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1.
The Fe L 2,3-edge spectra for a range of natural minerals and synthetic solid solutions have been measured using the technique of parallel electron energy-loss spectroscopy (PEELS) recorded in a transmission electron microscope (TEM). The Fe L 2,3 -edges of the minerals are characterised by two white-line features and exhibit electron energy-loss near-edge structure (ELNES) characteristic of Fe valence state. For divalent iron, the Fe L 3 -edge spectra are dominated by a sharp peak (white-line) at ca. 707.8 eV, followed by a broader and less intense peak at ca. 710.5 eV. The ELNES on the Fe L 3 -edge of trivalent iron consists of a white-line with its maximum at ca. 709.5 eV and a preceeding peak at ca. 708.0 eV. Mineral solid solutions that contain both Fe2+ and Fe3+ exhibit an Fe L 3 -edge shape that is composed of Fe L 3 -edges from the respective Fe2+- and Fe3+-bearing end members. The integral Fe L 2,3 -edge white-line intensity ratios I(L 3 )/I(L 2 ) show clear differences for Fe2+ and Fe3+. We demonstrate the feasibility of quantification of the ferrous/ferric ratio in minerals by determining the integral Fe L 2,3 -edge white-line intensity ratios I(L 3 )/I(L 2 ) as a function of the ferric iron concentration resulting in an universal curve within the experimental errors. The application of the universal curve combined with the high spatial resolution using the PEELS/TEM allows the quantification of the ferric iron concentration on a scale down to 10 nm, which is illustrated from a sample of ilmenite containing hematite exsolution lamellae that shows different Fe L 2,3 -edge shapes consistent with variations in the Fe2+-Fe3+ ratio over distances of ca. 100 nm. Received: 30 July 1997 / Revised, accepted: 26 October 1997  相似文献   

2.
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 L2,3-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.  相似文献   

3.
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.  相似文献   

4.
The determination of the oxidation states of copper and iron in sulfides, and chalcopyrite (CuFeS2) in particular, using 2p X-ray photoemission spectroscopy (XPS) and L2,3-edge X-ray absorption spectroscopy (XAS) is revisited. Reassessment of the published spectra derived by these methods produces consistent results and reveals the ‘d count’ in the copper compounds to be intermediate between d9 and d10. Nevertheless, these covalent copper compounds can be divided into those nominally monovalent and those nominally divalent. The Fe L2,3-edge XAS of chalcopyrite, along with Mössbauer data, confirm the presence of high-spin Fe3+. Chalcopyrite, despite recent published reports to the contrary, clearly belongs to the monovalent copper class.  相似文献   

5.
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6.
Experimental investigations have been performed at T = 1200°C, P = 200 MPa and fH2 corresponding to H2O-MnO-Mn3O4 and H2O-QFM redox buffers to study the effect of H2O activity on the oxidation and structural state of Fe in an iron-rich basaltic melt. The analysis of Mössbauer and Fe K-edge X-ray absorption nearedge structure (XANES) spectra of the quenched hydrous ferrobasaltic glasses shows that the Fe3+/ΣFe ratio of the glass is directly related to aH2O in a H2-buffered system and, consequently, to the prevailing oxygen fugacity (through the reaction of water dissociation H2O ↔ H2 + 1/2 O2). However, water as a chemical component of the silicate melt has an indistinguishable effect on the redox state of iron at studied conditions. The experimentally obtained relationship between fO2 and Fe3+/Fe2+ in the hydrous ferrobasaltic melt can be adequately predicted in the investigated range by the existing empiric and thermodynamic models. The ratio of ferric and ferrous Fe is proportional to the oxygen fugacity to the power of ∼0.25 which agrees with the theoretical value from the stoichiometry of the Fe redox reaction (FeO + ¼ O2 = FeO1.5). The mean centre shifts for Fe2+ and Fe3+ absorption doublets in Mössbauer spectra show little change with increasing Fe3+/ΣFe, suggesting no significant change in the type of iron coordination. Similarly, XANES preedge spectra indicate a mixed (C3h, Td, and Oh, i.e., 5-, 4-, and sixfold) coordination of Fe in hydrous basaltic glasses.  相似文献   

7.
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 Fe2– 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 Fe3—.
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.
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8.
Three natural lawsonites from Syke Rock, Mendocino Co., Reed Ranch, Marin Co., and Blake Gardens, Sonoma Co., all from the Coast Range Region in California, were studied by 57Fe Mössbauer spectroscopy, electron microprobe analysis, and X-ray powder diffraction. The samples contain about 0.6, 1.0, and 1.4 wt% of total iron oxide, respectively. 57Fe Mössbauer spectra are consistent with the assumption that high-spin Fe3+ substitutes for Al in the octahedrally coordinated site. The Mössbauer spectrum of lawsonite from Syke Rock exhibits a second doublet with 57Fe hyperfine parameters typical for octahedrally coordinated high-spin Fe2+. Electronic structure calculations in the local spin density approximation yield quadrupole splittings for Fe3+ in quantitative agreement with experiment indicating, however, that substitution of Al by Fe3+ must be accompanied by local distortion around the octahedral site. Model calculations also reproduce the room temperature hyperfine parameters of ferrous high-spin iron assuming the substitution of Ca by Fe2+. However, it cannot be excluded that Fe2+ may occupy a more asymmetric site within the microstructural cavity occupied by Ca and a H2O molecule.  相似文献   

9.
The Fe M 2,3-edge spectra of solid solutions of garnets (almandine-skiagite Fe3(Al1–xFex)2[SiO4]3 and andradite-skiagite (Fe1–xCax)3Fe2[SiO4]3), pyroxenes (acmite-hedenbergite (Ca1–xNax)(Fe2+ 1−xFe3+ x)Si2O6), and spinels (magnetite-hercynite Fe(Al1–xFex)2O4) have been measured using the technique of parallel electron energy-loss spectroscopy (EELS) conducted in a transmission electron microscope (TEM). The Fe M 2,3 electron energy-loss near-edge structures (ELNES) of the minerals exhibit a characteristic peak located at 4.2 eV and 2.2 eV for trivalent and divalent iron, respectively, prior to the main maximum at about 57 eV. The intensity and energy of the pre-edge feature varies depending on Fe3+/ΣFe. We demonstrate a new quantitative method to extract the ferrous/ferric ratio in minerals. A systematic relationship between Fe3+/ΣFe and the integral intensity ratio of the main maximum and the pre-edge peak of the Fe M 2,3 edge is observed. Since the partial cross sections of the Fe M 2,3 edges are some orders of magnitude higher than those of the Fe L 2,3 edges, the Fe M 2,3 edges are interesting for valence-specific imaging of Fe. The possibility of iron valence-specific imaging is illustrated by Fe M 2,3-ELNES investigations with high lateral resolution from a sample of ilmenite containing hematite exsolution lamellae that shows different edge shapes consistent with variations in the Fe3+/ΣFe ratio over distances on the order of 100 nm. Received: 14 April 1998 / Revised, accepted: 8 March 1999  相似文献   

10.
Ferrous and ferric iron concentrations in feldspars with low total iron content (<0.32 wt% total Fe) were determined from optical and electron paramagnetic resonance (EPR) spectra to better than ±15 percent of the amount present. Optical spectra indicate that Fe2+ occupies two distorted M-sites in plagioclases of intermediate structural state. The linear dependence of the Fe2+/Fe total ratio on An content demonstrates that Fe2+ substitutes for Ca (not Na) so that the number of Ca-sites is a principal factor in iron partitioning in plagioclase. EPR powder spectra show that the number of sites for Fe3+ depends on structural state rather than on plagioclase chemistry. The observed linear correspondence of EPR double-integrated intensities with optical peak areas shows that all Fe3+ is tetrahedrally coordinated in both plagioclase and disordered potassium feldspar. Microcline perthites show, in addition to tetrahedral Fe3+, a signal due to axially coordinated ferric iron, which we associate with formation of hematite inclusions.  相似文献   

11.
Assessing the ferric-ferrous ratio in magmas prior to eruption remains a challenging task. X-ray absorption near-edge structure (μXANES) spectra were collected at the iron K-edge in water-rich peralkaline silicic melt/glass inclusions trapped in quartz. These experiments were carried out between 800 and 20 °C. The chemical environment of iron was also determined in the naturally quenched samples (glass inclusions and matrix glass) and in the peralkaline rhyolitic reference glasses, with variable [Fe3+ / ∑Fe] ratios.In the reference glasses, both the intensity of the pre-peaks (Fe2+, Fe3+) and site geometry of iron change as the oxidation state increases. Fourfold-coordinated Fe3+ prevails in highly oxidised peralkaline silicic glasses, using alkalis for charge balance. The position of the pre-edge centroid of the 1s-3d transition correlates with the Fe3+ / ΣFe ratios that allowed calibration of the redox state of iron of our natural samples.At high temperatures, Fe2+ dominates in the pre-edge structure of melt inclusions. Upon cooling down to 20 °C, the intensity of the Fe3+ peak increases, the centroid position of the pre-edge features shifts by nearly 0.5 eV and the main edge moves slightly towards higher energies. The slower the cooling rate, the higher the ferric iron contribution. Iterative μXANES experiments performed on the same samples show that the process is reversible. However, this apparent oxidation of iron upon cooling is an artefact of changes in Fe coordination. It implies that the [Fe3+ / ΣFe] ratio of glassy samples, measured at 20 °C, may be overestimated by a factor > 1.7, and that this ratio cannot be reliably retrieved by probing naturally cooled glass inclusions, and most silicate glasses. High temperature μXANES experiments led first to an assessment of the ferric-ferrous ratio in the water-rich peralkaline melt in pre-eruptive magmatic conditions and second to the determination of the corresponding oxygen fugacity at 740 °C.  相似文献   

12.
The uranium LIII-edge XANES spectra for natural rocks at the concentration range of 0.96–124 mg kg−1 were measured using a log spiral bent crystal Laue analyzer (BCLA) combined with a multi-element Ge detector. It was found that the quality of the XANES spectra using the BCLA was greatly improved due to a reduction of interfering fluorescence from major components such as Rb and Sr. The ratio of signal to background intensities in the U LIII-edge XANES spectra increased by a factor of 2.9–17 with the use of the BCLA, which greatly enhanced the detection limit for the speciation of the oxidation states of U or the U(IV)/U(VI) ratio of natural samples. In addition, it was demonstrated that the fluorescence XANES method coupled with the BCLA enable determination of the speciation of U for various natural samples such as acidic igneous rocks, ferromanganese nodules, sediments, and some sedimentary rocks such as shale and limestone.  相似文献   

13.
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.  相似文献   

14.
We investigated the valence state and spin state of iron in an Al-bearing ferromagnesian silicate perovskite sample with the composition (Mg0.88Fe0.09)(Si0.94Al0.10)O3 between 1 bar and 100 GPa and at 300 K, using diamond cells and synchrotron Mössbauer spectroscopy techniques. At pressures below 12 GPa, our Mössbauer spectra can be sufficiently fitted by a “two-doublet” model, which assumes one ferrous Fe2+-like site and one ferric Fe3+-like site with distinct hyperfine parameters. The simplest interpretation that is consistent with both the Mössbauer data and previous X-ray emission data on the same sample is that the Fe2+-like site is high-spin Fe2+, and the Fe3+-like site is high-spin Fe3+. At 12 GPa and higher pressures, a “three-doublet” model is necessary and sufficient to fit the Mössbauer spectra. This model assumes two Fe2+-like sites and one Fe3+-like site distinguished by their hyperfine parameters. Between 12 and 20 GPa, the fraction of the Fe3+-like site, Fe3+/∑Fe, changes abruptly from about 50 to 70%, possibly due to a spin crossover in six-coordinate Fe2+. At pressures above 20 GPa, the fractions of all three sites remain unchanged to the highest pressure, indicating a fixed valence state of iron within this pressure range. From 20 to 100 GPa, the isomer shift between the Fe3+-like and Fe2+-like sites increases slightly, while the values and widths of the quadruple splitting of all three sites remain essentially constant. In conjunction with the previous X-ray emission data, the Mössbauer data suggest that Fe2+ alone, or concurrently with Fe3+, undergoes pressure-induced spin crossover between 20 and 100 GPa.  相似文献   

15.
Monoclinic and hexagonal pyrrhotites leached in 1 mol/L HCl and exposed to the air at 100% and ∼10% relative humidity for up to 5 months were studied using X-ray diffraction, Fourier transform infrared (FTIR) spectroscopy, X-ray photoelectron spectroscopy (XPS), X-ray emission spectroscopy, Mössbauer spectroscopy, and electron paramagnetic resonance (EPR). The amorphous, nonequilibrium, iron-depleted layer (NL) produced by the leaching amounted to half of the residue mass and was composed of predominantly low-spin ferrous iron and polysulfide anions. Elemental sulfur and goethite were the only crystalline products of the NL decomposition. FTIR spectroscopy and XPS also revealed several sulfoxy species and, at low humidity, a small amount of ferric oxide. Neither alterations of the underlying pyrrhotite nor new iron sulfide phases (pyrite, pyrrhotite, etc.) crystallized from the amorphous NL were found. The NL decomposition was faster in the wet environment than in the dry one, and the oxidation of the NL was much more rapid than that of starting pyrrhotites. The intensity and quadruple split of the Mössbauer signal from the product (an isomer shift of 0.36 mm/s) were found to increase over the aging, indicating that the NL structure becomes more rigid and the singlet Fe(II) gradually converts to Fe(III). X-ray Fe Lα,β emission spectra showed the formation of intermediate, high-spin Fe(II) within the NL oxidized in the humid environment, but not in the dry air. No unpaired electron spins were detected by EPR; lines of paramagnetic Fe3+ appeared after the samples were aged in the dry air for 49 d and even later in the humid atmosphere. These phenomena are explained in terms of the formation of defects with negative correlation energy, similar to noncrystalline semiconductor chalcogenides, and of the fast electron exchange between the iron species, respectively. Mechanisms for reactions involved with the weathering of iron sulfides, which take into consideration the NL lattice elasticity, S-S and S-O bonding, oxygen incorporation, and oxidative and spin state of iron, are discussed. It is suggested in particular that the surface layer, strongly enriched in sulfur, as well as elemental sulfur and ferric oxyhydroxides, do not inhibit sulfide oxidation and acid production under weathering conditions, but the partially oxidized, disordered, nonstoichiometric layer may be passive.  相似文献   

16.
A series of laboratory batch experiments was conducted to evaluate the potential for treatment of acid mine drainage (AMD) using organic C (OC) mixtures amended by zero-valent Fe (Fe0). Modest increases in SO4 reduction rates (SRRs) of up to 15% were achieved by augmenting OC materials with 5 and 10 dry wt% Fe0. However, OC was essential for supporting SO4 reducing bacteria (SRB) and therefore SO4 reduction. This observation suggests a general absence of autotrophic SRB which can utilize H2 as an electron donor. Sulfate reduction rates (SRRs), calculated using a mass-based approach, ranged from −12.9 to −14.9 nmol L−1 d−1  g−1 OC. Elevated populations of SRB, iron reducing bacteria (IRB), and acid producing (fermentative) bacteria (APB) were present in all mixtures containing OC. Effective removal of Fe (91.6–97.6%), Zn (>99.9%), Cd (>99.9%), Ni (>99.9%), Co (>99.9%), and Pb (>95%) was observed in all reactive mixtures containing OC. Abiotic metal removal was achieved with Fe0 only, however Fe, Co and Mn removal was less effective in the absence of OC. Secondary disordered mackinawite [Fe1+xS] was observed in field-emission scanning electron microscopy (FE-SEM) backscatter electron micrographs of mixtures that generated SO4 reduction. Energy dispersive X-ray (EDX) spectroscopy revealed that Fe–S precipitates were Fe-rich for mixtures containing OC and Fe0, and S-rich in the absence of Fe0 amendment. Sulfur K-edges determined by synchrotron-radiation based bulk X-ray absorption near-edge structure (XANES) spectroscopy indicate solid-phase S was in a reduced form in all mixtures containing OC. Pre-edge peaks on XANES spectra suggest tetragonal S coordination, which is consistent with the presence of an Fe–S phase such as mackinawite. The addition of Fe0 enhanced AMD remediation over the duration of these experiments, however long-term evaluation is required to identify optimal Fe0 and OC mixtures.  相似文献   

17.
X-ray absorption spectroscopy, including extended X-ray absorption fine structure (EXAFS) and X-ray absorption near-edge structure (XANES) techniques, have been used to determine the structure and speciation of complexes for Fe2+ and Fe3+ chloride solutions at a variety of pH's, ionic strengths, and chloride/iron ratios.Low intensity K-edge transition features and analysis of modified pair correlation functions, derived from Fourier transformation of EXAFS spectra, show a regular octahedral coordination of Fe(II) by water molecules with a first-shell Fe2+-O bond distance, closely matching octahedral Fe2+-O bonds obtained from solid oxide model compounds. Solution Fe2+-O bond distances decrease with chloride/iron ratio, pH, and total FeCl2 concentration. A slight intensification of the 1s → 3d transition with increasing FeCl2 concentration suggests that chloride may begin to mix with water as a nearest-neighbor octahedral ligand. Fe3+ solutions show a pronounced increase in the 1s → 3d transition intensities between 1.0 M FeCl3/7.8 M Cl? to 1.0 M FeCl3/ 15 M Cl?, indicating a coordination change from octahedral to tetrahedral complexes. EXAFS analyses of these solutions show an increase in first-shell Fe3+-ligand distances despite this apparent reduction in coordination number. This can be best explained by a change from regular octahedral complexes of ferric iron (either Fe(H2O)63+ or trans-Fe(H2O)4Cl2 or both; Fe3+-O bond distances of 2.10 Å) to tetra-chloro complexes [Fe3+-Cl bond distances of 2.25 Å].  相似文献   

18.
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.  相似文献   

19.
Microbial sulfidogenesis plays a potentially important role in Fe and As biogeochemistry within wetland soils, sediments and aquifers. This study investigates the specific effects of microbial sulfidogenesis on Fe mineralogy and associated As mobility in mildly acidic (pH 6) and mildly basic (pH 8) advective-flow environments. A series of experiments were conducted using advective-flow columns, with an initial solid-phase comprising As(III)-bearing ferrihydrite-coated quartz sand. Columns for each pH treatment were inoculated with the sulfate-reducing bacteria Desulfovibrio vulgaris, and were compared to additional abiotic control columns. Over a period of 28 days, microbial sulfidogenesis (as coupled to the incomplete oxidation of lactate) caused major changes in Fe mineralogy, including replacement of ferrihydrite by mackinawite and magnetite at the in-flow end of the inoculated columns. At pH 8, the Fe2+ produced by electron transfer between sulfide and ferrihydrite was mainly retained near its zone of formation. In contrast, at pH 6, much of the produced Fe2+ was transported with advecting groundwater, facilitating the downstream Fe2+-catalyzed transformation of ferrihydrite to goethite. At both pH 6 and pH 8, the sulfide-driven reductive dissolution of ferrihydrite and its replacement by mackinawite at the in-flow end of the inoculated columns resulted in substantial mobilization of As into the pore-water. At pH 8, this caused the downstream As concentrations within the inoculated columns to be greater than the corresponding abiotic column. However, the opposite occurred under pH 6 conditions, with the Fe2+-catalyzed transformation of ferrihydrite to goethite in the inoculated columns causing a decrease in downstream As concentrations compared to the abiotic column. Although thermodynamically favorable at intermediate times and depth intervals within the inoculated columns, solid As sulfide phases were undetectable by As XANES spectroscopy. Our findings show that microbial sulfidogenesis can trigger significant As mobilization in subsurface environments with advective groundwater flow. The results also demonstrate that formation of mackinawite by sulfidization of ferric (hydr)oxides is not effective for the immobilization of As, whereas the Fe2+-catalyzed transformation of ferrihydrite to goethite under mildly acidic conditions may mitigate As mobility.  相似文献   

20.
Experiments at high pressures and temperatures were carried out (1) to investigate the crystal-chemical behaviour of Fe4O5–Mg2Fe2O5 solid solutions and (2) to explore the phase relations involving (Mg,Fe)2Fe2O5 (denoted as O5-phase) and Mg–Fe silicates. Multi-anvil experiments were performed at 11–20 GPa and 1100–1600 °C using different starting compositions including two that were Si-bearing. In Si-free experiments the O5-phase coexists with Fe2O3, hp-(Mg,Fe)Fe2O4, (Mg,Fe)3Fe4O9 or an unquenchable phase of different stoichiometry. Si-bearing experiments yielded phase assemblages consisting of the O5-phase together with olivine, wadsleyite or ringwoodite, majoritic garnet or Fe3+-bearing phase B. However, (Mg,Fe)2Fe2O5 does not incorporate Si. Electron microprobe analyses revealed that phase B incorporates significant amounts of Fe2+ and Fe3+ (at least ~?1.0 cations Fe per formula unit). Fe-L2,3-edge energy-loss near-edge structure spectra confirm the presence of ferric iron [Fe3+/Fetot?=?~?0.41(4)] and indicate substitution according to the following charge-balanced exchange: [4]Si4+?+?[6]Mg2+?=?2Fe3+. The ability to accommodate Fe2+ and Fe3+ makes this potential “water-storing” mineral interesting since such substitutions should enlarge its stability field. The thermodynamic properties of Mg2Fe2O5 have been refined, yielding H°1bar,298?=???1981.5 kJ mol??1. Solid solution is complete across the Fe4O5–Mg2Fe2O5 binary. Molar volume decreases essentially linearly with increasing Mg content, consistent with ideal mixing behaviour. The partitioning of Mg and Fe2+ with silicates indicates that (Mg,Fe)2Fe2O5 has a strong preference for Fe2+. Modelling of partitioning with olivine is consistent with the O5-phase exhibiting ideal mixing behaviour. Mg–Fe2+ partitioning between (Mg,Fe)2Fe2O5 and ringwoodite or wadsleyite is influenced by the presence of Fe3+ and OH incorporation in the silicate phases.  相似文献   

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