Speciation and characterization of arsenic in gold ores and cyanidation tailings using X-ray absorption spectroscopy

The knowledge of mineralogy and molecular structure of As is needed to better understand the stability of As in wastes resulting from processing of gold ores. In this study, optical microscopy, scanning electron microscopy, electron microprobe, X-ray diffraction and X-ray absorption fine structure (XAFS) spectroscopy (including both XANES and EXAFS regimes) were employed to determine the mineralogical composition and local coordination environment of As in gold ores and process tailings from bench-scale tests designed to mimic a common plant practice. Arsenic-bearing minerals identified in the ores and tailings include iron (III) oxyhydroxides, scorodite (FeAsO₄·2H₂O), ferric arsenates, arseniosiderite (Ca₂Fe₃(AsO₄)₃O₂·3H₂O), Ca-Fe arsenates, pharmacosiderite (KFe₄(AsO₄)₃(OH)₄·6-7H₂O), jarosite (K₂Fe₆(SO₄)₄(OH)₁₂) and arsenopyrite (FeAsS). Iron (III) oxyhydroxides contain variable levels of As from trace to about 22 wt% and Ca up to approximately 9 wt%.Finely ground ore and tailings samples were examined by bulk XAFS and selected mineral grains were analyzed by microfocused XAFS (micro-EXAFS) spectroscopy to reconcile the ambiguities of multiple As sources in the complex bulk EXAFS spectra. XANES spectra indicated that As occurs as As⁵⁺in all the samples. Micro-EXAFS spectra of individual iron (III) oxyhydroxide grains with varying As concentrations point to inner-sphere bidentate-binuclear arsenate complexes as the predominant form of As. There are indications for the presence of a second Fe shell corresponding to bidentate-mononuclear arrangement. Iron (III) oxyhydroxides with high As concentrations corresponding to maximum adsorption densities probably occur as nanoparticles. The discovery of Ca atoms around As in iron (III) oxyhydroxides at interatomic distances of 4.14-4.17 Å and the coordination numbers suggest the formation of arseniosiderite-like nanoclusters by coprecipitation rather than simple adsorption of Ca onto iron (III) oxyhydroxides. Correlation of Ca with As in iron (III) oxyhydroxides as determined by electron microprobe analysis supports the coprecipitate origin for the presence of Ca in iron (III) oxyhydroxides.The samples containing higher abundances of ferric arsenates released higher As concentrations during the cyanidation tests. The presence of highly soluble ferric arsenates and Ca-Fe arsenates, and relatively unstable iron (III) oxyhydroxides with Fe/As molar ratios of less than 4 in the ore and process tailings suggests that not only the tailings in the impoundment will continue to release As, but also there is the potential for mobilization of As from the natural sources such as the unmined ore.     

Experimental study of europium (III) coprecipitation with calcite

Partitioning of Eu(III) in calcite, CaCO₃, was evaluated with the aim of collecting data on partition coefficients and to enhance understanding of the incorporation mechanisms. This information will aid in the interpretation of geological processes from rare Earth element (REE) data and in the use of Eu(III) as a chemical analogue for the trivalent actinides, particularly Am(III) and Cm(III). Coprecipitation experiments were carried out by the constant addition method at 25°C and P_CO2 = 1 atm. Eu(III) was strongly partitioned from the solution into calcite. For dilute solid solutions (X_Eu < 0.001), Eu partition coefficients were estimated to be 770 ± 290 and found to be independent of calcite precipitation rate in the range of 0.02 to 2.7 nmol mg⁻¹ min⁻¹. This could be explained by the approximately equal values of the Eu partition and adsorption coefficients. Several solid solution models were tested. A vacancy model for Eu₂(CO₃)₃-CaCO₃ is consistent with the experimental results and constraints on geometry for Eu fit in the calcite lattice. For low Eu content, vacancy density is independent of Eu concentration in the solid so logarithm of the ion activity product, log (Eu)²(CO₃²⁻)³, depends linearly on log X_Eu². The fit of the data to such a model is good evidence that Eu(III) is taken up as a true solid solution, not simply by physical trapping. A model using EuOHCO₃-CaCO₃ is also consistent with the uptake stoichiometry, but EuOH²⁺ substitution for Ca²⁺ would be expected to distort the calcite structure more than is compatible with such a high K_D. Several other models, including EuNa(CO₃)₂-CaCO₃, were abandoned because their stoichiometric relationships did not fit the experimental data.     

Iron isotope fractionation by Fe(II)-oxidizing photoautotrophic bacteria

Photoautotrophic bacteria that oxidize ferrous iron (Fe[II]) under anaerobic conditions are thought to be ancient in origin, and the ferric (hydr)oxide mineral products of their metabolism are likely to be preserved in ancient rocks. Here, two enrichment cultures of Fe(II)-oxidizing photoautotrophs and a culture of the genus Thiodictyon were studied with respect to their ability to fractionate Fe isotopes. Fe isotope fractionations produced by both the enrichment cultures and the Thiodictyon culture were relatively constant at early stages of the reaction progress, where the ⁵⁶Fe/⁵⁴Fe ratios of poorly crystalline hydrous ferric oxide (HFO) metabolic products were enriched in the heavier isotope relative to aqueous ferrous iron (Fe[II]_aq) by ∼1.5 ± 0.2‰. This fractionation appears to be independent of the rate of photoautotrophic Fe(II)-oxidation, and is comparable to that observed for Fe isotope fractionation by dissimilatory Fe(III)-reducing bacteria. Although there remain a number of uncertainties regarding how the overall measured isotopic fractionation is produced, the most likely mechanisms include (1) an equilibrium effect produced by biological ligands, or (2) a kinetic effect produced by precipitation of HFO overlaid upon equilibrium exchange between Fe(II) and Fe(III) species. The fractionation we observe is similar in direction to that measured for abiotic oxidation of Fe(II)_aq by molecular oxygen. This suggests that the use of Fe isotopes to identify phototrophic Fe(II)-oxidation in the rock record may only be possible during time periods in Earth’s history when independent evidence exists for low ambient oxygen contents.     

Raman spectroscopic study of CO2-NaCl-H2O mixtures in synthetic fluid inclusions at high temperatures

Mixtures of CO₂-NaCl-H₂O contained in synthetic fluid inclusions are studied by laser Raman spectroscopy at high temperatures. With increasing temperature, the band splitting (X) of υ₁-2υ₂ diad of spectrum of CO₂ presents more variations, and the intensity ratios of the hot bands to the υ₁-2υ₂ diad increase. For mixtures of gas phase rich in CO₂ and liquid phase rich in H₂O before homogenization, the strength of hydrogen bonding of water in the liquid phase decreases almost linearly with increasing temperature. When mixtures become homogeneous liquid phases, carbon dioxide content increases significantly as a result of the abrupt decrease in hydrogen bonds. Our results show that the hydrogen bonds change only slightly at higher temperatures above the homogeneous point, and a certain extent of the hydrogen bonds still remains at the highest temperature of 550°C of this work. The study is helpful to Raman spectroscopic analysis of natural fluid inclusions at high temperatures.     

Molecular modeling of water structure in nano-pores between brucite (001) surfaces

Molecular dynamics (MD) computer simulations of liquid water held in one-dimensional nano-confinement by two parallel, electrostatically neutral but hydrophilic surfaces of brucite, Mg(OH)₂, provide greatly increased, atomistically detailed understanding of surface-related effects on the spatial variation in the structural ordering, hydrogen bond (H-bond) organization, and local density of H₂O molecules at this important model hydroxide surface. NVT-ensemble MD simulations (i.e., at constant number of atoms, volume and temperature) were performed for a series of model systems consisting of 3 to 30 Å-thick water layers (containing 35 to 360 H₂O molecules) confined between two 19 Å-thick brucite substrate layers. The results show that the hydrophilic substrate significantly influences the near-surface water structure, with both H-bond donation to the surface oxygen atoms and H-bond acceptance from the surface hydrogen atoms in the first surface layer of H₂O molecules playing key roles. Profiles of oxygen and hydrogen atomic density and H₂O dipole orientation show significant deviation from the corresponding structural properties of bulk water to distances as large as 15 Å (∼5 molecular water layers) from the surface, with the local structural environment varying significantly with the distance from the surface. The water molecules in the first layer at about 2.45 Å from the surface have a two-dimensional hexagonal arrangement parallel to brucite layers, reflecting the brucite surface structure, have total nearest neighbor coordinations of 5 or 6, and are significantly limited in their position and orientation. The greatest degree of the tetrahedral (ice-like) ordering occurs at about 4 Å from the surface. The translational and orientational ordering of H₂O molecules in layers further from the surface become progressively more similar to those of bulk liquid water. A quantitative statistical analysis of the MD-generated instantaneous molecular configurations in terms of local density, molecular orientation, nearest neighbor coordination, and the structural details of the H-bonding network shows that the local structure of interfacial water at the brucite surface results from a combination of “hard wall” (geometric and confinement) effects, highly directional H-bonding, and thermal motion. This structure does not resemble that of bulk water at ambient conditions or at elevated or reduced temperature, but shares some similarities with that of water under higher pressure.     

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

     

Formation of Fe(III)-minerals by Fe(II)-oxidizing photoautotrophic bacteria

It has been suggested that Fe(II)-oxidizing photoautotrophic bacteria may have catalyzed the precipitation of an ancient class of sedimentary deposits known as Banded Iron Formations. In order to evaluate this claim, it is necessary to define and understand this process at a molecular level so that putative Fe-isotope “biosignatures” in ancient rocks can be interpreted. In this report, we characterize the substrates and products of photoautotrophic Fe(II)-oxidation by three phylogenetically distinct Fe(II)-oxidizing bacteria. In every case, dissolved Fe(II) is used as the substrate for oxidation, and there is no evidence for active dissolution of poorly soluble Fe(II)-minerals by biogenic organic ligands. Poorly crystalline Fe(III) (hydr)oxide mineral phases are initially precipitated, and as they age, rapidly convert to the crystalline minerals goethite and lepidocrocite. Although the precipitates appear to associate with the cell wall, they do not cover it entirely, and precipitate-free cells represent a significant portion of the population in aged cultures. Citrate is occasionally detected at nanomolar concentrations in all culture fluids, whereas an unknown organic molecule is always present in two out of the three bacterial cultures. Whether these molecules are released by the cell to bind Fe(III) and prevent the cell from encrustation by Fe(III) (hydr)oxides is uncertain, but seems unlikely if we assume Fe(II)-oxidation occurs at the cell surface. In light of the energetic requirement the cell would face to produce ligands for this purpose, and given the local acidity metabolically generated in the microenvironment surrounding Fe(II)-oxidizing cells, our results suggest that Fe(III) is released in a dissolved form as an inorganic aqueous complex and/or as a colloidal aggregate prior to mineral precipitation. The implication of these results for the interpretation of Fe-isotope fractionation measured for this class of bacteria (Croal et al., 2004) is that equilibrium processes involving free biological ligands do not account for the observed fractionation.     

Analysis of long-term bacterial vs. chemical Fe(III) oxide reduction kinetics

Data from studies of dissimilatory bacterial (10⁸ cells mL⁻¹ of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L⁻¹) were analyzed in relation to a generalized rate law for mineral dissolution (J_t/m₀ = k′(m/m₀)^γ, where J_t is the rate of dissolution and/or reduction at time t, m₀ is the initial mass of oxide, and m/m₀ is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.     

Approaches to surface complexation modeling of Uranium(VI) adsorption on aquifer sediments

Uranium(VI) adsorption onto aquifer sediments was studied in batch experiments as a function of pH and U(VI) and dissolved carbonate concentrations in artificial groundwater solutions. The sediments were collected from an alluvial aquifer at a location upgradient of contamination from a former uranium mill operation at Naturita, Colorado (USA). The ranges of aqueous chemical conditions used in the U(VI) adsorption experiments (pH 6.9 to 7.9; U(VI) concentration 2.5 · 10⁻⁸ to 1 · 10⁻⁵ M; partial pressure of carbon dioxide gas 0.05 to 6.8%) were based on the spatial variation in chemical conditions observed in 1999-2000 in the Naturita alluvial aquifer. The major minerals in the sediments were quartz, feldspars, and calcite, with minor amounts of magnetite and clay minerals. Quartz grains commonly exhibited coatings that were greater than 10 nm in thickness and composed of an illite-smectite clay with occluded ferrihydrite and goethite nanoparticles. Chemical extractions of quartz grains removed from the sediments were used to estimate the masses of iron and aluminum present in the coatings. Various surface complexation modeling approaches were compared in terms of the ability to describe the U(VI) experimental data and the data requirements for model application to the sediments. Published models for U(VI) adsorption on reference minerals were applied to predict U(VI) adsorption based on assumptions about the sediment surface composition and physical properties (e.g., surface area and electrical double layer). Predictions from these models were highly variable, with results overpredicting or underpredicting the experimental data, depending on the assumptions used to apply the model. Although the models for reference minerals are supported by detailed experimental studies (and in ideal cases, surface spectroscopy), the results suggest that errors are caused in applying the models directly to the sediments by uncertain knowledge of: 1) the proportion and types of surface functional groups available for adsorption in the surface coatings; 2) the electric field at the mineral-water interface; and 3) surface reactions of major ions in the aqueous phase, such as Ca²⁺, Mg²⁺, HCO₃⁻, SO₄²⁻, H₄SiO₄, and organic acids. In contrast, a semi-empirical surface complexation modeling approach can be used to describe the U(VI) experimental data more precisely as a function of aqueous chemical conditions. This approach is useful as a tool to describe the variation in U(VI) retardation as a function of chemical conditions in field-scale reactive transport simulations, and the approach can be used at other field sites. However, the semi-empirical approach is limited by the site-specific nature of the model parameters.     

Controls on iron-isotope fractionation in organic-rich sediments (Kimmeridge Clay, Upper Jurassic, Southern England)

This study explores the fractionation of iron isotopes (⁵⁷Fe/⁵⁴Fe) in an organic-rich mudstone succession, focusing on core and outcrop material sampled from the Upper Jurassic Kimmeridge Clay Formation type locality in south Dorset, UK. The organic-rich environments recorded by the succession provide an excellent setting for an investigation of the mechanisms by which iron isotopes are partitioned among mineral phases during biogeochemical sedimentary processes.Two main types of iron-bearing assemblage are defined in the core material: mudstones with calcite ± pyrite ± siderite mineralogy, and ferroan dolomite (dolostone) bands. A cyclic data distribution is apparent, which reflects variations in isotopic composition from a lower range of δ⁵⁷Fe values associated with the pyrite/siderite mudstone samples to the generally higher values of the adjacent dolostone samples. Most pyrite/siderite mudstones vary between −0.4 and 0.1‰ while dolostones range between −0.1 and 0.5‰, although in very organic-rich shale samples below 360 m core depth higher δ⁵⁷Fe values are noted. Pyrite nodules and pyritized ammonites from the type exposure yield δ⁵⁷Fe values of −0.3 to −0.45‰. A fractionation model consistent with the δ⁵⁷Fe variations relates the lower δ⁵⁷Fe pyrite and siderite ± pyrite mudstones values to the production of isotopically depleted Fe(II) during biogenic reduction of the isotopically heavier lithogenic Fe(III) oxides. A consequence of this reductive dissolution is that a ⁵⁷Fe-enriched iron species must be produced that potentially becomes available for the formation of the higher δ⁵⁷Fe dolostones. An isotopic profile across a dolostone band reveals distinct zonal variations in δ⁵⁷Fe, characterized by two peaks, respectively located above and below the central part of the band, and decoupling of the isotopic composition from the iron content. This form of isotopic zoning is shown to be consistent with a one-dimensional model of diffusional-chromatographic Fe-isotope exchange between dolomite and isotopically enriched pore water. An alternative mechanism envisages the infiltration of dissolved ferrous iron from variable (high and low) δ⁵⁷Fe sources during coprecipitation of Fe(II) ion with dolomite. The study provides clear evidence that iron isotopes are cycled during the formation and diagenesis of organic carbon-rich sediments.     

Reduction of TcO4 by sediment-associated biogenic Fe(II)

The potential for reduction of ⁹⁹TcO₄⁻_(aq) to poorly soluble ⁹⁹TcO₂ · nH₂O_(s) by biogenic sediment-associated Fe(II) was investigated with three Fe(III)-oxide containing subsurface materials and the dissimilatory metal-reducing subsurface bacterium Shewanella putrefaciens CN32. Two of the subsurface materials from the U.S. Department of Energy’s Hanford and Oak Ridge sites contained significant amounts of Mn(III,IV) oxides and net bioreduction of Fe(III) to Fe(II) was not observed until essentially all of the hydroxylamine HCl-extractable Mn was reduced. In anoxic, unreduced sediment or where Mn oxide bioreduction was incomplete, exogenous biogenic TcO₂ · nH₂O_(s) was slowly oxidized over a period of weeks. Subsurface materials that were bioreduced to varying degrees and then pasteurized to eliminate biological activity, reduced TcO₄⁻_(aq) at rates that generally increased with increasing concentrations of 0.5 N HCl-extractable Fe(II). Two of the sediments showed a common relationship between extractable Fe(II) concentration (in mM) and the first-order reduction rate (in h⁻¹), whereas the third demonstrated a markedly different trend. A combination of chemical extractions and ⁵⁷Fe Mössbauer spectroscopy were used to characterize the Fe(III) and Fe(II) phases. There was little evidence of the formation of secondary Fe(II) biominerals as a result of bioreduction, suggesting that the reactive forms of Fe(II) were predominantly surface complexes of different forms. The reduction rates of Tc(VII)O₄⁻ were slowest in the sediment that contained plentiful layer silicates (illite, vermiculite, and smectite), suggesting that Fe(II) sorption complexes on these phases were least reactive toward pertechnetate. These results suggest that the in situ microbial reduction of sediment-associated Fe(III), either naturally or via redox manipulation, may be effective at immobilizing TcO₄⁻_(aq) associated with groundwater contaminant plumes.     

Partitioning of Ru, Rh, Pd, Re, Ir, and Au between Cr-bearing spinel, olivine, pyroxene and silicate melts

A series of high temperature experiments was undertaken to study partitioning of several highly siderophile elements (HSE; Ru, Rh, Pd, Re, Os, Ir, Pt and Au) between Cr-rich spinel, olivine, pyroxene and silicate melt. Runs were carried out on a Hawaiian ankaramite, a synthetic eucrite basalt, and a DiAn eutectic melt, at one bar, 19 kbar, and 20 kbar, respectively, in the temperature range of 1200 to 1300°C, at oxygen fugacities between the nickel-nickel oxide (NNO) and hematite-magnetite (HM) oxygen buffers. High oxygen fugacities were used to suppress the formation of HSE-rich “nuggets” in the silicate melts. The resulting oxide and silicate crystals (<100 μm) were analyzed using both SIMS and LA-ICP-MS, with a spatial resolution of 15 to 50 μm. Rhenium, Au and Pd were all found to be incompatible in Cr-rich spinel (D_Re^sp/melt = 0.0012-0.21, D_Au^sp/melt = 0.076, D_Pd^sp/melt = 0.14), whereas Rh, Ru and Ir were all found to be highly compatible (D_Rh^sp/melt = 41-530, D_Ru^sp/melt = 76-1143, D_Ir^sp/melt = 5-22000). Rhenium, Pd, Au and Ru were all found to be incompatible in olivine (D_Re^oliv/melt = 0.017-0.073, D_Pd^oliv/melt = 0.12, D_Au^oliv/melt = 0.12, D_Ru^oliv/melt = 0.23), Re is incompatible in orthopyroxene and clinopyroxene (D_Re^opx/melt = 0.013, D_Re^cpx/melt = 0.18-0.21), and Pt is compatible in clinopyroxene (D_Pt^cpx/melt = 1.5). The results are compared to and combined with previous work on HSE partitioning among spinel-structured oxides, and applied to some natural magmatic suites to demonstrate consistency.     

Reduction of uranium(VI) under sulfate-reducing conditions in the presence of Fe(III)-(hydr)oxides

Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(III)-(hydr)oxide mineral was varied to give equivalent Fe(III)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 growth, along with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and, to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L₃-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)-(hydr)oxides are incompletely reduced.     

An exotic kind of cosmic material: graphite-containing xenoliths from the Krymka (LL3.1) chondrite

Seven graphite-containing xenoliths were found in the Krymka (LL3.1) chondrite. The xenoliths have the following chemical and mineralogical characteristics which distinguish them from the Krymka host: (1) low totals in bulk chemical analyses obtained by electron microprobe; (2) high bulk Fe abundances; (3) a uniform recrystallized, chondrule-free texture; (4) the presence of euhedral graphite and carbon-rich material; (5) higher quantities of troilite and metal; (6) a relatively homogeneous composition of silicates; (7) a distinctive composition of metal, chromite and phosphate; (8) isotopically heavy C in graphite compared to both bulk Krymka and graphite in other ordinary chondrites. The xenoliths are mineralogically similar, but not identical, to the Krymka carbonaceous clast K1, which bears graphite microcrystals, organic compounds and mysterite. They resemble carbonaceous chondrites, both chemically and isotopically. The mineralogical, chemical and isotopic data for the graphite-containing fragments suggest that this material represents metamorphosed varieties of a previously unknown type of unequilibrated carbonaceous matter. Most likely, the graphite has a metamorphic origin and was crystallized from C-containing precursor materials through the following transformation sequence: organic compounds → C-rich material → graphite.     

Biomineralization of As(V)-hydrous ferric oxyhydroxide in microbial mats of an acid-sulfate-chloride geothermal spring, Yellowstone National Park

Acid-sulfate-chloride (pH∼3) geothermal springs in Yellowstone National Park (YNP) often contain Fe(II), As(III), and S(-II) at discharge, providing several electron donors for chemolithotrophic metabolism. The microbial populations inhabiting these environments are inextricably linked with geochemical processes controlling the behavior of As and Fe. Consequently, the objectives of the current study were to (i) characterize Fe-rich microbial mats of an ASC thermal spring, (ii) evaluate the composition and structure of As-rich hydrous ferric oxides (HFO) associated with these mats, and (iii) identify microorganisms that are potentially responsible for mat formation via the oxidation of Fe(II) and or As(III). Aqueous and solid phase mat samples obtained from a spring in Norris Basin, YNP (YNP Thermal Inventory NHSP35) were analyzed using a complement of chemical, microscopic and spectroscopic techniques. In addition, molecular analysis (16S rDNA) was used to identify potentially dominant microbial populations within different mat locations. The biomineralization of As-rich HFO occurs in the presence of nearly equimolar aqueous As(III) and As(V) (∼12 μM), and ∼ 48 μM Fe(II), forming sheaths external to microbial cell walls. These solid phases were found to be poorly ordered nanocrystalline HFO containing mole ratios of As(V):Fe(III) of 0.62 ± 0.02. The bonding environment of As(V) and Fe(III) is consistent with adsorption of arsenate on edge and corner positions of Fe(III)-OH octahedra. Numerous archaeal and bacterial sequences were identified (with no closely related cultured relatives), along with several 16S sequences that are closely related to Acidimicrobium, Thiomonas, Metallosphaera and Marinithermus isolates. Several of these cultured relatives have been implicated in Fe(II) and or As(III) oxidation in other low pH, high Fe, and high As environments (e.g. acid-mine drainage). The unique composition and morphologies of the biomineralized phases may be useful as modern-day analogs for identifying microbial life in past Fe-As rich environments.     

Revealing forms of iron in river-borne material from major tropical rivers of the Amazon Basin (Brazil)

The present study deals with the direct determination of colloidal forms of iron in river-borne solids from main rivers of the Amazon Basin. The contribution of different forms of colloidal iron have been assessed using ultrafiltration associated with various techniques including electron paramagnetic resonance spectroscopy (EPR), high resolution transmission electron microscopy (HRTEM), and micro proton-induced X ray emission analysis (μPIXE). EPR shows the presence of Fe³⁺ bound to organic matter (Fe³⁺-OM) and colloidal iron oxides. Quantitative estimate of Fe³⁺-OM content in colloidal matter ranges from 0.1 to 1.6 weight % of dried solids and decreases as the pH of the river increases in the range 4 to 6.8. The modeling of the field data with the Equilibrium Calculation of Speciation and Transport (ECOSAT) code demonstrates that this trend is indicative of a geochemical control resulting from the solubility equilibrium of Fe oxyhydroxide phase and Fe binding to organic matter. Combining EPR and μPIXE data quantitatively confirms the presence of colloidal iron phase (min. 35 to 65% of iron content), assuming no divalent Fe is present. In the Rio Negro, HRTEM specifies the nature of colloidal iron phase mainly as ferrihydrite particles of circa 20 to 50 Å associated with organic matter. The geochemical forms of colloidal iron differentiate the pedoclimatic regions drained by the different rivers, corresponding to different major weathering/erosion processes. Modeling allows the calculation of the speciation of iron as mineral, organic and dissolved phases in the studied rivers.     

XPS identification of bulk hole defects and itinerant Fe 3d electrons in natural troilite (FeS)

XPS measurements have been made of vacuum-fractured monoclinic pyrrhotite and troilite that highlight sulfur coordination (S 2p) and iron electronic state (Fe 2p) differences between these two minerals as a result of iron lattice site occupancy. Metal-like Fe states are observed in the Fe 2p spectrum of troilite due to increased occupancy of Fe lattice sites and increased Fe-Fe 3d orbital interaction within the constraints of the mineral structure. Additional electron population near the top of the troilite valence band is confirmed by XPS measurement. These results provide comprehensive experimental evidence for itinerent 3d electrons in the natural iron sulfides.     

Speciation of aqueous Ni(II)-carboxylate and Ni(II)-fulvic acid solutions: Combined ATR-FTIR and XAFS analysis

Aqueous solutions containing Ni(II) and a series of structurally related carboxylic acids were analyzed using attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) and Ni K-edge X-ray absorption fine structure spectroscopy (XAFS). XAFS spectra were also collected for solutions containing Ni²⁺ and chelating ligands (ethylenediaminetetraacetic acid, nitrilotriacetic acid (NTA)) as well as soil fulvic acid. Limited spectral changes are observed for aqueous Ni(II) complexes with monocarboxylates (formate, acetate) and long-chain polycarboxylates (succinate, tricarballylate), where individual donor groups are separated by multiple bridging methylene groups. These spectral changes indicate weak interactions between Ni(II) and carboxylates, and the trends are similar to some earlier reports for crystalline Ni(II)-acetate solids, for which X-ray crystallography studies have indicated monodentate Ni(II)-carboxylate coordination. Nonetheless, electrostatic or outer-sphere coordination cannot be ruled out for these complexes. However, spectral changes observed for short-chain dicarboxylates (oxalate, malonate) and carboxylates that contain an alcohol donor group adjacent to one of the carboxylate groups (lactate, malate, citrate) demonstrate inner-sphere metal coordination by multiple donor groups. XAFS spectral fits of Ni(II) solutions containing soil fulvic acid are consistent with inner-sphere Ni(II) coordination by one or more carboxylate groups, but spectra are noisy and outer-sphere modes of coordination cannot be ruled out. These molecular studies refine our understanding of the interactions between carboxylates and weakly complexing divalent transition metals, such as Ni(II).     

The role of trace minerals in chemical weathering in a high-elevation granitic watershed (Estibère, France): chemical and mineralogical evidence

We investigated chemical weathering in a high elevation granitic environment in three selected watersheds located in the Pyrenees (France). The sites were located on glacial deposits derived from similar Hercynian (∼300 Ma) granites characterized by the occurrence of zoned plagioclases and trace calcic phases (epidote, prehnite, sphene, apatite). The surface waters at those sites show high Ca/Na molar ratios (>1) which could not be explained by the dissolution of the major plagioclase (oligoclase) present in the rocks. The coupled approach of investigating stream water chemistry and the mineralogy and chemistry of rocks and soils allowed us to explore the role of the weathering of trace calcic minerals in calcium export at the watershed scale. The weathering of the trace calcic minerals which represent ∼ 1% of the total rock volume are responsible for more than 90% of the calcium export at the sites. Annual cationic fluxes (∼ 23.10⁴ eq/km²/yr) calculated for the Estibère watershed are among the highest reported for high elevation systems draining granitic rocks and ∼ 80% of this annual cationic flux can be attributed to the weathering of trace calcic phases. Calculations based on isotopic values (⁸⁷Sr/⁸⁶Sr) go in the same direction. Except apatite, the trace calcic phases appear to be mainly silicates, thus the type of chemical weathering observed in the Estibère watershed may have an influence on atmospheric CO₂ consumption by granite weathering. However, comparison with other watersheds draining granitic environments worldwide, and with the two other sites in the Pyrenees, indicate that the role of trace calcic phases is important in most young environments exposed to chemical weathering (e.g., high elevation catchments on glacial deposits). Other factors such as the date of glacial retreat, the physical denudation rate, the hydrological functioning of the watershed and the nature and structure of the soil cover are also important.