and mobility of Fe(III) in natural waters. The silica “poisoning” of the free corner sites of iron-hydroxide colloids should reduce the adsorption and incorporation of trace elements by these colloids in Si-rich natural waters.     

Quantification of the ferric/ferrous iron ratio in silicates by scanning transmission X-ray microscopy at the Fe L2,3 edges

Estimation of Fe³⁺/ΣFe ratios in materials at the submicrometre scale has been a long-standing challenge in the Earth and environmental sciences because of the usefulness of this ratio in estimating redox conditions as well as for geothermometry. To date, few quantitative methods with submicrometric resolution have been developed for this purpose, and most of them have used electron energy-loss spectroscopy carried out in the ultra-high vacuum environment of a transmission electron microscope (TEM). Scanning transmission X-ray microscopy (STXM) is a relatively new technique complementary to TEM and is increasingly being used in the Earth sciences. Here, we detail an analytical procedure to quantify the Fe³⁺/ΣFe ratio in silicates using Fe L_2,3-edge X-ray absorption near edge structure (XANES) spectra obtained by STXM, and we discuss its advantages and limitations. Two different methods for retrieving Fe³⁺/ΣFe ratios from XANES spectra are calibrated using reference samples with known Fe³⁺ content by independent approaches. The first method uses the intensity ratio of the two major peaks at the L₃-edge. This method allows mapping of Fe³⁺/ΣFe ratios at a spatial scale better than 50 nm by the acquisition of 5 images only. The second method employs a 2-eV-wide integration window centred on the L₂ maximum for Fe³⁺, which is compared to the total integral intensity of the Fe L₂-edge. These two approaches are applied to metapelites from the Glarus massif (Switzerland), containing micrometre-sized chlorite and illite grains and prepared as ultrathin foils by focused ion beam milling. Nanometre-scale mapping of iron redox in these samples is presented and shows evidence of compositional zonation. The existence of such zonation has crucial implications for geothermometry and illustrates the importance of being able to measure Fe³⁺/ΣFe ratios at the submicrometre scale in geological samples.     

Soft X-ray spectroscopy of ferrous silicates

Energy gaps and electrical conductivities in the ferrous silicates, Fe₂SiO₄ and FeSiO₃, depend primarily on Fe-O bonding and may be studied by ultraviolet and soft X-ray spectroscopy. We have measured FeL_II–III X-ray band spectra under conditions of “minimal” (I₄, at 4.0 keV) and “high” (I₁₀, at 10.0 keV) self absorption to determine 3d orbital energy levels, to delineate d states in the valence band, and to construct band gap models. Absorption spectra, I₄/I₁₀, were computed to determine vacant orbital levels in the gap. A difference function (I₄–I₁₀) has been proposed to identify X-radiation at photon energies above the measured L_III absorption edge, including high-energy, double-vacancy satellites and radiative transitions involving the anti-parallel (spin-down) d ⁶ electron in the ground state. The proposed band gap model for Fe₂SiO₄ is consistent with that of Nitsan and Shankland (1976), including an intrinsic transition of 6.5 eV and an energy gap of 7.8 eV. The 3d orbital energy level electronic structures are in general agreement with levels computed by Tossell et al. (1974) for [FeO₆]^10? in FeO using an SCF Xα cluster MO method. A high-energy, double-vacancy satellite was found at ～710.7 eV, and is presumed to originate from an L_IIIM_II,III initial state. The intensity of these satellites for the ferrous silicates and other iron compounds, and corresponding Fe L_II/L_III intensity ratios are correlated with differences in band gap magnitudes and gap structure. Fe L_II/L_III intensity ratios are not well correlated with iron oxidation state.     

Spectroscopic characterisation and crystal field calculations of varicoloured kyanites from Loliondo, Tanzania

Orange, ochre-coloured, light green and dark blue varieties of kyanite, ideally Al₂SiO₅, from Loliondo, Tanzania, have been characterised by electron microprobe analysis and polarised infrared and optical absorption spectroscopy. All colour varieties show elevated Fe contents of 0.39 to 1.31 wt.% FeO, but Ti contents only in the range of the EMP detection limit. Orange and ochre-coloured crystals have Mn contents of 0.23 and 0.06 wt.% MnO, respectively, the dark blue kyanite contains 0.28 wt.% Cr₂O₃, while the light green sample is nearly free from transition metal cations other than Fe. Polarised infrared spectra reveal OH defect concentrations of 3 to 17 wt.ppm H₂O with structural OH defects partially replacing the O_B (O2) oxygen atoms. Polarised optical absorption spectra show that the colour of all four varieties is governed by crystal field d-d transitions of trivalent cations, i.e. Fe³⁺ (all samples), Mn³⁺ (orange and ochre) and Cr³⁺ (blue kyanite), replacing Al in sixfold coordinated triclinic sites of the kyanite structure. Intervalence charge transfer, the prevalent colour-inducing mechanism in ‘usual’ (Cr-poor) blue kyanites, seems to play a very minor, if any, role in the present samples. Crystal field calculations in both a ‘classic’ tetragonal and in the semiempirical Superposition Model approach, accompanied by distance- and angle-least-squares refinements, indicate that Fe³⁺ preferably occupies the Al4 site, Cr³⁺ prefers the Al1 and Al2 sites, and Mn³⁺ predominantly enters the Al1 site. In each case specific local relaxation effects were observed according to the crystal chemical preferences of these transition metal cations. Furthermore, the high values obtained in the calculations for the interelectronic repulsion parameter Racah B correspond to a high ionic contribution to Me³⁺–O bonding in the kyanite structure. In the particular case of the blue sample, band positions specifically related to the high Racah B value enable this ‘unusual’ type of blue colouration of kyanite solely due to Cr³⁺ cations.     

The bonding of ferrous iron to sulfur and oxygen in tetrahedral coordination: A comparative study using SCF Xα scattered wave molecular orbital calculations

Molecular quantum mechanical calculations have been performed on high-spin ferrous iron tetrahedrally coordinated to sulfur and oxygen, respectively. The molecular orbital energies obtained from the calculations are compared with experimental optical and X-ray emission spectra. Good agreement was found between calculated and experimental spectral transition energies for the optical absorption spectra of Fe²⁺ in sphalerite, of Fe²⁺ in FeAl₂O₄, staurolite and (Zn, Fe)O, and for the FeKβ X-ray emission spectra of FeCr₂O₄. This both clarified interpretation of the spectra and established the validity of the calculations. Distinct differences occur in the molecular orbital structures of the sulfide and oxide clusters. In the sulfide, the crystal field type (mainly Fe 3d) molecular orbitals lie within the nonbonding (mainly S 3p) orbitais in energy, whereas in the oxide, they lie well above the 02p nonbonding orbitals. This also results in a wider valence band in the oxide than in the sulfide. The crystal field type (Fe 3d) molecular orbitais have more ligand character in the sulfide than the oxide and the chalcophilic properties of iron are partly attributed to this observation.     

Atmospheric chemical composition of the halo star HD 221170 from a synthetic-spectrum analysis

The atmospheric abundances of 30 chemical elements in the halo star HD 221170 are analyzed by fitting synthetic spectra to observed spectra (i) with a resolution of 60 000 and signal-to-noise ratios of about 200 taken with the 1.93-m telescope of the Observatoire de Haute Provence and (ii) with a resolution of 35 000 and signal-to-noise ratios of more than 100 taken with the 2-m telescope of the Terskol Peak Observatory. The derived parameters of the stellar atmosphere are T_eff=4475 K, log g=1.0, [Fe/H]=?2.03, V_micro=1.7 km/s, and V_macro=4 km/s. The parameters T_eff, log g, [Fe/H], and V_micro can be determined by analyzing the variations of the rms error of the mean iron abundance derived using different model atmospheres. The chemical composition of the star’s atmosphere is analyzed. The abundances of a total of 35 elements in HD 221170 have been derived in this paper and in previous studies. Overall, the abundances of elements lighter than praseodymium are consistent with the elemental abundances in the atmospheres of stars with similar metal deficits. Copper and manganese are underabundant by ?2.9 and ?2.6 dex, respectively, relative to the Sun (when the analysis includes the effects of hyperfine structure). Heavy r-process elements (starting from praseodymium) are overabundant compared to iron-group elements. This can be explained by an enrichment in r-process elements of the material from which the star was formed.     

Geochemistry of diffuse low-temperature hydrothermal fluids in the North Fiji basin

Low-temperature (<13°C) diffuse hydrothermal fluids were sampled directly at the seafloor with a specially designed Hydro Bottom Station in the North Fiji Basin and analyzed for gases, major and minor elements, and a large number of trace metals. The fluids were significantly enriched in CO₂, Si, Li, Rb, Cs, Ba, Mn, and several trace metals compared to ambient seawater, had high CH₄ and H₂S concentrations, and had a slightly decreased salinity. Calculated end-member concentrations of the low-temperature fluids show a strong similarity to the neighboring hot vents, implying that the diffuse fluids are hot vent waters diluted by seawater. According to the chemical composition, the sampled fluids derive from vapor-phase fluids produced by subseafloor boiling and phase separation. Compared to hot vents from other regions, Mn, Fe, and other trace metal concentrations are low. Subsurface metal sulfide precipitation during cooling and dilution with seawater has further decreased the dissolved metal contents of the diffuse fluids, thus creating a very favorable environment for the hydrothermal fauna, as indicated by a very low Fe/H₂S ratio. Therefore, the fluids support high bioproductivity but no hydrothermal mineral precipitation. The emanation of the condensed vapor phase appears to have been stable during the past 10 years; however, the occurrence of metal sulfide particles in some fluid and sediment samples and small areas of dead fauna indicate that the hydrothermal system may be evolving toward the emanation of the stored brine phase.     

多壁碳纳米管固相萃取快速检测水样中铅镉铜铁

传统的固相萃取填料应用于环境样品的重金属处理过程中,存在pH不稳定和不同极性萃取物共同萃取较为困难等方面的不足,因此寻找新型固相萃取填料显得尤为重要。本文采用多壁碳纳米管填充固相萃取柱,萃取水中金属元素铅、镉、铜和铁,采用石墨炉原子吸收光谱法测定铅和镉,电感耦合等离子体发射光谱法测定铜和铁。实验考察了多壁碳纳米管的性质、溶液pH值、洗脱溶液、样品流速以及基体效应对测定结果的影响。结果显示:溶液pH=9,1 mol/L硝酸为洗脱溶液,样品流速为2 mL/min时,外径8 nm未修饰的多壁碳纳米管有较好的萃取效率,对溶液中铅、镉、铜和铁的最大吸附容量分别为44.91、42.31、54.68和49.07 mg/g,四种元素的吸附容量均衡;钾、钠、钙、镁离子以及苯和甲苯等基质对四种金属元素的萃取影响不大。方法回收率为95.3%~99.5%,精密度(RSD,n=7)为1.2%~3.2%。本方法采用外径8 nm的多壁碳纳米管固相萃取,与传统萃取方法相比,富集效果好、回收率较高,而且操作简便、准确度高;与前人采用外径20~30 nm的多壁碳纳米管的性能相比,镉和铜的吸附容量更高,还可实现对铁的吸附,且铅、镉、铜和铁四种元素的吸附容量均衡,更适合用于检测水样中的金属元素。     

Theory of electronic structures of chemisorption on oxide surfaces

Surface electronic structures of metal oxides such as MgO, TiO₂, SrTiO₃, ReO₃ and transition-metal monoxides are discussed based on the first-principles DV-Xα cluster and slab methods. Particular attention is paid to the origin and properties of intrinsic and extrinsic surface states. A close correlation between the surface structure and electronic states is confirmed. Some exotic properties of polar oxide surfaces, for example the formation of a two-dimensional metallic band, are predicted.