Arsenite sequestration at the surface of nano-Fe(OH)2, ferrous-carbonate hydroxide, and green-rust after bioreduction of arsenic-sorbed lepidocrocite by Shewanella putrefaciens

X-ray Absorption Fine Structure (XAFS) spectroscopy was used in combination with high resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), X-ray energy dispersive spectroscopy (XEDS), X-ray powder diffraction, and Mössbauer spectroscopy to obtain detailed information on arsenic and iron speciation in the products of anaerobic reduction of pure and As(V)- or As(III)-adsorbed lepidocrocite (γ-FeOOH) by Shewanella putrefaciens ATCC 12099. We found that this strain of S. putrefaciens is capable of using Fe(III) in lepidocrocite and As(V) in solution or adsorbed on lepidocrocite surfaces as electron acceptors. Bioreduction of lepidocrocite in the absence of arsenic resulted in the formation of hydroxycarbonate green rust 1 [Fe^II₄Fe^III₂(OH)₁₂CO₃: GR1(CO₃)], which completely converted into ferrous-carbonate hydroxide (Fe^II₂(OH)₂CO₃: FCH) over nine months. This study thus provides the first evidence of bacterial reduction of stoichiometric GR1(CO₃) into FCH. Bioreduction of As(III)-adsorbed lepidocrocite also led to the formation of GR1(CO₃) prior to formation of FCH, but the presence of As(III) slows down this transformation, leading to the co-occurrence of both phases after 22-month of aging. At the end of this experiment, As(III) was found to be adsorbed on the surfaces of GR1(CO₃) and FCH. After five months, bioreduction of As(V)-bearing lepidocrocite led directly to the formation of FCH in association with nanometer-sized particles of a minor As-rich Fe(OH)₂ phase, with no evidence for green rust formation. In this five-month experiment, As(V) was fully converted to As(III), which was dominantly sorbed at the surface of the Fe(OH)₂ nanoparticles as oligomers binding to the edges of Fe(OH)₆ octahedra at the edges of the octahedral layers of Fe(OH)₂. These multinuclear As(III) surface complexes are characterized by As-As pairs at a distance of 3.32 ± 0.02 Å and by As-Fe pairs at a distance of 3.50 ± 0.02 Å and represent a new type of As(III) surface complex. Chemical analyses show that the majority of As(III) produced in the experiments with As present is associated with iron-bearing hydroxycarbonate or hydroxide solids, reinforcing the idea that, at least under some circumstances, bacterial reduction can promote As(III) sequestration instead of mobilizing it into solution.     

Schwertmannite transformation to goethite via the Fe(II) pathway: Reaction rates and implications for iron-sulfide formation

Schwertmannite (Fe₈O₈(OH)₆SO₄) is a common Fe(III)-oxyhydroxysulfate mineral in acid-sulfate systems, where its formation and fate strongly influence water quality. The present study examines transformation of schwertmannite to goethite (FeOOH), as catalyzed by interactions with Fe(II) in anoxic aquatic environments. This study also evaluates the role of the Fe(II) pathway in influencing the formation of iron-sulfide minerals in such environments. At pH > 5, the rates of Fe(II)-catalyzed schwertmannite transformation were several orders of magnitude faster than transformation in the absence of Fe(II). Complete transformation of schwertmannite occurred within only 3-5 h at pH > 6 and Fe(II)_(aq) ? 5 mmol L⁻¹. Model calculations indicate that the Fe(II)-catalyzed transformation of schwertmannite to goethite greatly decreases the reactivity of the Fe(III) pool, thereby favoring SO₄-reduction and facilitating the formation of iron-sulfide minerals (particularly mackinawite, tetragonal FeS). Examination of in situ sediment geochemistry in an acid-sulfate system revealed that the rapid Fe(II)-catalyzed transformation was consistent with an abrupt shift from an acidic Fe(III)-reducing regime with abundant schwertmannite near the sediment surface, to a near-neutral mackinawite-forming regime where goethite was dominant. This study demonstrates that the Fe(II) pathway exerts a major influence on schwertmannite transformation and iron-sulfide formation in anoxic acid-sulfate systems. These findings have important implications for understanding acidity dynamics and trace element mobility in such systems.     

The mechanisms of reduction of hexavalent chromium by green rust sodium sulphate: Formation of Cr-goethite

The molecular-level processes that control green rust sodium sulphate (GR_Na,SO4) reaction with chromate were studied using high-resolution techniques. Changes in solid morphology, structure and composition were observed with atomic force microscopy, transmission electron microscopy and X-ray diffraction. The results suggest the following mechanisms: Chromate replaces sulphate in the GR interlayer and is reduced by Fe(II). Formation of sparingly soluble Cr(III)-solid blocks further chromate entry, but Cr(VI) reduction continues at the GR solid/solution interface. Electron transfer from the centre of the GR crystals to the surface facilitates rapid reaction. Less stable zones of the reacted GR_Na,SO4 dissolve and amorphous Cr(III),Fe(III)-solid forms. During equilibration, Cr-substituted goethite evolves in association with remaining GR_Na,SO4, fed by material from the amorphous phase and dissolving oxidised GR. In contrast, previous Cr(VI) experiments with the carbonate form of GR, GR_CO3, have suggested only reaction and deposition at the surface. From the perspective of environmental protection, these results have important implications. Goethite is sparingly soluble and the inclusion of Cr(III) as a solid-solution makes it even less soluble. Compared to Cr adsorbed at the surface of an Fe(III)-phase, Cr(III) incorporated in goethite is much less likely to be released back to groundwater.     

Reduction of pertechnetate [Tc(VII)] by aqueous Fe(II) and the nature of solid phase redox products

The subsurface behaviour of ⁹⁹Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)_(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10⁻⁹ atm O₂). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)_(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. ⁵⁷Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)_aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O₂·nH₂O_(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O₂·nH₂O_(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit ⁹⁹Tc remobilization upon the return of oxidizing conditions.     

Reversible surface-sorption-induced electron-transfer oxidation of Fe(II) at reactive sites on a synthetic clay mineral

The sorption of ⁵⁷Fe(II) onto an Fe-free, mineralogically pure and Ca-saturated synthetic montmorillonite sample (structural formula: Ca_0.15(Al_1.4Mg_0.6)(Si₄)O₁₀(OH,F)₂), was studied as a function of pH under strictly anoxic conditions (N₂ glove box atmosphere, O₂ content <1 ppm), using wet chemistry and cryogenic (T = 77 K) ⁵⁷Fe Mössbauer spectrometry. No Fe(III) was detected in solution at any pH. However, in pH conditions where Fe(II) is removed from solution, a significant amount of surface-bound Fe(III) was produced, which increased with pH from 0% to 3% of total Fe in a pre-sorption edge region (i.e. at pH < 7.5 where about 15% of total Fe is sorbed) to 7% of total Fe when all Fe is sorbed. At low pH, where the pre-sorption edge plateau occurs (2 < pH < 7.5), the total sorbed-Fe amount remained constant but, within this sorbed-Fe pool, the Fe(III)/Fe(II) ratio increased with pH, from 0.14 at pH 2 up to 0.74 at pH 7. The pre-sorption edge plateau is interpreted as cation exchange on interlayer surfaces together with a sorption phenomenon occurring on highly reactive (i.e. high affinity) surface sites. As pH increases and protons are removed from the clay edge surface, we propose that more and more of these highly reactive sites acquire a steric configuration that stabilizes Fe(III) relative to Fe(II), thereby inducing a Fe to clay particle electron transfer. A sorption model based on cation exchange combined with surface complexation and electron transfers reproduces both wet chemical as well as the Mössbauer spectrometric results. The mechanism is fully reversible: sorbed-Fe is reduced as pH decreases (Mössbauer solid-state analyses) and all Fe returned to solution is returned as Fe(II) (solution analyses). This would not be the case if the observed oxidations were due to contaminant oxidizing agents in solution. The present work shows that alternating pH may induce surface redox phenomena in the absence of an electron acceptor in solution other than H₂O.     

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

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

Fe(II) adsorption on hematite (0 0 0 1)

The surface structure of α-Fe₂O₃(0 0 0 1) was studied using crystal truncation rod (CTR) X-ray diffraction before and after reaction with aqueous Fe(II) at pH 5. The CTR results show the unreacted α-Fe₂O₃(0 0 0 1) surface consists of two chemically distinct structural domains: an O-layer terminated domain and a hydroxylated Fe-layer terminated domain. After exposing the α-Fe₂O₃(0 0 0 1) surface to aqueous Fe(II), the surface structure of both co-existing structural domains was modified due to adsorption of Fe at crystallographic lattice sites of the substrate, resulting in six-coordinated adsorbed Fe at the surface. The average Fe-O bond lengths of the adsorbed Fe are consistent with typical Fe(III)-O bond lengths (in octahedral coordination), providing evidence for the oxidation of Fe(II) to Fe(III) upon adsorption. These results highlight the important role of substrate surface structure in controlling Fe(II) adsorption. Furthermore, the molecular scale structural characterization of adsorbed Fe provides insight into the process of Fe(II) induced structural modification of hematite surfaces, which in turn aids in assessing the effective reactivity of hematite surfaces in Fe(II) rich environments.     

Enhancement and inhibition of iron photoreduction by individual ligands in open ocean seawater

In laboratory experiments, we investigated the effect of five individual Fe-binding ligands: phaeophytin, ferrichrome, desferrioxamine B (DFOB), inositol hexaphosphate (phytic acid), and protoporphyrin IX (PPIX) on the Fe(II) photoproduction using seawater of the open Southern Ocean. Addition of 10-100 nM Fe(III) to open Southern Ocean seawater without the model ligands and containing; 1.1 nM dissolved Fe(III), 1.75 ± 0.28 equivalents of nM Fe of natural ligands with a conditional stability constant (log K′) of 21.75 ± 0.34 and a concentration DOC of 86.8 ± 1.13 μM C leads to the formation of amorphous Fe(III) hydroxides. These amorphous Fe(III) hydroxides are the major source for the photoproduction of Fe(II). The addition of the model ligands changed the Fe(II) photoproduction considerably and in various ways. Phaeophytin showed higher Fe(II) photoproduction than ferrichrome and the control, i.e., amorphous Fe(III) hydroxides. Additions of phytic acid between 65 and 105 nM increased the concentration of photoproduced Fe(II) with 0.16 nM Fe(II) per nM phytic acid, presumably due to the co-aggregation of Fe(III) and phytic acid leading via an increasing colloidal surface to an increasing photoreducible Fe(III) fraction. DFOB and PPIX strongly decreased the photoproduced Fe(II) concentration. The low Fe(II) photoproduction with DFOB confirmed reported observations that Fe(III) complexed to DFOB is photo-stable. The PPIX hardly binds Fe(III) in the open Southern Ocean seawater but decreased the photoproduced Fe(II) concentration by complexing the Fe(II) with a binding rate constant of k_Fe(II)PPIX = 1.04 × 10⁻⁴ ± 1.53 × 10⁻⁵ s⁻¹ nM⁻¹ PPIX. Subsequently, PPIX is suggested to act as a photosensitizing producer of superoxide, thus increasing the dark reduction of Fe(III) to Fe(II). Our research shows that the photochemistry of Fe(III) and the resulting photoproduced Fe(II) concentration is strongly depending on the identity of the Fe-binding organic ligands and that a translation to natural conditions is not possible without further characterization of the natural occurring ligands.     

Experimental study of germanium adsorption on goethite and germanium coprecipitation with iron hydroxide: X-ray absorption fine structure and macroscopic characterization

Adsorption of germanium on goethite was studied at 25 °C in batch reactors as a function of pH (1-12), germanium concentration in solution (10⁻⁷ to 0.002 M) and solid/solution ratio (1.8-17 g/L). The maximal surface site density determined via Ge adsorption experiments at pH from 6 to 10 is equal to 2.5 ± 0.1 μmol/m². The percentage of adsorbed Ge increases with pH at pH < 9, reaches a maximum at pH ∼ 9 and slightly decreases when pH is further increased to 11. These results allowed generation of a 2-pK Surface Complexation Model (SCM) which implies a constant capacitance of the electric double layer and postulates the presence of two Ge complexes, and , at the goethite-solution interface. Coprecipitation of Ge with iron oxy(hydr)oxides formed during Fe(II) oxidation by atmospheric oxygen or by Fe(III) hydrolysis in neutral solutions led to high Ge incorporations in solid with maximal Ge/Fe molar ratio close to 0.5. The molar Ge/Fe ratio in precipitated solid is proportional to that in the initial solution according to the equation (Ge/Fe)_solid = k × (Ge/Fe)_solution with 0.7 ? k ? 1.0. The structure of adsorbed and coprecipitated Ge complexes was further characterized using XAFS spectroscopy. In agreement with previous data on oxyanions adsorption on goethite, bi-dentate bi-nuclear surface complexes composed of tetrahedrally coordinated Ge attached to the corners of two adjacent Fe octahedra represent the dominant contribution to the EXAFS signal. Coprecipitated samples with Ge/Fe molar ratios >0.1, and samples not aged in solution (<1 day) having intermediate Ge/Fe ratios (0.01-0.1) show 4 ± 0.3 oxygen atoms at 1.76 ± 0.01 Å around Ge. Samples less concentrated in Ge (0.001 < Ge/Fe < 0.10) and aged longer times in solution (up to 280 days) exhibit a splitting of the first atomic shell with Ge in both tetrahedral (R = 1.77 ± 0.02 Å) and octahedral (R = 1.92 ± 0.03 Å) coordination with oxygen. In these samples, octahedrally coordinated Ge accounts for up to ∼20% of the total Ge. For the least concentrated samples (Ge/Fe < 0.001-0.0001) containing lepidocrocite, 30-50% of total co-precipitated germanium substitutes for Fe in octahedral sites with the next-nearest environment dominated by edge-sharing GeO₆-FeO₆ linkages (R_Ge-Fe ∼ 3.06 Å). It follows from the results of our study that the largest structural change of Ge (from tetrahedral to octahedral environment) occurs during its coprecipitation with Fe hydroxide at Ge/Fe molar ratio ?0.0001. These conditions are likely to be met in many superficial aquatic environments at the contact of anoxic groundwaters with surficial oxygenated solutions. Adsorption and coprecipitation of Ge with solid Fe oxy(hydr)oxides and organo-mineral colloids and its consequence for Ge/Si fractionation and Ge geochemical cycle are discussed.     

Arsenite sorption at the magnetite-water interface during aqueous precipitation of magnetite: EXAFS evidence for a new arsenite surface complex

The interaction of aqueous As(III) with magnetite during its precipitation from aqueous solution at neutral pH has been studied as a function of initial As/Fe ratio. Arsenite is sequestered via surface adsorption and surface precipitation reactions, which in turn influence the crystal growth of magnetite. Sorption samples were characterized using EXAFS spectroscopy at the As K-edge in combination with HRTEM observations, energy dispersive X-ray analysis at the nanoscale, electron energy loss spectroscopy at the Fe L₃-edge, and XRD-Rietveld analyses of reaction products. Our results show that As(III) forms predominantly tridentate hexanuclear As(III)O₃ complexes (³C), where the As(III)O₃ pyramids occupy vacant tetrahedral sites on {1 1 1} surfaces of magnetite particles. This is the first time such a tridentate surface complex has been observed for arsenic. This complex, with a dominant As-Fe distance of 3.53 ± 0.02 Å, occurs in all samples examined except the one with the highest As/Fe ratio (0.33). In addition, at the two highest As/Fe ratios (0.133 and 0.333) arsenite tends to form mononuclear edge-sharing As(III)O₃ species (²E) within a highly soluble amorphous As(III)-Fe(III,II)-containing precipitate. At the two lowest As/Fe ratios (0.007 and 0.033), our results indicate the presence of additional As(III) species with a dominant As-Fe distance of 3.30 ± 0.02 Å, for which a possible structural model is proposed. The tridentate ³C As(III)O₃ complexes on the {1 1 1} magnetite surface, together with this additional As(III) species, dramatically lower the solubility of arsenite in the anoxic model systems studied. They may thus play an important role in lowering arsenite solubility in putative magnetite-based water treatment processes, as well as in natural iron-rich anoxic media, especially during the reductive dissolution-precipitation of iron minerals in anoxic environments.     

Transformations of mercury, iron, and sulfur during the reductive dissolution of iron oxyhydroxide by sulfide

Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS⁻) was added at 40 to 250 μM h⁻¹ to 5 g L⁻¹ goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m⁻²) at pH 7.5. Dissolved Hg initially decreased from 10³ or 10⁴ nM (depending on initial conditions) to 10⁻¹ nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS_(s)) formed, based on identification using Hg L_III-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS_(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g⁻¹) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS_(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.     

Speciation and thermodynamic properties for cobalt chloride complexes in hydrothermal fluids at 35-440 °C and 600 bar: An in-situ XAS study

Aqueous Co(II) chloride complexes play a crucial role in cobalt transport and deposition in ore-forming hydrothermal systems, ore processing plants, and in the corrosion of special Co-bearing alloys. Reactive transport modelling of cobalt in hydrothermal fluids relies on the availability of thermodynamic properties for Co complexes over a wide range of temperature, pressure and salinity. Synchrotron X-ray absorption spectroscopy was used to determine the speciation of cobalt(II) in 0-6 m chloride solutions at temperatures between 35 and 440 °C at a constant pressure of 600 bar. Qualitative analysis of XANES spectra shows that octahedral species predominate in solution at 35 °C, while tetrahedral species become increasingly important with increasing temperature. Ab initio XANES calculations and EXAFS analyses suggest that in high temperature solutions the main species at high salinity (Cl:Co >> 2) is CoCl₄²⁻, while a lower order tetrahedral complex, most likely CoCl₂(H₂O)_2(aq), predominates at low salinity (Cl:Co ratios ∼2). EXAFS analyses further revealed the bonding distances for the octahedral Co(H₂O)₆²⁺ (^octCo-O = 2.075(19) Å), tetrahedral CoCl₄²⁻ (^tetCo-Cl = 2.252(19) Å) and tetrahedral CoCl₂(H₂O)_2(aq) (^tetCo-O = 2.038(54) Å and ^tetCo-Cl = 2.210(56) Å). An analysis of the Co(II) speciation in sodium bromide solutions shows a similar trend, with tetrahedral bromide complexes becoming predominant at higher temperature/salinity than in the chloride system. EXAFS analysis confirms that the limiting complex at high bromide concentration at high temperature is CoBr₄²⁻. Finally, XANES spectra were used to derive the thermodynamic properties for the CoCl₄²⁻ and CoCl₂(H₂O)_2(aq) complexes, enabling thermodynamic modelling of cobalt transport in hydrothermal fluids. Solubility calculations show that tetrahedral CoCl₄²⁻ is responsible for transport of cobalt in hydrothermal solutions with moderate chloride concentration (∼2 m NaCl) at temperatures of 250 °C and higher, and both cooling and dilution processes can cause deposition of cobalt from hydrothermal fluids.     

Gitterkonstanten und Raumgruppe von Rhomboklas,FeH(SO4)2.4H2O

Zusammenfassung Rhomboklas, FeH(SO₄)₂.4H₂O, wurde aus einer mit Salpetersäure oxidierten, schwefelsauren, wäßrigen Eisen(II)-sulfatlösung hergestellt. Die Be stimmung der Gitterkonstanten ergab: a₀=9,78₅ Å, b₀=18,36₃ Å, c₀=5,43₁ Å; Raumgruppe: P nma oder P n2a, Z=4.

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Lattice constants and space-group of rhomboclase, FeH(SO₄)₂.4H₂O

Summary Rhomboclase, FeH(SO₄)₂.4H₂O was precipitated from a solution of ferrous sulphate in water by oxydation with HNO₃ and the addition of excess H₂SO₄. The lattice constants are a₀=9.78₅ Å, b₀=18.36₃ Å, c₀=5.43₁ Å; space-group P nma or P n2a, Z=4.

     

Role of Fe(II) and phosphate in arsenic uptake by coprecipitation

Natural attenuation of arsenic by simple adsorption on oxyhydroxides may be limited due to competing oxyanions, but uptake by coprecipitation may locally sequester arsenic. We have systematically investigated the mechanism and mode (adsorption versus coprecipitation) of arsenic uptake in the presence of carbonate and phosphate, from solutions of inorganic composition similar to many groundwaters. Efficient arsenic removal, >95% As(V) and ∼55% in initial As(III) systems, occurred over 24 h at pHs 5.5-6.5 when Fe(II) and hydroxylapatite (Ca₅(PO₄)₃OH, HAP) “seed” crystals were added to solutions that had been previously reacted with HAP, atmospheric CO_2(g) and O_2(g). Arsenic adsorption was insignificant (<10%) on HAP without Fe(II). Greater uptake in the As(III) system in the presence of Fe(II) was interpreted as due to faster As(III) to As(V) oxidation by molecular oxygen in a putative pathway involving Fe(IV) and As(IV) intermediate species. HAP acts as a pH buffer that allows faster Fe(II) oxidation. Solution analyses coupled with high-resolution transmission electron microscopy (HRTEM), X-ray Energy-Dispersive Spectroscopy (EDS), and X-Ray Absorption Spectroscopy (XAS) indicated the precipitation of sub-spherical particles of an amorphous, chemically-mixed, nanophase, Fe^III[(OH)₃(PO₄)(As^VO₄)]·nH₂O or Fe^III[(OH)₃( PO₄)(As^VO₄)(As^IIIO₃)_minor]·nH₂O, where As^IIIO₃ is a minor component.The mode of As uptake was further investigated in binary coprecipitation (Fe(II) + As(III) or P), and ternary coprecipitation and adsorption experiments (Fe(II) + As(III) + P) at variable As/Fe, P/Fe and As/P/Fe ratios. Foil-like, poorly crystalline, nanoparticles of Fe^III(OH)₃ and sub-spherical, amorphous, chemically-mixed, metastable nanoparticles of Fe^III[(OH)₃, PO₄]·nH₂O coexisted at lower P/Fe ratios than predicted by bulk solubilities of strengite (FePO₄·2H₂O) and goethite (FeOOH). Uptake of As and P in these systems decreased as binary coprecipitation > ternary coprecipitation > ternary adsorption.Significantly, the chemically-mixed, ferric oxyhydroxide-phosphate-arsenate nanophases found here are very similar to those found in the natural environment at slightly acidic to circum-neutral pHs in sub-oxic to oxic systems, such phases may naturally attenuate As mobility in the environment, but it is important to recognize that our system and the natural environment are kinetically evolving, and the ultimate environmental fate of As will depend on the long-term stability and potential phase transformations of these mixed nanophases. Our results also underscore the importance of using sufficiently complex, yet systematically designed, model systems to accurately represent the natural environment.     

Structural characterization of poorly-crystalline scorodite, iron(III)-arsenate co-precipitates and uranium mill neutralized raffinate solids using X-ray absorption fine structure spectroscopy

X-ray absorption fine structure (XAFS) is used to characterize the mineralogy of the iron(III)-arsenate(V) precipitates produced during the raffinate (aqueous effluent) neutralization process at the McClean Lake uranium mill in northern Saskatchewan, Canada. To facilitate the structural characterization of the precipitated solids derived from the neutralized raffinate, a set of reference compounds were synthesized and analyzed. The reference compounds include crystalline scorodite, poorly-crystalline scorodite, iron(III)-arsenate co-precipitates obtained under different pH conditions, and arsenate-adsorbed on goethite. The poorly-crystalline scorodite (prepared at pH 4 with Fe/As = 1) has similar As local structure as that of crystalline scorodite. Both As and Fe K-edge XAFS of poorly-crystalline scorodite yield consistent results on As-Fe (or Fe-As) shell. From As K-edge analysis the As-Fe shell has an inter-atomic distance of 3.33 ± 0.02 Å and coordination number of 3.2; while from Fe K-edge analysis the Fe-As distance and coordination number are 3.31 ± 0.02 Å and 3.8, respectively. These are in contrast with the typical arsenate adsorption on bidentate binuclear sites on goethite surfaces, where the As-Fe distance is 3.26 ± 0.03 Å and coordination number is close to 2. A similar local structure identified in the poorly-crystalline scorodite is also found in co-precipitation solids (Fe(III)/As(V) = 3) when precipitated at the same pH (pH = 4): As-Fe distance 3.30 ± 0.03 Å and coordination number 3.9; while at pH = 8 the co-precipitate has As-Fe distance of 3.27 ± 0.03 Å and coordination number about 2, resembling more closely the adsorption case. The As local structure in the two neutralized raffinate solid series (precipitated at pH values up to 7) closely resembles that in the poorly-crystalline scorodite. All of the raffinate solids have the same As-Fe inter-atomic distance as that in the poorly-crystalline scorodite, and a systematic decrease in the As-Fe coordination is observed when pH is progressively increased; the basic poorly-crystalline scorodite structural feature remains in the raffinate solid up to pH 7.     

Reductive biotransformation of Fe in shale-limestone saprolite containing Fe(III) oxides and Fe(II)/Fe(III) phyllosilicates

A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)_TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)_TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe²⁺, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)₂, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.     

Sorption and catalytic oxidation of Fe(II) at the surface of calcite

The effect of sorption and coprecipitation of Fe(II) with calcite on the kinetics of Fe(II) oxidation was investigated. The interaction of Fe(II) with calcite was studied experimentally in the absence and presence of oxygen. The sorption of Fe(II) on calcite occurred in two distinguishable steps: (a) a rapid adsorption step (seconds-minutes) was followed by (b) a slower incorporation (hours-weeks). The incorporated Fe(II) could not be remobilized by a strong complexing agent (phenanthroline or ferrozine) but the dissolution of the outmost calcite layers with carbonic acid allowed its recovery. Based on results of the latter dissolution experiments, a stoichiometry of 0.4 mol% Fe:Ca and a mixed carbonate layer thickness of 25 nm (after 168 h equilibration) were estimated. Fe(II) sorption on calcite could be successfully described by a surface adsorption and precipitation model (Comans & Middelburg, GCA51 (1987), 2587) and surface complexation modeling (Van Cappellen et al., GCA57 (1993), 3505; Pokrovsky et al., Langmuir16 (2000), 2677). The surface complex model required the consideration of two adsorbed Fe(II) surface species, >CO₃Fe⁺ and >CO₃FeCO₃H⁰. For the formation of the latter species, a stability constant is being suggested. The oxidation kinetics of Fe(II) in the presence of calcite depended on the equilibration time of aqueous Fe(II) with the mineral prior to the introduction of oxygen. If pre-equilibrated for >15 h, the oxidation kinetics was comparable to a calcite-free system (t_1/2 = 145 ± 15 min). Conversely, if Fe(II) was added to an aerated calcite suspension, the rate of oxidation was higher than in the absence of calcite (t_1/2 = 41 ± 1 min and t_1/2 = 100 ± 15 min, respectively). This catalysis was due to the greater reactivity of the adsorbed Fe(II) species, >CO₃FeCO₃H⁰, for which the species specific rate constant was estimated.     

Iron isotope fractionation during microbially stimulated Fe(II) oxidation and Fe(III) precipitation

Interpretation of the origins of iron-bearing minerals preserved in modern and ancient rocks based on measured iron isotope ratios depends on our ability to distinguish between biological and non-biological iron isotope fractionation processes. In this study, we compared ⁵⁶Fe/⁵⁴Fe ratios of coexisting aqueous iron (Fe(II)_aq, Fe(III)_aq) and iron oxyhydroxide precipitates (Fe(III)_ppt) resulting from the oxidation of ferrous iron under experimental conditions at low pH (<3). Experiments were carried out using both pure cultures of Acidothiobacillus ferrooxidans and sterile controls to assess possible biological overprinting of non-biological fractionation, and both SO₄²⁻ and Cl⁻ salts as Fe(II) sources to determine possible ionic/speciation effects that may be associated with oxidation/precipitation reactions. In addition, a series of ferric iron precipitation experiments were performed at pH ranging from 1.9 to 3.5 to determine if different precipitation rates cause differences in the isotopic composition of the iron oxyhydroxides. During microbially stimulated Fe(II) oxidation in both the sulfate and chloride systems, ⁵⁶Fe/⁵⁴Fe ratios of residual Fe(II)_aq sampled in a time series evolved along an apparent Rayleigh trend characterized by a fractionation factor α_{Fe(III)aq-Fe(II)aq} ∼ 1.0022. This fractionation factor was significantly less than that measured in our sterile control experiments (∼1.0034) and that predicted for isotopic equilibrium between Fe(II)_aq and Fe(III)_aq (∼1.0029), and thus might be interpreted to reflect a biological isotope effect. However, in our biological experiments the measured difference in ⁵⁶Fe/⁵⁴Fe ratios between Fe(III)_aq, isolated as a solid by the addition of NaOH to the final solution at each time point under N₂-atmosphere, and Fe(II)_aq was in most cases and on average close to 2.9‰ (α_{Fe(III)aq-Fe(II)aq} ∼ 1.0029), consistent with isotopic equilibrium between Fe(II)_aq and Fe(III)_aq. The ferric iron precipitation experiments revealed that ⁵⁶Fe/⁵⁴Fe ratios of Fe(III)_aq were generally equal to or greater than those of Fe(III)_ppt, and isotopic fractionation between these phases decreased with increasing precipitation rate and decreasing grain size. Considered together, the data confirm that the iron isotope variations observed in our microbial experiments are primarily controlled by non-biological equilibrium and kinetic factors, a result that aids our ability to interpret present-day iron cycling processes but further complicates our ability to use iron isotopes alone to identify biological processing in the rock record.     

Geochemistry of an acidic chromium sulfate plume

The historical disposal of acidic chromium sulfate solutions into unlined lagoons between 1953 and 1970 at an industrial site resulted in formation of a dense aqueous phase liquid (DAPL) plume [specific gravity 1.11 g/cm³, pH 3, up to 4700 mg/L Cr(III), and up to 90,000 mg/L SO₄]. The DAPL sank through the shallow glacial till aquifer to an underlying impermeable gneissic bedrock from where it migrated downgradient along buried channels incised in the bedrock. Because of its high density, the plume chemistry is sharply stratified vertically. Chromium(III) predominates in the DAPL because excess Cr(VI) not reduced in the original process has been reduced by Fe(II) derived from silicates, while Cr(OH)₃(am) occurs as surface coatings on silicate minerals and as discrete particles mixed with Fe(OH)₃(am) and Al(OH)₃(am). The solubility of Cr(OH)₃(am) accurately describes Cr(III) concentrations in the plume and nearby groundwater, while Al and Fe in solution are also consistent with solubility-controlling oxyhydroxides. Because of these solubility controls, metal cations are attenuated relative to more mobile Cl and SO₄, resulting in a chromatographic separation of solutes downgradient from the plume origin. The good agreement between predicted and observed solution concentrations illustrates the utility of equilibrium modeling when interpreting metal transport characteristics and in determining the efficacy of natural attenuation in subsurface systems.     

Arsenic repartitioning during biogenic sulfidization and transformation of ferrihydrite

Iron (hydr)oxides are strong sorbents of arsenic (As) that undergo reductive dissolution and transformation upon reaction with dissolved sulfide. Here we examine the transformation and dissolution of As-bearing ferrihydrite and subsequent As repartitioning amongst secondary phases during biotic sulfate reduction. Columns initially containing As(V)-ferrihydrite coated sand, inoculated with the sulfate reducing bacteria Desulfovibrio vulgaris (Hildenborough), were eluted with artificial groundwater containing sulfate and lactate. Rapid and consistent sulfate reduction coupled with lactate oxidation is observed at low As(V) loading (10% of the adsorption maximum). The dominant Fe solid phase transformation products at low As loading include amorphous FeS within the zone of sulfate reduction (near the inlet of the column) and magnetite downstream where Fe(II)_(aq) concentrations increase; As is displaced from the zone of sulfidogenesis and Fe(III)_(s) depletion. At high As(V) loading (50% of the adsorption maximum), sulfate reduction and lactate oxidation are initially slow but gradually increase over time, and all As(V) is reduced to As(III) by the end of experimentation. With the higher As loading, green rust(s), as opposed to magnetite, is a dominant Fe solid phase product. Independent of loading, As is strongly associated with magnetite and residual ferrihydrite, while being excluded from green rust and iron sulfide. Our observations illustrate that sulfidogenesis occurring in proximity with Fe (hydr)oxides induce Fe solid phase transformation and changes in As partitioning; formation of As sulfide minerals, in particular, is inhibited by reactive Fe(III) or Fe(II) either through sulfide oxidation or complexation.