Heterogeneous Fe(II) oxidation and zeta potential

The determination of electrophoretic mobility and zeta potential was used as a diagnostic tool, alongside kinetic experiments, to delineate between three plausible mechanisms for the heterogeneous oxidation of Fe(II) by dissolved oxygen. One of these mechanisms is dependant on the positive surface charge that exists on Fe(III) (oxy)hydroxide surfaces at pH values below the Iso-Electric Point (IEP). However, this mechanism can be disputed as catalysis is observed on Fe(III) (oxy)hydroxide surfaces above the IEP despite a negative zeta potential. As well as an IEP shift an overall reduction of the magnitude of the zeta potential is observed in samples of field Fe(III) (oxy)hydroxide collected from the Taff Merthyr mine water treatment site in South Wales, UK. Low zeta potentials determined in mine water treatment systems will have beneficial effects for particle coagulation and settling in passive mine water treatment systems.     

Biogeochemistry of Fe(II) oxidation in a photosynthetic microbial mat: Implications for Precambrian Fe(II) oxidation

We studied the role of microbial photosynthesis in the oxidation of Fe(II) to Fe(III) in a high Fe(II) and high Mn(II) hot spring devoid of sulfide and atmospheric oxygen in the source waters. In situ light and dark microelectrode measurements of Fe(II), Mn(II) and O₂ were made in the microbial mat consisting of cyanobacteria and anoxygenic photosynthetic Chloroflexus sp. We show that Fe(II) oxidation occurred when the mat was exposed to varying intensities of sunlight but not near infrared light. We did not observe any Mn(II) oxidation under any light or dark condition over the pH range 5-7. We observed the impact of oxygenic photosynthesis on Fe(II) oxidation, distinct from the influence of atmospheric O₂ and anoxygenic photosynthesis. In situ Fe(II) oxidation rates in the mats and cell suspensions exposed to light are consistent with abiotic oxidation by O₂. The oxidation of Fe(II) to form primary Fe(III) phases contributed to banded iron-formations (BIFs) during the Precambrian. Both oxygenic photosynthesis, which produces O₂ as an oxidizing waste product, and anoxygenic photosynthesis in which Fe(II) is used to fix CO₂ have been proposed as Fe(II) oxidation mechanisms. Although we do not know the specific mechanisms responsible for all Precambrian Fe(II) oxidation, we assessed the relative importance of both mechanisms in this modern hot spring environment. In this environment, cyanobacterial oxygen production accounted for all the observed Fe(II) oxidation. The rate data indicate that a modest population of cyanobacteria could have mediated sufficient Fe(II) oxidation for some BIFs.     

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.     

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

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

Superoxide-mediated Fe(II) formation from organically complexed Fe(III) in coastal waters

Fe(III) complexed by organic ligands (Fe(III)L) is the primary form of dissolved Fe in marine and coastal environments. Superoxide, typically produced in biological and photochemical processes, is one of the reducing agents that contributes to transformation of Fe(III)L to bioavailable, free dissolved Fe(II) (Fe(II)′). In this work, the kinetics of superoxide-mediated Fe(II)′ formation from Fe(III)L in a simulated coastal water system were investigated and a comprehensive kinetic model was developed using citrate and fulvic acid as exemplar Fe-binding ligands. To simulate a coastal environment in laboratory experiments, Fe(III)L samples with various ligand/Fe ratios were incubated for 5 min to 1 week in seawater medium. At each ratio and incubation time, the rate of superoxide-mediated Fe(II)′ formation was determined in the presence of the strong Fe(II) binding ligand ferrozine by spectrophotometrically measuring the ferrous-ferrozine complex generated at a constant concentration of superoxide. The Fe(II)′ formation rate generally decreased with incubation time, as Fe(III)L gradually dissociated to form less reactive Fe(III) oxyhydroxide. However, when the ligand/Fe ratio was sufficiently high, the dissociation of Fe(III)L (and subsequent Fe precipitation) was suppressed and Fe(II)′ was formed at a higher rate. The rate of Fe(II)′ produced during the experiment was explained by the kinetic model. The model confirmed that both the ligand/Fe ratio and incubation time have a significant effect on the pathway via which Fe(II)′ is formed from Fe(III)-fulvic acid complexes.     

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.     

Kinetic and equilibrium Fe isotope fractionation between aqueous Fe(II) and Fe(III)

Equilibrium and kinetic Fe isotope fractionation between aqueous ferrous and ferric species measured over a range of chloride concentrations (0, 11, 110 mM Cl⁻) and at two temperatures (0 and 22°C) indicate that Fe isotope fractionation is a function of temperature, but independent of chloride contents over the range studied. Using ⁵⁷Fe-enriched tracer experiments the kinetics of isotopic exchange can be fit by a second-order rate equation, or a first-order equation with respect to both ferrous and ferric iron. The exchange is rapid at 22°C, ∼60-80% complete within 5 seconds, whereas at 0°C, exchange rates are about an order of magnitude slower. Isotopic exchange rates vary with chloride contents, where ferrous-ferric isotope exchange rates were ∼25 to 40% slower in the 11 mM HCl solution compared to the 0 mM Cl⁻ (∼10 mM HNO₃) solutions; isotope exchange rates are comparable in the 0 and 110 mM Cl⁻ solutions.The average measured equilibrium isotope fractionations, Δ_{Fe(III)-Fe(II)}, in 0, 11, and 111 mM Cl⁻ solutions at 22°C are identical within experimental error at +2.76±0.09, +2.87±0.22, and +2.76±0.06 ‰, respectively. This is very similar to the value measured by Johnson et al. (2002a) in dilute HCl solutions. At 0°C, the average measured Δ_{Fe(III)-Fe(II)} fractionations are +3.25±0.38, +3.51±0.14 and +3.56±0.16 ‰ for 0, 11, and 111 mM Cl⁻ solutions. Assessment of the effects of partial re-equilibration on isotope fractionation during species separation suggests that the measured isotope fractionations are on average too low by ∼0.20 ‰ and ∼0.13 ‰ for the 22°C and 0°C experiments, respectively. Using corrected fractionation factors, we can define the temperature dependence of the isotope fractionation from 0°C to 22°C as: where the isotopic fractionation is independent of Cl⁻ contents over the range used in these experiments. These results confirm that the Fe(III)-Fe(II) fractionation is approximately half that predicted from spectroscopic data, and suggests that, at least in moderate Cl⁻ contents, the isotopic fractionation is relatively insensitive to Fe-Cl speciation.     

Relative contributions of abiotic and biological factors in Fe(II) oxidation in mine drainage

The oxidation of Fe(II) is apparently the rate-limiting step in passive treatment of coal mine drainage. Little work has been done to determine the kinetics of oxidation in such field systems, and no models of passive treatment systems explicitly consider iron oxidation kinetics. A Stella II^™ model using Fe(II)_init concentration, pH, temperature, Thiobacillus ferrooxidans and O₂ concentration, flow rate, and pond volume is used to predict Fe(II) oxidation rates and concentrations in seventeen ponds under a wide range of conditions (pH 2.8 to 6.8 with Fe(II) concentrations of less than 240 mg L⁻¹) from 6 passive treatment facilities. The oxidation rate is modeled based on the combination of published abiotic and biological laboratory rate laws. Although many other variables have been observed to influence Fe(II) oxidation rates, the 7 variables above allow field systems to be modeled reasonably accurately for conditions in this study.Measured T. ferrooxidans concentrations were approximately 10⁷ times lower than concentrations required in the model to accurately predict field Fe(II) concentrations. This result suggests that either 1) the most probable number enumeration method underestimated the bacterial concentrations, or 2) the biological rate law employed underestimated the influence of bacteria, or both. Due to this discrepancy, bacterial concentrations used in the model for pH values of less than 5 are treated as fit parameters rather than empirically measured values.Predicted Fe(II) concentrations in ponds agree well with measured Fe(II) concentrations, and predicted oxidation rates also agree well with field-measured rates. From pH 2.8 to approximately pH 5, Fe(II) oxidation rates are negatively correlated with pH and catalyzed by T. ferrooxidans. From pH 5 to 6.4, Fe(II) oxidation appears to be primarily abiotic and is positively correlated with pH. Above pH 6.4, oxidation appears to be independent of pH. Above pH 5, treatment efficiency is affected most by changing design parameters in the following order: pH>temperature≈influent Fe(II)>pond volume≈O₂. Little to no increase in Fe(II) oxidation rate occurs due to pH increases above pH 6.4. Failure to consider Fe(II) oxidation rates in treatment system design may result in insufficient Fe removal.     

Fe(II) oxidation by Acidithiobacillus ferrooxidans in pure and mixed cultures in the presence of arsenate

Fe²⁺ oxidation by Acidithiobacillus ferrooxidans in pure and mixed cultures was investigated in batch cultures in the presence of arsenate. The pH value was periodically monitored and Fe²⁺ content was analyzed by the 1,10-phenanthroline method. ICP-AES was employed for the analysis of As(V) concentration in the solution phase. Precipitates were collected and analyzed by X-ray diffraction. Slight enhancement of iron bio-oxidation was observed in mixed cultures with the two greatest As(V) concentrations (1.0 and 5.0 mg/L As), which were enriched from sediment samples in an abandoned copper mine site. As(V) concentrations decreased with time, indicating either the co-precipitation with or the adsorption by jarosite, the major sink of solid phase. Our data suggest that biogenically synthesized jarosite may play an important role in the attenuation of soluble arsenate in natural aquatic environments.     

Nitrite reduction by Fe(II) associated with kaolinite

Interactions of iron (Fe) with the nitrogen (N) cycle have emerged and contain elements of abiotic and biological reactions. One such abiotic reaction which has received little study is the reactivity of NO₂ ^? and Fe(II) associated with a major clay mineral, kaolinite. The main objective of this study was to evaluate the reactivity of NO₂ ^? with Fe(II) added to kaolinite under anoxic conditions. Stirred batch reactivity experiments were carried out with 10 g L^?1 kaolinite spiked with 25 and 100 µM Fe(II) at pH 6.45 in an anaerobic chamber. Approximately 500 µM NO₂ ^? was added to initiate the reaction with Fe(II)-loaded kaolinite. The rate of nitrite removal from solution was 2.4-fold slower in the high Fe(II) treatment when compared with the low Fe(II) treatment. A large portion of the NO₂ ^? removed from solution was confirmed to be reduced to N₂O_(g) in the Fe(II)-kaolinite slurries. However, NO₂ ^? reduction was also noticed in the presence of kaolinite-alone and to somewhat lesser extent in the presence of dithionite-citrate-bicarbonate (DCB)-treated kaolinite. Chemical extractions coupled with infrared spectroscopy suggest that Fe(III) oxide mineral impurities and structural Fe(III) in kaolinite may participate in NO₂ ^? removal from solution. Furthermore, a magnetite mineral was identified based on X-ray diffraction analysis of untreated kaolinite and DCB-treated kaolinite. Our findings reveal a novel pathway of NO₂ ^? transformation in the environment in the presence of Fe(II) associated (sorbed and impurity) with kaolinite.     

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.     

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.     

Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions

Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)_aq - oxide interaction will produce low δ⁵⁶Fe values for Fe(II)_aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ⁵⁶Fe Fe(II)_aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ⁵⁶Fe aqueous Fe(II) in many natural systems.     

Abiotic reduction of uranium by Fe(II) in soil

Structural Fe(II) has been shown to reduce several oxidized environmental contaminants, including NO₃, chlorinated solvents, Cr(VI), and U(VI). Studies investigating reduction of U(VI) by soils and sediments, however, suggest that abiotic reduction of U(VI) by Fe(II) is not significant, and that direct enzymatic reduction of U(VI) by metal-reducing bacteria is required for U(VI) immobilization as U(IV). Here evidence is presented for abiotic reduction and immobilization of U(VI) by structural Fe(II) in a redoximorphic soil collected from a hillside spring in Iowa. Oxidation of Fe(II) in the soil after reaction with U(VI) was demonstrated by Mössbauer spectroscopy and reduction of U(VI) by the pasteurized soil using U L_III-edge X-ray absorption spectroscopy (XAS). XAS indicates that both reduced U(IV) and oxidized U(VI) or U(V) are present after U(VI) interaction with the Fe(II) containing soil. The EXAFS data show the presence of a non-uraninite U(IV) phase and evidence of the oxidized U(V) or U(VI) fraction being present as a non-uranyl species. Little U(VI) reduction is observed by soil that has been exposed to air and oxidation of Fe(II) to goethite has occurred. Soil characterization based on chemical extractions, Mössbauer spectroscopy, and Fe K-edge XAS indicate that the majority of Fe(II) in the soil is structural in nature, existing in clay minerals and possibly a green rust-like phase. These data provide compelling evidence for abiotic reduction of U(VI) by structural Fe(II) from soil near Fe-rich oxic–anoxic boundaries in natural environments. The work highlights the potential for abiotic reduction of U(VI) by Fe(II) in reduced, Fe-rich environments.     

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.     

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.     

Structure and oxidation state of hematite surfaces reacted with aqueous Fe(II) at acidic and neutral pH

Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m² on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange process appears to be a significant subsystem within macroscopic pH-dependent Fe(II) adsorption.     

Heterogeneous reduction of Tc(VII) by Fe(II) at the solid-water interface

Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ? structural Fe(II) in phyllosilicates ? Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO₂ monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with ⁵⁶Fe-goethite with adsorbed ⁵⁷Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.     

Natural attenuation of TCE, As, Hg linked to the heterogeneous oxidation of Fe(II): an AFM study

Hydrous ferric oxide (HFO) colloids formed, in strictly anoxic conditions upon oxidation of Fe²⁺ ions adsorbed on mineral surface, were investigated under in situ conditions by contact mode atomic force microscopy (AFM). Freshly cleaved and acid-etched large single crystals of near endmember phlogopite were pre-equilibrated with dissolved Fe(II) and then reacted with Hg(II), As(V) and trichlorethene (TCE)-bearing solutions at 25 °C and 1 atm. HFO structures are found to be of nanometer scale. The As(V)–Fe(II) and Hg(II)–Fe(II) reaction products are round (25 nm) microcrystallites located predominantly on the layer edges and are indicative of an accelerated Fe(II) oxidation rate upon formation of Fe(II) inner sphere surface complexes with the phyllosilicate edge surface sites. On the other hand, TCE–Fe(II)–phlogopite reaction products are needle-shaped (45 nm long) particles located on the basal plane along the Periodic Bond Chains (PCBs) directions. Experiments with additions of sodium chloride confirm the importance of the Fe(II) adsorption step in the control of the overall heterogeneous Fe(II)–TCE electron transfer reaction.

Kinetic measurements at the nanomolar level of Hg° formed upon reduction of Hg(II) by Fe(II) in presence of phlogopite particles provide further convincing evidence for reduction of Hg(II)_aq coupled to the oxidation of Fe(II) adsorbed at the phlogopite–fluid interface, and indicate that sorption of Fe(II) to mineral surfaces enhances the reduction rate of Hg(II) species. The Hg(II) reduction reaction follows a first-order kinetic law. Under our experimental conditions, which were representative of many natural systems, 80% of the mercury is transferred to the atmosphere as Hg° in less than 2 h.

The reduction of a heavy metal (Hg), a toxic oxyanion (arsenate ion) and a chlorinated solvent (TCE) thus appear to be driven by the high reactivity of adsorbed Fe(II). This is of environmental relevance since these three priority pollutants are that way reductively transformed to a volatile, an immobilizable and a biodegradable species, respectively. Such kinetic data and reaction pathways are important in the evaluation of natural evaluation scenarios, in the optimization of Fe(II)/mineral mixtures as reductants in technical systems, and in general, in predicting the fate and transport of pollutants in natural systems.