Acid-base properties of a goethite surface model: A theoretical view

Density functional theory is used to compute the effect of protonation, deprotonation, and dehydroxylation of different reactive sites of a goethite surface modeled as a cluster containing six iron atoms constructed from a slab model of the (1 1 0) goethite surface. Solvent effects were treated at two different levels: (i) by inclusion of up to six water molecules explicitly into the quantum chemical calculation and (ii) by using additionally a continuum solvation model for the long-range interactions. Systematic studies were made in order to test the limit of the fully hydrated cluster surfaces by a monomolecular water layer. The main finding is that from the three different types of surface hydroxyl groups (hydroxo, μ-hydroxo, and μ₃-hydroxo), the hydroxo group is most active for protonation whereas μ- and μ₃-hydroxo sites undergo deprotonation more easily. Proton affinity constants (pK_a values) were computed from appropriate protonation/deprotonation reactions for all sites investigated and compared to results obtained from the multisite complexation model (MUSIC). The approach used was validated for the consecutive deprotonation reactions of the [Fe(H₂O)₆]³⁺ complex in solution and good agreement between calculated and experimental pK_a values was found. The computed pK_a for all sites of the modeled goethite surface were used in the prediction of the pristine point of zero charge, pH_PPZN. The obtained value of 9.1 fits well with published experimental values of 7.0-9.5.     

A theoretical study of bond distances,X-ray spectra and electron density distributions in borate polyhedra

The borate polyhedra BO ₃ ^3? , B(OH)₃, BO ₄ ^5? , and B(OH) ₄ ^? are studied using the ab initio and multiple scattering Xα quantum mechanical methods. The ab initio self-consistent-field (SCF) molecular orbital (MO) method, at the minimum basis set level, predicts equilibrium B-O distances within 0.04 Å of their average values in solids so long as the polyhedron charge is small. Orbital energies from double zeta basis set ab initio calculations and analogies with isoelectric compounds are used to assign the X-ray spectra of BO ₃ ^3? and to predict the valence region spectra of BO ₄ ^5? . Contour maps of the difference between molecular and superimposed free atom electron densities show charge buildup along the B-O bond which is only slightly smaller than that observed in CO ₃ ^2? .     

Dissolution mechanisms of water in depolymerized silicate melts: Constraints from H and Si NMR spectroscopy and ab initio calculations

Dissolution of water in magmas significantly affects phase relations and physical properties. To shed new light on the this issue, we have applied ¹H and ²⁹Si nuclear magnetic resonance (NMR) spectroscopic techniques to hydrous silicate glasses (quenched melts) in the CaO-MgO-SiO₂ (CMS), Na₂O-SiO₂, Na₂O-CaO-SiO₂ and Li₂O-SiO₂ systems. We have also carried out ab initio molecular orbital calculations on representative clusters to gain insight into the experimental results.The most prominent result is the identification of a major peak at ∼1.1 to 1.7 ppm in the ¹H MAS NMR spectra for all the hydrous CMS glasses. On the basis of experimental NMR data for crystalline phases and ab initio calculation results, this peak can be unambiguously attributed to (Ca,Mg)OH groups. Such OH groups, like free oxygens, are only linked to metal cations, but not part of the silicate network, and are thus referred to as free hydroxyls in the paper. This represents the first direct evidence for a substantial proportion (∼13∼29%) of the dissolved water as free hydroxyl groups in quenched hydrous silicate melts. We have found that free hydroxyls are favored by (1) more depolymerized melts and (2) network-modifying cations of higher field strength (Z/R²: Z: charge, R: cation-oxygen bond length) in the order Mg > Ca > Na. Their formation is expected to cause an increase in the melt polymerization, contrary to the effect of SiOH formation. The ²⁹Si MAS NMR results are consistent with such an interpretation. This water dissolution mechanism could be particularly important for ultramafic and mafic magmas.The ¹H MAS NMR spectra for glasses of all the studied compositions contain peaks in the 4 to 17 ppm region, attributable to SiOH of a range of strength of hydrogen bonding and molecular H₂O. The relative population of SiOH with strong hydrogen bonding grows with decreasing field strength of the network-modifying cations. Ab initio calculations confirmed that this trend largely reflects hydrogen bonding with nonbridging oxygens.     

论安徽省姑山铁矿床的热液成矿特征

姑山铁矿床产在燕山期辉石闪长岩与中三叠统黄马青组砂页岩的接触带上。矿石具有典型的斑状、球颗状和骨架状结构。镜下研究表明,这些结构不是矿浆结晶的产物,而是热液成因微晶赤铁矿在后期地质过程中发生变晶生长所致。矿床中的蚀变和矿化自下而上呈现规律性的分带。碳酸盐化是特征性的蚀变类型,其形成与成矿密切有关,并可作为一种近矿找矿标志。在热液成矿过程中,辉石闪长岩中的铁很可能以羰基络合物的形式发生活化转移。在热液演化过程中由于氧逸度的升高和碱度、压力的降低,羰基络合物发生分解而使铁在接触带附近沉淀成矿。     

The oxidation states of copper and iron in mineral sulfides, and the oxides formed on initial exposure of chalcopyrite and bornite to air

Metal L_2,3, sulfur K and oxygen K near-edge X-ray absorption fine structure (NEXAFS) spectra for chalcopyrite, bornite, chalcocite, covellite, pyrrhotite and pyrite have been determined from single-piece natural mineral specimens in order to assess claims that chalcopyrite should be regarded as Cu^IIFe^IIS₂ rather than Cu^IFe^IIIS₂, and that copper oxide species are the principal initial oxidation products on chalcopyrite and bornite exposed to air. Spectra were obtained using both fluorescence and electron yields to obtain information representative of the bulk as well as the surface. Where appropriate, NEXAFS spectra have been interpreted by comparison with the densities of unfilled states and simulated spectra derived from ab initio calculations using primarily the FEFF8 code and to a lesser extent WIEN2k. Metal 2p and S 2p photoelectron spectra excited by monochromatised Al K_α X-rays were determined for each of the surfaces characterised by NEXAFS spectroscopy. The X-ray excited Cu LMM Auger spectrum was also determined for each copper-containing sulfide. FEFF8 calculations were able to simulate the experimental NEXAFS spectra quite well in most cases. For covellite and chalcocite, it was found that FEFF8 did not provide a good simulation of the Cu L₃-edge spectra, but WIEN2k simulations were in close agreement with the experimental spectra. Largely on the basis of these simulations, it was concluded that there was no convincing evidence for chalcopyrite to be represented as Cu^IIFe^IIS₂, and no strong argument for some of the Cu in either bornite or covellite to be regarded as Cu(II). The ab initio calculations for chalcopyrite and bornite indicated that the density of Cu d-states immediately above the Fermi level was sufficient to account for the Cu L₃-edge absorption spectrum, however these incompletely filled Cu d-states should not be interpreted as indicating some Cu(II) in the sulfide structure. It was also concluded that the X-ray absorption spectra were quite consistent with the initial oxidation products on chalcopyrite and bornite surfaces being iron oxide species, and inconsistent with the concomitant formation of copper-oxygen species.     

Correlations between 11B NMR parameters and structural characters in borate and borosilicate minerals investigated by high-resolution MAS NMR and ab initio calculations

Borates consisting of diverse fundamental building blocks (FBB) formed from complex polymerization of planar triangular [Bϕ₃] groups and tetrahedral [Bϕ₄] groups, where ϕ = O and OH, provide an excellent opportunity for investigation of correlations between the NMR parameters and local structures. However, previous studies suggested that the ¹¹B NMR parameters in borates are insensitive to local structural environments other than the B coordination number, in contrast to those documented for ²⁹Si, ²³Na and ²⁷Al in silicates, and no correlation between ¹¹B chemical shifts and the sum of bond valences has been established for borate minerals with hydroxyl groups or molecular water in the structures. In this study, high-resolution NMR spectra have been acquired at the ultra high field of 21 T as well as at 14 T for selected borate and borosilicate minerals, and have been used to extract high-precision NMR parameters by using combined ab initio theoretical calculations and spectral simulations. These new NMR parameters reveal subtle correlations with various structural characters, especially the effects of the ¹¹B chemical shifts from the bridging oxygen atom(s), site symmetry, symmetry of FBB, the sum of bond valences, as well as the next-nearest-neighbor cations and hydrogen bonding. Also, these results provide new insights into the shielding mechanism for ¹¹B in borate and borosilicate minerals. In particular, this study demonstrates that the small variation in ¹¹B chemical shifts can still be used to probe the local structural environments and that the established correlations can be used to investigate the structural details in borates and amorphous materials.     

Quantum mechanical calculations of the vibrational spectra of quartz- and rutile-type GeO2

Heat-treatment and stepwise cooling of as-delivered, water-containing quartz-type GeO₂ powder resulted in transformation into a water-free form. A rutile-type modification could be prepared by impregnation of the quartz-type phase with RbOH solutions, drying and annealing. Raman- and FTIR-absorption spectra of quartz- and rutile-type GeO₂ were measured and compared to quantum-mechanical ab initio calculations based on a hybrid functional using the Perdew–Burke–Ernzerhof correlation functional with 16.7% Hartree–Fock exchange density functional. Maximum and mean deviations between measured spectral bands and assigned vibrational modes are 14 and ±8 cm⁻¹ for the quartz-type and 30 and ±13 cm⁻¹ for the rutile-type polymorphic form. Water is incorporated into GeO₄ entities of quartz-type GeO₂; a water-free and structurally stable form can be prepared by a heating up to 1,425 K, tempering at 1,323 K and stepwise cooling. Spectral bands not explained by the calculations suggest defects and distortions in both quartz- and rutile-type structures, in case of the quartz-type one by incomplete transformation into an ideal structure after removing the water, whereas the rutile-type modification most probably incorporates Rb during its synthesis.     

Effects of changing solution chemistry on Fe/Fe isotope fractionation in aqueous Fe-Cl solutions

The range in ⁵⁶Fe/⁵⁴Fe isotopic compositions measured in naturally occurring iron-bearing species is greater than 5‰. Both theoretical modeling and experimental studies of equilibrium isotopic fractionation among iron-bearing species have shown that significant fractionations can be caused by differences in oxidation state (i.e., redox effects in the environment) as well as by bond partner and coordination number (i.e., nonredox effects due to speciation).To test the relative effects of redox vs. nonredox attributes on total Fe equilibrium isotopic fractionation, we measured changes, both experimentally and theoretically, in the isotopic composition of an Fe²⁺-Fe³⁺-Cl-H₂O solution as the chlorinity was varied. We made use of the unique solubility of FeCl₄⁻ in immiscible diethyl ether to create a separate spectator phase against which changes in the aqueous phase could be quantified. Our experiments showed a reduction in the redox isotopic fractionation between Fe²⁺- and Fe³⁺-bearing species from 3.4‰ at [Cl⁻] = 1.5 M to 2.4‰ at [Cl⁻] = 5.0 M, due to changes in speciation in the Fe-Cl solution. This experimental design was also used to demonstrate the attainment of isotopic equilibrium between the two phases, using a ⁵⁴Fe spike.To better understand speciation effects on redox fractionation, we created four new sets of ab initio models of the ferrous chloride complexes used in the experiments. These were combined with corresponding ab initio models for the ferric chloride complexes from previous work. At 20 °C, 1000 ln β (β = ⁵⁶Fe/⁵⁴Fe reduced partition function ratio relative to a dissociated Fe atom) values range from 6.39‰ to 5.42‰ for Fe(H₂O)₆²⁺, 5.98‰ to 5.34‰ for FeCl(H₂O)₅⁺, and 5.91‰ to 4.86‰ for FeCl₂(H₂O)₄, depending on the model. The theoretical models predict ferric-ferrous fractionation about half as large (depending on model) as the experimental results.Our results show (1) oxidation state is likely to be the dominant factor controlling equilibrium Fe isotope fractionation in solution and (2) nonredox attributes (such as ligands present in the aqueous solution, speciation and relative abundances, and ionic strength of the solution) can also have significant effects. Changes in the isotopic composition of an Fe-bearing solution will influence the resultant Fe isotopic signature of any precipitates.     

Crossover of cation partitioning in olivines: a combination of ab initio and Monte Carlo study

We report studies based on a combination of ab initio electronic structure and Monte Carlo (MC) technique on the problem of cation partitioning among inequivalent octahedral sites, M1 and M2 in mixed olivines containing Mg²⁺ and Fe²⁺ ions. Our MC scheme uses interactions derived out of ab initio, density functional calculations carried out on measured crystal structure data. Our results show that there is no reversal of the preference of Fe for M1 over M2 as a function of temperature. Our findings do not agree with the experimental findings of Redfern et al. (Phys Chem Miner 27:630–637, 2000), but are in agreement with those of Heinemann et al. (Eur J Mineral 18:673–689, 2006) and Morozov et al. (Eur J Mineral 17:495–500, 2005).     

Copper(II) sorption onto goethite, hematite and lepidocrocite: a surface complexation model based on ab initio molecular geometries and EXAFS spectroscopy

We measured the adsorption of Cu(II) onto goethite (α-FeOOH), hematite (α-Fe₂O₃) and lepidocrocite (γ-FeOOH) from pH 2-7. EXAFS spectra show that Cu(II) adsorbs as (CuO₄H_n)ⁿ⁻⁶ and binuclear (Cu₂O₆H_n)ⁿ⁻⁸ complexes. These form inner-sphere complexes with the iron (hydr)oxide surfaces by corner-sharing with two or three edge-sharing Fe(O,OH)₆ polyhedra. Our interpretation of the EXAFS data is supported by ab initio (density functional theory) geometries of analogue Fe₂(OH)₂(H₂O)₈Cu(OH)₄and Fe₃(OH)₄(H₂O)₁₀Cu₂(OH)₆ clusters. We find no evidence for surface complexes resulting from either monodentate corner-sharing or bidentate edge-sharing between (CuO₄H_n)ⁿ⁻⁶ and Fe(O,OH)₆ polyhedra. Sorption isotherms and EXAFS spectra show that surface precipitates have not formed even though we are supersaturated with respect to CuO and Cu(OH)₂. Having identified the bidentate (FeOH)₂Cu(OH)₂⁰ and tridentate (Fe₃O(OH)₂)Cu₂(OH)₃⁰ surface complexes, we are able to fit the experimental copper(II) adsorption data to the reactions

     

Polarized EXAFS, distance-valence least-squares modeling (DVLS), and quantitative texture analysis approaches to the structural refinement of Garfield nontronite

This paper reports on the new application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to fine-grained layer silicates taking the Garfield nontronite as a case study. Up to now application of P-EXAFS to structural studies of layer silicates has been restricted to single phyllosilicate crystals (Manceau et al. 1988; Manceau et al. 1990), but we show here that P-EXAFS can rigorously be applied to self-supporting clay films without loss of spatial resolution. The quantitative analysis of P-EXAFS requires however the preparation of highly oriented clay films, the orientation distribution of which can be assessed by texture goniometry. The Fe K-edge linear dichroism measurements were simulated by ab initio EXAFS modeling performed on a nontronite cluster whose structure was refined by distance-valence least-squares calculations. It is shown that ab initio modeling quantitatively accounts for the angular dependence of experimental EXAFS spectra. These calculations allowed for the identification of the fundamental character of single- and multiple-scattering paths of the photoelectron, and the structural interpretation of all spectral features observed up to 6.5?Å for the in-plane and out-of-plane radial structure functions of nontronite. In practice, P-EXAFS measurements allow the determination of the flattening angle of Fe(O,OH)₆ octahedra, cations distribution in the octahedral sheet with an enhanced sensitivity, and differentiation between dioctahedral and trioctahedral structures.     

Experimental studies of equilibrium iron isotope fractionation in ferric aquo-chloro complexes

Here we compare new experimental studies with theoretical predictions of equilibrium iron isotopic fractionation among aqueous ferric chloride complexes (Fe(H₂O)₆³⁺, FeCl(H₂O)₅²⁺, FeCl₂(H₂O)₄⁺, FeCl₃ (H₂O)₃, and FeCl₄^-), using the Fe-Cl-H₂O system as a simple, easily-modeled example of the larger variety of iron-ligand compounds, such as chlorides, sulfides, simple organic acids, and siderophores. Isotopic fractionation (⁵⁶Fe/⁵⁴Fe) among naturally occuring iron-bearing species at Earth surface temperatures (up to ∼3‰) is usually attributed to redox effects in the environment. However, theoretical modeling of reduced isotopic partition functions among iron-bearing species in solution also predicts fractionations of similar magnitude due to non-redox changes in speciation (i.e., ligand bond strength and coordination number). In the present study, fractionations are measured in a series of low pH ([H⁺] = 5 M) solutions of ferric chloride (total Fe = 0.0749 mol/L) at chlorinities ranging from 0.5 to 5.0 mol/L. Advantage is taken of the unique solubility of FeCl₄^- in immiscible diethyl ether to create a separate spectator phase, used to monitor changing fractionation in the aqueous solution. Δ⁵⁶Fe_aq-eth = δ⁵⁶Fe (total Fe remaining in aqueous phase)−δ⁵⁶Fe (FeCl₄^- in ether phase) is determined for each solution via MC-ICPMS analysis.Both experiments and theoretical calculations of Δ⁵⁶Fe_aq-eth show a downward trend with increasing chlorinity: Δ⁵⁶Fe_aq-eth is greatest at low chlorinity, where FeCl₂(H₂O)₄⁺ is the dominant species, and smallest at high chlorinity where FeCl₃(H₂O)₃ is dominant. The experimental Δ⁵⁶Fe_aq-eth ranges from 0.8‰ at [Cl^-] = 0.5 M to 0.0‰ at [Cl^-] = 5.0 M, a decrease in aqueous-ether fractionation of 0.8‰. This is very close to the theoretically predicted decreases in Δ⁵⁶Fe_aq-eth, which range from 1.0 to 0.7‰, depending on the ab initio model.The rate of isotopic exchange and attainment of equilibrium are shown using spiked reversal experiments in conjunction with the two-phase aqueous-ether system. Equilibrium under the experimental conditions is established within 30 min.The general agreement between theoretical predictions and experimental results points to substantial equilibrium isotopic fractionation among aqueous ferric chloride complexes and a decrease in ⁵⁶Fe/⁵⁴Fe as the Cl^-/Fe³⁺ ion ratio increases. The effects on isotopic fractionation shown by the modeling of this simple iron-ligand system imply that ligands present in an aqueous environment are potentially important drivers of fractionation, are indicative of possible fractionation effects due to other speciation effects (such as iron-sulfide systems or iron bonding with organic ligands), and must be considered when interpreting iron isotope fractionation in the geological record.     

Raman spectroscopy, vibrational analysis, and heating of buergerite tourmaline

Polarized Raman spectra were collected for single crystal buergerite (NaFe₃Al₆(BO₃)₃Si₆O₁₈(O_0.92(OH)_0.08)₃F) from room temperature to near 1,375°C. Vibrational assignments to features in the room temperature spectra were determined by lattice dynamics calculations, where internal BO₃ motions dominate modes near 1,300 cm⁻¹, internal SiO₄ displacements dominate modes between 900 and 1,200 cm⁻¹, while less localized displacements within the isolated Si₆O₁₈ ring mix with motions within Na, Fe, Al, F, and BO₃ environments for fundamental modes below 780 cm⁻¹. At elevated temperatures, most buergerite Raman features broaden and shift to lower frequencies up to 900°C. Above this temperature, the lattice mode peaks evolve into broad bands, while OH stretch modes near 3,550 cm⁻¹ disappear. According to Raman spectroscopy, X-ray diffraction, differential thermal analysis, and scanning electron microscopy, buergerite undergoes a complex transition that starts near 700°C and extends over a 310°C interval, where initially, Al and Fe probably become disordered within the Y- and Z-sites, and most F and all OH are later liberated. A reversible crystal-to-amorphous transition is seen by Raman for buergerite fragments heated as high as 930°C. Buergerite becomes permanently altered when heated to temperatures greater than 930°C; after cooling to room temperature, these altered fragments are comprised of mullite and Fe-oxide crystals suspended in an amorphous borosilicate matrix.     

Calculated trends of oh infrared stretching vibrations with composition and structure in aluminosilicate molecules

Ab initio, molecular orbital calculations have been performed on a variety of hypothetical aluminosilicate molecules to investigate relationships among composition, structure, and infrared spectra of OH. Vibrational analyses of the full-optimized molecular geometries at the 3–21G^** level were performed with Gaussian 92 to determine theoretical infrared spectra. Theoretical infrared OH frequencies, ν(OH), shift 10 to 100 cm^?1 with ionic substitutions. The inverse correlation of theoretical infrared OH intensities with OH stretching frequencies in these aluminosilicate molecules is similar to that observed for aluminosilicate glasses (Paterson 1982). O-H bond lengths, H-bond distances, and H?nd angles correlate with frequency. The dominant factor affecting ν(OH) is the H-bond distance, if this distance is less than 2 Å. Beyond H-bond distances of 2 Å, structural and compositional effects exert competitive influences on ν(OH).     

Effect of hydroxamate siderophores on Fe release and Pb(II) adsorption by goethite

Hydroxamate siderophores are biologically-synthesized, Fe(III)-specific ligands which are common in soil environments. In this paper, we report an investigation of their adsorption by the iron oxyhydroxide, goethite; their influence on goethite dissolution kinetics; and their ability to affect Pb(II) adsorption by the goethite surface. The siderophores used were desferrioxamine B (DFO-B), a fungal siderophore, and desferrioxamine D₁, an acetyl derivative of DFO-B (DFO-D1). Siderophore adsorption isotherms yielded maximum surface concentrations of 1.5 (DFO-B) or 3.5 (DFO-D1) μmol/g at pH 6.6, whereas adsorption envelopes showed either cation-like (DFO-B) or ligand-like (DFO-D1) behavior. Above pH 8, the adsorbed concentrations of both siderophores were similar. The dissolution rate of goethite in the presence of 240 μM DFO-B or DFO-D1 was 0.02 or 0.17 μmol/g hr, respectively. Comparison of these results with related literature data on the reactions between goethite and acetohydroxamic acid, a monohydroxamate ligand, suggested that the three hydroxamate groups in DFO-D1 coordinate to Fe(III) surface sites relatively independently. The results also demonstrated a significant depleting effect of 240 μM DFO-B or DFO-D1 on Pb(II) adsorption by goethite at pH > 6.5, but there was no effect of adsorbed Pb(II) on the goethite dissolution rate.     

Photochemical activity and characterization of the complex of humic acids with iron(III)

This study examined the effects of humic acids (HA) and Fe(III)–HA complex on the photodegradation of atrazine, one of the most widely used herbicides. It was shown that the photolysis of atrazine proceeded via first-order reaction kinetics and that atrazine photodegradation was inhibited by the presence of HA, whereas the rate for atrazine photolysis was promoted in solutions containing both HA and Fe(III). Interactions of Fe(III) with HA were characterized by SEM, EDX, UV–Vis and FTIR, revealing that Fe(III)–HA complex was formed by ligand exchange between oxygen groups of HA and Fe(III). Using fluorescence spectrometry the stability constant (K_c) and the fraction of fluorophores available for complexation (f) were obtained as log K_c = 4.28 and f = 74%. Photoformed Fe(II) by ligand-to-metal charge-transfer (LMCT) within the Fe(III)–HA complex was the most important factor involved in photolysis of atrazine, since Fe(II) was the reactant to generate hydroxyl radical. Thus, the rate of atrazine photodegradation in natural sunlit waters is dependent on both the amount of iron present and the interaction between HA and iron.     

Anomalous birefringence in andradite–grossular solid solutions: a quantum-mechanical approach

The static linear optical properties (refractive indices, birefringence and axial angle) of andradite–grossular (Ca₃Fe₂Si₃O₁₂–Ca₃Al₂Si₃O₁₂) solid solutions have been computed at the ab initio quantum-mechanical level through the Coupled Perturbed Kohn–Sham scheme, using an all-electron Gaussian-type basis set. Geometry relaxation after substitution of 1–8 Al for Fe atoms in the primitive cell of andradite yields 23 non-equivalent configurations ranging from cubic to triclinic symmetry. Refractive indices vary quite regularly between the andradite (1.860) and grossular (1.671) end-members; the birefringence δ and the axial angle 2V at intermediate compositions can be as large as 0.02° and 89°, respectively. Comparison with experiments suffers from inhomogeneities and impurities of natural samples; however, semi-quantitative agreement is observed.     

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.     

Adsorption and surface oxidation of Fe(II) on metal (hydr)oxides

The Fe(II) adsorption by non-ferric and ferric (hydr)oxides has been analyzed with surface complexation modeling. The CD model has been used to derive the interfacial distribution of charge. The fitted CD coefficients have been linked to the mechanism of adsorption. The Fe(II) adsorption is discussed for TiO₂, γ-AlOOH (boehmite), γ-FeOOH (lepidocrocite), α-FeOOH (goethite) and HFO (ferrihydrite) in relation to the surface structure and surface sites. One type of surface complex is formed at TiO₂ and γ-AlOOH, i.e. a surface-coordinated Fe²⁺ ion. At the TiO₂ (Degussa) surface, the Fe²⁺ ion is probably bound as a quattro-dentate surface complex. The CD value of Fe²⁺ adsorbed to γ-AlOOH points to the formation of a tridentate complex, which might be a double edge surface complex. The adsorption of Fe(II) to ferric (hydr)oxides differs. The charge distribution points to the transfer of electron charge from the adsorbed Fe(II) to the solid and the subsequent hydrolysis of the ligands that coordinate to the adsorbed ion, formerly present as Fe(II). Analysis shows that the hydrolysis corresponds to the hydrolysis of adsorbed Al(III) for γ-FeOOH and α-FeOOH. In both cases, an adsorbed M(III) is found in agreement with structural considerations. For lepidocrocite, the experimental data point to a process with a complete surface oxidation while for goethite and also HFO, data can be explained assuming a combination of Fe(II) adsorption with and without electron transfer. Surface oxidation (electron transfer), leading to adsorbed Fe(III)(OH)₂, is favored at high pH (pH > ∼7.5) promoting the deprotonation of two Fe_III-OH₂ ligands. For goethite, the interaction of Fe(II) with As(III) and vice versa has been modeled too. To explain Fe(II)-As(III) dual-sorbate systems, formation of a ternary type of surface complex is included, which is supposed to be a monodentate As(III) surface complex that interacts with an Fe(II) ion, resulting in a binuclear bidentate As(III) surface complex.     

Phosphate bonding configuration on ferrihydrite based on molecular orbital calculations and XANES fingerprinting

Sorption of phosphate by Fe(III)- and Al(III)-(hydr)oxide minerals regulates the mobility of this potential water pollutant in the environment. The objective of this research was to determine the molecular configuration of phosphate bound on ferrihydrite at pH 6 by interpreting P K-edge XANES spectra in terms of bonding mode. XANES and UV-visible absorption spectra for aqueous Fe(III)-PO₄ solutions (Fe/P molar ratio = 0-2.0) provided experimental trends for energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals. Molecular orbitals for Fe(III)-PO₄ or Al(III)-PO₄ complexes in idealized monodentate or bidentate bonding mode were generated by conceptual bonding arguments, and Extended-Hückel molecular orbital computations were used to understand and assign XANES spectral features to bound electronic states. The strong white line at the absorption edge in P K-edge XANES spectra for Fe-PO₄ or Al-PO₄ systems is attributable to an electronic transition from a P 1s atomic orbital into P(3p)-O(2p) or P(3p)-O(2p)-Al(3p) antibonding molecular orbitals, respectively. For Fe-PO₄ systems, a XANES peak at 2-5 eV below the edge was assigned to a P 1s electron transition into Fe(4p)-O(2p) antibonding molecular orbitals. Similarly, a shoulder on the low-energy side of the white line for variscite corresponds to a transition into Al(3p)-O(2p) orbitals. In monodentate-bonded phosphate, Fe-O bonding is optimized and P-O bonding is weakened, and the converse is true of bidentate-bonded phosphate. These differences explained an inverse correlation between energies of P(3p)-O(2p) and Fe(3d)-O(2p) antibonding molecular orbitals consistent with a monodentate-to-bidentate transition in aqueous Fe(III)-PO₄ solutions. The intensity of the XANES pre-edge feature in Fe(III)-bonded systems increased with increasing number of Fe(III)-O-P bonds. Based on the similarity of intensity and splitting of the pre-edge feature for phosphate sorbed on ferrihydrite at 750 mmol/kg at pH 6 and aqueous Fe-PO₄ solutions containing predominantly bidentate complexes, XANES results indicated that phosphate adsorbed on ferrihydrite was predominantly a bidentate-binuclear surface complex.