Iron local structure in tektites and impact glasses by extended X-ray absorption fine structure and high-resolution X-ray absorption near-edge structure spectroscopy

The local structure of iron in three tektites has been studied by means of Fe K-edge extended X-ray absorption fine structure (EXAFS) and high-resolution X-ray absorption near-edge structure (XANES) spectroscopy in order to provide quantitative data on <Fe-O> distance and Fe coordination number. The samples studied are a moldavite and two australasian tektites. Fe model compounds with known Fe oxidation state and coordination number were used as standards in order to extract structural information from the XANES pre-edge peak. EXAFS-derived grand mean <Fe-O> distances and Fe coordination numbers for the three tektite samples are constant within the estimated error (<Fe-O > =2.00 Å ± 0.02 Å, CN = 4.0 ± 0.4). In contrast to other data from the literature on Fe-bearing silicate glasses, the tektites spectra could not be fitted with a single Fe-O distance, but rather were fit with two independent distances (2 × 1.92 Å and 2 × 2.08 Å). High-resolution XANES spectra of the three tektites display a pre-edge peak whose intensity is intermediate between those of staurolite and grandidierite, thus suggesting a mean coordination number intermediate between 4 and 5. Combining the EXAFS and XANES data for Fe, we infer the mean coordination number to be close to 4.5.Comparison of the tektites XANES spectra with those of a suite of different impact glasses clearly shows that tektites display a relatively narrow range of Fe oxidation state and coordination numbers, whereas impact glasses data span a much wider range of Fe oxidation states (from divalent to trivalent) and coordination numbers (from tetra-coordinated to esa-coordinated). These data suggest that the tektite production process is very similar for all the known strewn fields, whereas impact glasses can experience a wide variety of different temperature-pressure-oxygen fugacity conditions, leading to different Fe local structure in the resulting glasses. These data could be of aid in discriminating between tektite-like impact glasses and impact glasses sensu strictu.     

X-ray absorption spectroscopic studies of silicate glasses and minerals

Selected results of x-ray absorption spectroscopy (XAS) studies of amorphous silicates and minerals are presented in order to show their utility in providing short-and, in certain cases, medium-range structural and bonding information for cations and anions. EXAFS and XANES studies of amorphous silicates are reviewed with the objective of illustrating variations in structural environments of the various types of glass-forming cations, including Si, Al, Na, K, Ca, Ti, Fe, Yb, and U. Al is shown to occur in tetrahedral coordination in all aluminosilicate glasses examined, including peraluminous compositions. The weakly bonded Na and Ca cations are shown to occur in sites with observed coordination numbers (ranging from 6 to 7) and distances similar to those predicted by molecular dynamics simulations. Elements like Ti, which form bonds of intermediate strength, may show some order beyond the first coordination shell at low concentrations in silicate glasses. EXAFS studies of Yb and U in silicate glasses at trace to minor concentration levels provide unique structural information about the environments of these cations. K-edges and XANES of transition element sulfides, third-row tetrahedral oxyanions, and oxygen in minerals are interpreted in terms of band theory or molecular orbital theory.     

Structure of Mn and Fe oxides and oxyhydroxides: A topological approach by EXAFS

The structure of Mn and Fe oxides and oxyhydroxides has been probed by EXAFS. It is shown that EXAFS spectroscopy is sensitive to the nature of interpolyhedral linkages relying on metal-two nearest metal distances. Spectra recorded at 290 K and 30 K indicate that intercationic distances can be determined by EXAFS with a good accuracy (0.02 Å) assuming a purely Gaussian distribution function, even at room temperature. Although the accuracy on atomic numbers determination is fair for these disordered systems, EXAFS can differentiate structures with contrasted edge- over corner-sharing ratio like pyrolusite, ramsdellite, todorokite and lithiophorite or lepidocrocite and goethite. A direct application of this result has shown that the proportion of pyrolusite domains within the lattice of nsutite from Ghana is equal to 35±15 percent. The systematic study of Mn dioxides also put forward the sensitivity of EXAFS to the presence of corner-sharing octahedra, with a detection limit found to be less than 8 percent. In spite of their similar XRD patterns, the EXAFS study of todorokite and asbolane confirms that they possess a distinct structure; that is, a tunnel structure for the former and a layered structure for the second. Such a topological approach has been used to probe the structure of ferruginous vernadite; a highly disordered iron-bearing Mn oxide. Fe and Mn K-edges EXAFS spectra are very dissimilar, traducing a different short range order. The Mn phase is constituted by MnO₂ layers. Its large local structural order contrasts with the short range disorder of the iron phase. This hydrous Fe oxyhydroxide is constituted by face-, edge- and corner-sharing octahedra. This iron phase possesses the same local order as feroxy-hyte, but is long range disordered. The presence of face-sharing Fe(O,OH)₆ octahedra prevents its direct solid-state transformation into well crystallized oxyhydroxides, and explains the necessary dissolution-reprecipitation mechanism generally invoked for the hydrous ferric gel → goethite transformation.     

Characterization of the amorphous state in metamict silicates and niobates by EXAFS and XANES analyses

X-ray absorption spectroscopy using synchrotron radiation has been applied to the investigation of the coordination geometries around Y, Zr and Nb atoms in metamict zircon, gadolinite, fergusonite, euxenite and samarskite. EXAFS and XANES spectra of their crystalline counterparts and synthetic compounds including ZrO₂, Y₂O₃, YNbTiO₆, YNbO₄, LiNbO₃, and NiNb₂O₆ were also measured for comparison. Metamict zircon shows a significant decrease in its Zr-O bond distances accompanying an increase in distortion of the Zr-O coordination polyhedra as compared with crystalline zircon. On the contrary, the average Nb-O bond distances and the symmetry of the coordination polyhedra around the Nb atoms in metamict euxenite and samarskite resemble those in the crystalline euxenite. Compared with crystalline fergusonite, a decrease in the distortion of the Nb-O octahedra is observed in metamict fergusonite. The structures of the second nearest neighbors (the metal-metal interactions) are largely disrupted in the metamict specimens except for metamict zircon and samarskite with high trivalent iron concentration. Nb in metamict samarskite is in octahedral coordination by oxygen and is similar to that in euxenite.     

Texture effect on polarized EXAFS amplitude

 Application of polarized extended X-ray absorption fine structure (P-EXAFS) spectroscopy to thin films of fine-grained minerals is emerging as a powerful method to investigate the in-plane and out-of-plane local structure of phyllosilicates. Mineral platelets have no preferential orientation in the plane of the film, and their c* axes are oriented essentially along the film normal. The angular dependence of the EXAFS amplitude critically depends on the orientation distribution of c* axes due to mosaic spread. The effect of film texture on EXAFS amplitude has been calculated as a function of the mosaic spread, the orientation of the electric field vector, and the crystallographic orientation of the atomic pair. Calculations show that the reduction in amplitude for partially ordered films is more important when the electric field vector is perpendicular to the film plane. For phyllosilicates, no significant deviation from single crystal dichroism occurs when the mosaic spread is less than ±20–25° half-width at half-maximum (HWHM) for parallel measurement, and ±15–20° HWHM for normal measurement. Graphs are given for correcting EXAFS-derived coordination numbers for texture effects. Received: 3 February 2000 / Accepted: 26 July 2000     

New insight into the structure of nanocrystalline ferrihydrite: EXAFS evidence for tetrahedrally coordinated iron(III)

Ferrihydrite (Fh) is a short-range ordered nanocrystalline iron(III) (oxyhydr)oxide that has been recognized to play an important role in contaminant sequestration and in iron cycling in geological and biological systems. Despite intensive research for the two last decades, the structure of Fh is still a subject of debate. In the present study, we report extended X-ray absorption fine structure (EXAFS) spectroscopy data collected on a large set of ferrihydrites and model compounds samples including especially nano-crystalline maghemite (Mh), goethite (Gt), and akaganeite (Aka). This set of EXAFS data recorded at cryogenic temperature over a wide energy range allows us to precisely determine the Fe-O mean distance (〈Fe-O〉) in the first coordination shell of iron for this large set of iron (oxyhydr)oxides. Our EXAFS analysis includes both classical shell-by-shell fits of Fourier-filtered and unfiltered data as well as analysis of Fe-O distance distribution in the first coordination shell of iron using the Landweber iteration method. 〈Fe-O〉 determined by these complementary EXAFS analyses are similar: 〈Fe-O〉 is shorter in Mh (1.96 ± 0.01 Å) that contains 37.5% of tetrahedral iron, than in Gt (2.01 ± 0.01 Å), Aka (2.00 ± 0.01 Å) and hematite (Hm) (2.01 ± 0.01 Å) that do not contain tetrahedral iron. 〈Fe-O〉 for the five Fh samples investigated (1.97 ± 0.01 Å) was found to be slightly longer than in Mh and significantly shorter than those in Gt, Aka and Hm. This short 〈Fe-O〉 distance in Fh indicates the presence of significant amount of tetrahedrally coordinated iron(III) in all Fh samples studied, which ranges between 20 ± 5% and 30 ± 5% of total iron. In addition, our analysis of Fe-Fe distances observed by EXAFS is consistent with a Keggin-like motif at a local scale (∼5 Å) in the Fh structure.     

Iron speciation in minerals and glasses probed by $$\hbox{M}_{2/3}$$-edge X-ray Raman scattering spectroscopy

We present a spectroscopic study of the iron \(\hbox{M}_{2/3}\)-edge for several minerals and compounds to reveal information about the oxidation state and the local coordination of iron. We describe a novel approach to probe the iron \(\hbox{M}_{2/3}\)-edge bulk sensitively using X-ray Raman scattering. Significant changes in the onset and shape of the Fe \(\hbox{M}_{2/3}\)-edge were observed on ferrous and ferric model compounds with Fe in octahedral and tetrahedral coordination. Simulation of the spectra is possible using an atomic multiplet code, which potentially allows determination of, e.g., crystal-field parameters in a quantitative manner. A protocol is discussed for determination of the Fe oxidation state in compounds by linear combination of spectra of ferric and ferrous end members. The presented results demonstrate the capabilities of Fe \(\hbox{M}_{2/3}\)-edge spectroscopy by X-ray Raman scattering to extract information on the ratio of trivalent to total iron \(\hbox{Fe}^{3+}/\sum \hbox{Fe}\) and local coordination. As X-ray Raman scattering is performed with hard X-rays, this approach is suitable for in situ experiments at high pressure and temperature. It thus may provide indispensable information on oxidation state, electronic structure and local structure of materials that are important for physical and chemical processes of the deep Earth.     

Long-range vs. short-range ordering in synthetic Cr-substituted goethites

A series of Cr-substituted goethites with (Cr:Fe molar ratio up to 0.12) were prepared. Thermal analysis of the solids indicates the formation of cation-deficient compounds that are more stable towards the transformation to hematite as the Cr content increases. Powder X-ray diffraction (PXRD) and extended X-ray absorption fine structure (EXAFS) techniques were used to assess the structural characteristics of the whole series of the substituted solids. XRD patterns demonstrate that the order around Fe remains typical of a goethite-like structure. Rietveld refinement of X-ray diffraction data indicates that the incorporation of Cr causes a slight decrease in the cell volume with the c-cell parameter following the Vegard’s law. This decrease is accompanied by changes in opposite directions of the various Me-Me distances. EXAFS spectra at the Fe K-edge indicate that the local order around the Fe atom changes slightly upon Cr substitution: Measurements in the Cr K-edge show that the Cr environment remains unchanged in the whole series. All the observed trends in both average Rietveld and local EXAFS distances can be traced back to the differences in the coordination polyhedra around Cr and Fe. The polyhedron around Cr is more symmetric and can be described as Cr(OH_0.5)₆ as opposed to the polyhedron around Fe that contains two distinct sets of ligands, FeO₃(OH)₃. The effects caused by substitution are governed by this difference, rather than by the smaller size of Cr(III) as compared to Fe(III). Simultaneous use of XAS and Rietveld refinement of XRD data permits tracing the trends in the average long range ordering (Me-Me distances) to local changes in distances and angles when Cr³⁺ substitutes Fe³⁺ in goethite. Complex changes in the various interatomic distances and angles may result in deceivingly simple long-range trends. These trends are therefore of limited value as probes for the atomic scale changes. On the other hand, XAS provide direct information on the fundamental, atomic-scale changes.     

Structure and specification of iron complexes in aqueous solutions determined by X-ray absorption spectroscopy

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 $\text{1s → 3d}$ 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 $\text{1s → 3d}$ 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].     

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

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

A Fe K-edge XAS study of amethyst

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

Distribution of Fe in the octahedral sheet of trioctahedral micas by polarized EXAFS

The distribution of Fe atoms within the octahedral sheet of a series of trioctahedral micas has been investigated by polarized Fe K-edge EXAFS spectroscopy. Single crystals have been oriented in the X-ray beam with the layer plane at 35° with respect to the electric field vector. At this “magic angle”, contributions to the EXAFS spectrum of nearest cation shells are equal to those recorded on a completely disoriented powder. The average number of Fe and Mg cations surrounding each Fe atom has been determined and compared with those deduced from NMR spectra. It is shown that the distribution of Fe atoms is not random, the deviation from this distribution depending on the fluorine content. The agreement between these independent results proves the reliability of the structural information deduced from EXAFS and NMR spectra as well as the usefulness of these two methods in analyzing the local distribution of cations in minerals.     

High-pressure perovskites on the join CaTiO3-FeTiO3

An exploratory high-pressure study of the join CaTiO₃-FeTiO₃ has uncovered two intermediate perovskites with the compositions CaFe₃Ti₄O₁₂ and CaFeTi₂O₆. These perovskites have ordering of Ca²⁺ and Fe²⁺ on the A sites. Both of these perovskites are unusual in that the A sites containing Fe²⁺ are either square planar or tetrahedral, due to the particular tilt geometries of the octahedral frameworks. For CaFe₃Ti₄O₁₂, the structure has been refined from a powder using the Rietveld technique. This compound is a cubic double perovskite (SG Im $\bar 3$ , a = 7.4672 Å), isostructural with NaMn₇O₁₂. Fe²⁺ is in a square-planar A site (similar to Mn³⁺ in NaMn₇O₁₂) with Fe-O = 2.042(3) Å, with distant second neighbors in a rectangle at Fe-O = 2.780(6) Å. Calcium is in a distorted icosahedron with Ca-O =2.635(5) Å. CaFeTi₂O₆ crystallizes in a unique tetragonal double perovskite structure (SG P4₂/nmc, a = 7.5157(2), c = 7.5548(2)), with A-site iron in square-planar (Fe-O = 2.097(2) Å) and tetrahedral (Fe-O = 2.084(2) Å) coordination, again with distant second neighbor oxygens near 2.8 Å. Rietveld refinement was also performed for the previously known perovskite-related form of FeTiO₃ recovered from high pressure (lithium niobate type). This compound is trigonal R3c, with a = 5.1233(1) and c = 13.7602(2). The ordered perovskites appear to be stable at 1215 GPa and CaFe₃Ti₄O₁₂ is found as low as 5 GPa. Thus these perovskites may be important to upper mantle mineralogy, particularly in kimberlites. These compounds are the first known quenchable perovskites with large amounts of A-site ferrous iron, and add greatly to the known occurrences of ferrous iron in perovskites.     

A Stucture—mineralogical Study of Ringwoodite

The powder XRD analysis of ringwoodite(γ-Fe2SiO4),which was synthesized in a II-stage anvil high-pressure capsule,was made,Its unit-cell parameter was calculated:a=8.219A,After the refinements,for several cycles,of the oxygen parameter x and the occupancy rate of Si in octahedron site,i.e.,the iversion degree u,the final result is R=0.077,when x=0.379A and u=27.5%,with the structural formula (Fe1.725 Si0.275)VI(Si0.725Fe0.275)IV O4 and atomic distances(Fe,Si)VI-O=2.022 A and (Si,Fe)IV-O=1.836A,Meanwhile,the Moessbauer spectroscopic analysis of the sample was conducted and the results obtained are in good agreement with those of X-ray structural analysis ,This paper focuses on the phase transformation and the properties of bonds of α－Fe2SiO4→γ-Fe2SiO4.     

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.     

Xanes analysis on pyroxenes with different ca concentration in M2 site

X-ray Absorption Near-Edge Structure (XANES) analysis of the calcium K-edge of a series of natural pyroxenes is reported. The samples belong to the solid solution series diopside (CaMgSi₂O₆) — jadeite (NaAlSi₂O₆). In diopside, the M2 site is occupied by Ca only, but along the join Na substitutes Ca in this position. From XANES analysis of different samples we found a distortion of the polyhedron around the M2 site varying as a function of Ca content. This is probably due to compression of the site in a selected direction with an unchanged average distance, so that the coordination around the Ca atom changes from the 4-2-2 configuration typical of the diopside structure to the 6-2 configuration typical of Na in the jadeite structure. Intermediate pyroxenes exhibit both configurations, and acquire therefrom the structural order as already detected by X-ray diffraction techniques.     

Molecular orbitals of Si2O 7 6− , Si3O 10 8− , etc., and mixed (B,Al,P,Si) m applied to clusters and X-ray spectroscopy data of silicates

The Si, Al L_{II, III} and OK_α emission and quantum yield spectra were obtained for 24 silicates. It was found that in minerals of a homogeneous anion composition the Si L_{II, III} line has double-humped structure, and when in addition to SiO ₄ ^4? ions of other composition (BeO ₄ ^6? , AlO ₄ ^5? etc.) are present it has triple-humped structure. The process of crystal-glass transition was studied by X-ray spectroscopy. The result is that in spite of the original form of the Si L_{II, III} line of the mineral this line changes its structure in glass and exhibits a typical double-humped structure. The CNDO/2 approach was used to calculate the electronic structure of basic structural groups of silicates from SiO ₄ ^4? to Si₅O ₁₆ ^12? by replacing one or two of the Si atoms by Be, B, Al and P. A qualitative interpretation of the X-ray spectra is presented.     

Surface complexation and precipitate geometry for aqueous Zn(II) sorption on ferrihydrite I: X-ray absorption extended fine structure spectroscopy analysis

“Two-line” ferrihydrite samples precipitated and then exposed to a range of aqueous Zn solutions (10⁻⁵ to 10⁻³ M), and also coprecipitated in similar Zn solutions (pH 6.5), have been examined by Zn and Fe K-edge X-ray absorption spectroscopy. Typical Zn complexes on the surface have Zn-O distances of 1.97(.02) Å and coordination numbers of about 4.0(0.5), consistent with tetrahedral oxygen coordination. This contrasts with Zn-O distances of 2.11(.02) Å and coordination numbers of 6 to 7 in the aqueous Zn solutions used in sample preparation. X-ray absorption extended fine structure spectroscopy (EXAFS) fits to the second shell of cation neighbors indicate as many as 4 Zn-Fe neighbors at 3.44(.04) Å in coprecipitated samples, and about two Zn-Fe neighbors at the same distance in adsorption samples. In both sets of samples, the fitted coordination number of second shell cations decreases as sorption density increases, indicating changes in the number and type of available complexing sites or the onset of competitive precipitation processes. Comparison of our results with the possible geometries for surface complexes and precipitates suggests that the Zn sorption complexes are inner sphere and at lowest adsorption densities are bidentate, sharing apical oxygens with adjacent edge-sharing Fe(O,OH)₆ octahedra. Coprecipitation samples have complexes with similar geometry, but these are polydentate, sharing apices with more than two adjacent edge-sharing Fe(O,OH)₆ polyhedra. The results are inconsistent with Zn entering the ferrihydrite structure (i.e., solid solution formation) or formation of other Zn-Fe precipitates. The fitted Zn-Fe coordination numbers drop with increasing Zn density with a minimum of about 0.8(.2) at Zn/(Zn + Fe) of 0.08 or more. This change appears to be attributable to the onset of precipitation of zinc hydroxide polymers with mainly tetrahedral Zn coordination. At the highest loadings studied, the nature of the complexes changes further, and a second type of precipitate forms. This has a structure based on a brucite layer topology, with mainly octahedral Zn coordination. Amorphous zinc hydroxide samples prepared for comparison had a closely similar local structure. Analysis of the Fe K-edge EXAFS is consistent with surface complexation reactions and surface precipitation at high Zn loadings with little or no Fe-Zn solid solution formation. The formation of Zn-containing precipitates at solution conditions two or more orders of magnitude below their solubility limit is compared with other sorption and spectroscopic studies that describe similar behavior.     

Analysis of the Major Fe Bearing Mineral Phases in Recent Lake Sediments by EXAFS Spectroscopy

Extended X-ray absorption fine structure (EXAFS) spectroscopy and chemical analyses were combined to determine the Fe bearing minerals in recent lake sediments from Baldeggersee (Switzerland). The upper section of a laminated sediment core, deposited under eutrophic conditions, was compared to the lower part from an oligotrophic period. Qualitative analysis of FeK EXAFS agreed well with chemical data: In the oligotrophic section Fe(II)–O and Fe(III)–O specieswere present, whereas a significant fraction of Fe(II)–S sulfides was strongly indicated in the eutrophic part. A statistical analysis was performed by least square fitting of normalized reference spectra. The set of reference minerals included Fe(III) oxides and Fe(II) sulfides, carbonates and phosphates. In the oligotrophic regime no satisfying fit was obtained using the set of reference spectra, indicating that siderite (FeCO₃) was not present in a significant amount in these carbonate-rich sediments. Simulated EXAFS spectra for a(Ca_x, Fe_1-x)CO₃solid solution allowed reconstructing the specificfeatures of the experimental spectra, suggesting that this phase was the dominant Fe carrier in the oligotrophic section of the core. In the eutrophic part, mackinawite was positively identified and represented the dominant Fe(II) sulfide phase. This finding agreed with chemical extraction, which indicated that18–40 mol% of Fe was contained in the acid volatile iron sulfide fraction. EXAFS spectra of the eutrophic section were best fitted by considering the admixture of mackinawite and the Fe–Ca carbonate phase inferred to be predominant in the oligotrophic regime.     

Effect of citrate on the local Fe coordination in ferrihydrite, arsenate binding, and ternary arsenate complex formation

In oxic environments contaminated with arsenate (As(V)), small polyhydroxycarboxylates such as citrate may impact the structure of precipitating ferrihydrite (Fh) and thus the surface speciation of As(V). In this study, ‘2-line’ Fh was precipitated from ferric nitrate solutions that were neutralized to pH 6.5 in the presence of increasing citrate concentrations and in the absence or presence of As(V). The initial citrate/Fe and As/Fe ratios were 0-50 mol% and 5 mol%, respectively. The reaction products, enriched with up to 0.32 mol citrate per mole Fe, were characterized by X-ray diffraction, transmission electron microscopy, and Fe and As K-edge X-ray absorption spectroscopy. Citrate decreased the particle size of Fh by impairing the polymerization of Fe(O,OH)₆ octahedra via edge and corner linkages. In the presence of citrate and As(V), coordination numbers of Fe decreased by up to 28% relative to pure Fh. Citrate significantly reduced the static disorder of Fe-O bonds, implying a decreased octahedral distortion in Fh. Mean bond distances in Fh were not affected by citrate and remained constant within error at 1.98 Å for Fe-O, 3.03 Å for Fe-Fe1, and 3.45 Å for Fe-Fe2. Likewise, citrate had no effect on the As-Fe (3.31 Å) bond distance in As(V) coprecipitated with Fh. The As K-edge EXAFS data comply with the formation of (i) only monodentate binuclear (²C) As(V) surface complexes and (ii) combinations of ²C, monodentate mononuclear (¹V), and outersphere As(V) surface complexes. Our results suggest that increasing citrate concentrations led to a decreasing ¹V/²C ratio and/or that citrate increasingly impaired the formation of outersphere As(V) complexes. Moreover, citrate stabilized colloidal suspensions of Fh (pH 4.3-6.6, I ∼0.45 M) and reduced Fh formation at the expense of soluble Fe(III)-citrate complexes. At initial citrate/Fe ratios ?25 mol%, between 8% and 41% of total Fe was bound in Fe(III)-citrate complexes after Fh formation. Polynuclear Fe(III)-citrate species were found to bind As(V) via surface complexes indistinguishable by EXAFS from those of As(V) adsorbed to or coprecipitated with Fh. Our study implies that low molecular weight polyhydroxycarboxylates may enhance the mobility of As(V) in aqueous systems of high ionic strength (e.g., neutralizing acid mine drainage) by colloidal stabilization of suspended Fh particles and the formation of ternary As(V) complexes.