Redox Potentials of Magnetite Suspensions under Reducing Conditions.

Predicting the redox behavior of magnetite in reducing soils and sediments is challenging because there is neither agreement among measured potentials nor consensus on which Fe(III) | Fe(II) equilibria are most relevant. Here, we measured open-circuit potentials of stoichiometric magnetite equilibrated over a range of solution conditions. Notably, electron transfer mediators were not necessary to reach equilibrium. For conditions where ferrous hydroxide precipitation was limited, Nernstian behavior was observed with an EH vs pH slope of -179 ± 4 mV and an EH vs Fe(II)aq slope of -54 ± 4 mV. Our estimated EHo of 857 ± 8 mV closely matches a maghemite|aqueous Fe(II) EHo of 855 mV, suggesting that it plays a dominant role in poising the solution potential and that it's theoretical Nernst equation of EH[mV] = 855 - 177 pH - 59 log [Fe2+] may be useful in predicting magnetite redox behavior under these conditions. At higher pH values and without added Fe(II), a distinct shift in potentials was observed, indicating that the dominant Fe(III)|Fe(II) couple(s) poising the potential changed. Our findings, coupled with previous Mössbauer spectroscopy and kinetic data, provide compelling evidence that the maghemite/Fe(II)aq couple accurately predicts the redox behavior of stoichiometric magnetite suspensions in the presence of aqueous Fe(II) between pH values of 6.5 and 8.5.

Abiotic Degradation of Chlorinated Solvents by Clay Minerals and Fe(II): Evidence for Reactive Mineral Intermediates.

For decades, there has been evidence that Fe-containing minerals might contribute to abiotic degradation of chlorinated ethene (CE) plumes. Here, we evaluated whether Fe(II) in clay minerals reduces tetrachloroethene (PCE) and trichloroethene (TCE). We found that structural Fe(II) in both low (SWy-2) and high (NAu-1) Fe clay minerals did not reduce PCE or TCE under anoxic conditions. There was also no reduction of PCE or TCE after adding 5 mM dissolved Fe(II) to the clay mineral suspensions. In the presence of high Fe(II) concentrations (20 mM), however, PCE and TCE reduction products were observed in the presence of low Fe-content clay mineral SWy-2. Mössbauer spectroscopy results indicate that a mixed-valent Fe(II)-Fe(III) precipitate formed in the reactive SWy-2 suspensions. In contrast, in suspensions containing 20 mM Fe(II) alone or Fe-free clay mineral (Syn-1), we observed a purely Fe(II)-containing precipitate (Fe(OH)2) and also PCE and TCE reduction products. Interestingly, the amount of CE products decreased in the order of Fe-free clay mineral Syn-1 > Fe(OH)2 > low Fe-content clay mineral SWy-2, suggesting that clay mineral Fe controlled the formation of the reactive mineral phase. Additional experiments with hexachloroethane (HCA) revealed that faster HCA reduction occurred with decreasing clay mineral Fe content. Kinetic modeling yielded invariable second-order rate constants and increasing concentrations of reactive Fe(II) as the Fe(II)/Fe(total) content of the precipitates increased. Our data suggest that clay mineral Fe(III) is a sink for electrons from added Fe(II) that otherwise might have reduced the CEs. Furthermore, our findings are consistent with the hypothesis that active precipitation of Fe(II)-containing reactive mineral intermediates (RMI) may be important to CE reduction and suggest that RMI formation depends on clay mineral presence and Fe content.

Mineral Defects Enhance Bioavailability of Goethite toward Microbial Fe(III) Reduction.

Surface defects have been shown to facilitate electron transfer between Fe(II) and goethite (α-FeOOH) in abiotic systems. It is unclear, however, whether defects also facilitate microbial goethite reduction in anoxic environments where electron transfer between cells and Fe(III) minerals is the limiting factor. Here, we used stable Fe isotopes to differentiate microbial reduction of goethite synthesized by hydrolysis from reduction of goethite that was further hydrothermally treated to remove surface defects. The goethites were reduced by Geobacter sulfurreducens in the presence of an external electron shuttle, and we used ICP-MS to distinguish Fe(II) produced from the reduction of the two types of goethite. When reduced separately, goethite with more defects has an initial rate of Fe(III) reduction about 2-fold higher than goethite containing fewer defects. However, when reduced together, the initial rate of reduction is 6-fold higher for goethite with more defects. Our results suggest that there is a suppression of the reduction of goethite with fewer defects in favor of the reduction of minerals with more defects. In the environment, minerals are likely to contain defects and our data demonstrates that even small changes at the surface of iron minerals may change their bioavailability and determine which minerals will be reduced.

Fe(II)-Catalyzed Transformation of Organic Matter-Ferrihydrite Coprecipitates: A Closer Look Using Fe Isotopes.

Ferrihydrite is a common Fe mineral in soils and sediments that rapidly transforms to secondary minerals in the presence of Fe(II). Both the rate and products of Fe(II)-catalyzed ferrihydrite transformation have been shown to be significantly influenced by natural organic matter (NOM). Here, we used enriched Fe isotope experiments and 57Fe Mössbauer spectroscopy to track the formation of secondary minerals, as well as electron transfer and Fe mixing between aqueous Fe(II) and ferrihydrite coprecipitated with several types of NOM. Ferrihydrite coprecipitated with humic acids transformed primarily to goethite after reaction with Fe(II). In contrast, ferrihydrite coprecipitated with fulvic acids and Suwannee River NOM (SRNOM) resulted in no measurable formation of secondary minerals. Despite no secondary mineral transformation, Mössbauer spectra indicated electron transfer still occurred between Fe(II) and ferrihydrite coprecipitated with fulvic acid and SRNOM. In addition, isotope tracer experiments revealed that a significant fraction of structural Fe in the ferrihydrite mixed with the aqueous phase Fe(II) (∼85%). After reaction with Fe(II), Mössbauer spectroscopy indicated some subtle changes in the crystallinity, particle size, or particle interactions in the coprecipitate. Our observations suggest that ferrihydrite coprecipitated with fulvic acid and SRNOM remains a highly dynamic phase even without ferrihydrite transformation.

The Role of Defects in Fe(II)-Goethite Electron Transfer.

Despite substantial experimental evidence for Fe(II)-Fe(III) oxide electron transfer, computational chemistry calculations suggest that oxidation of sorbed Fe(II) by goethite is kinetically inhibited on structurally perfect surfaces. We used a combination of 57Fe Mössbauer spectroscopy, synchrotron X-ray absorption and magnetic circular dichroism (XAS/XMCD) spectroscopies to investigate whether Fe(II)-goethite electron transfer is influenced by defects. Specifically, Fe L-edge and O K-edge XAS indicates that the outermost few Angstroms of goethite synthesized by low temperature Fe(III) hydrolysis is iron deficient relative to oxygen, suggesting the presence of defects from Fe vacancies. This nonstoichiometric goethite undergoes facile Fe(II)-Fe(III) oxide electron transfer, depositing additional goethite consistent with experimental precedent. Hydrothermal treatment of this goethite, however, appears to remove defects, decrease the amount of Fe(II) oxidation, and change the composition of the oxidation product. When hydrothermally treated goethite was ground, surface defect characteristics as well as the extent of electron transfer were largely restored. Our findings suggest that surface defects play a commanding role in Fe(II)-goethite redox interaction, as predicted by computational chemistry. Moreover, it suggests that, in the environment, the extent of this interaction will vary depending on diagenetic history, local redox conditions, as well as being subject to regeneration via seasonal fluctuations.

Fe(II) reduction of pyrolusite (ß-MnO2) and secondary mineral evolution.

Iron (Fe) and manganese (Mn) are the two most common redox-active elements in the Earth's crust and are well known to influence mineral formation and dissolution, trace metal sequestration, and contaminant transformations in soils and sediments. Here, we characterized the reaction of aqueous Fe(II) with pyrolusite (ß-MnO2) using electron microscopy, X-ray diffraction, aqueous Fe and Mn analyses, and 57Fe Mössbauer spectroscopy. We reacted pyrolusite solids repeatedly with 3 mM Fe(II) at pH 7.5 to evaluate whether electron transfer occurs and to track the evolving reactivity of the Mn/Fe solids. We used Fe isotopes (56 and 57) in conjunction with 57Fe Mössbauer spectroscopy to isolate oxidation of Fe(II) by Fe(III) precipitates or pyrolusite. Using these complementary techniques, we determined that Fe(II) is initially oxidized by pyrolusite and that lepidocrocite is the dominant Fe oxidation product. Additional Fe(II) exposures result in an increasing proportion of magnetite on the pyrolusite surface. Over a series of nine 3 mM Fe(II) additions, Fe(II) continued to be oxidized by the Mn/Fe particles suggesting that Mn/Fe phases are not fully passivated and remain redox active even after extensive surface coverage by Fe(III) oxides. Interestingly, the initial Fe(III) oxide precipitates became further reduced as Fe(II) was added and additional Mn was released into solution suggesting that both the Fe oxide coating and underlying Mn phase continue to participate in redox reactions when freshly exposed to Fe(II). Our findings indicate that Fe and Mn chemistry is influenced by sustained reactions of Fe(II) with Mn/Fe oxides.

Oxygen Isotope Evidence for Mn(II)-Catalyzed Recrystallization of Manganite (γ-MnOOH).

Manganese is biogeochemically cycled between aqueous Mn(II) and Mn(IV) oxides. Aqueous Mn(II) often coexists with Mn(IV) oxides, and redox reactions between the two (e.g., comproportionation) are well known to result in the formation of Mn(III) minerals. It is unknown, however, whether aqueous Mn(II) exchanges with structural Mn(III) in manganese oxides in the absence of any mineral transformation (similar to what has been reported for aqueous Fe(II) and some Fe(III) minerals). To probe whether atoms exchange between a Mn(III) oxide and water, we use a (17)O tracer to measure oxygen isotope exchange between structural oxygen in manganite (γ-MnOOH) and water. In the absence of aqueous Mn(II), about 18% of the oxygen atoms in manganite exchange with the aqueous phase, which is close to the estimated surface oxygen atoms (∼11%). In the presence of aqueous Mn(II), an additional 10% (for a total of 28%) of the oxygen atoms exchange with water, suggesting that some of the bulk manganite mineral (i.e., beyond surface) is exchanging with the fluid. Exchange of manganite oxygen with water occurs without any observable change in mineral phase and appears to be independent of the rapid Mn(II) sorption kinetics. These experiments suggest that Mn(II) catalyzes manganese oxide recrystallization and illustrate a new pathway by which these ubiquitous minerals interact with their surrounding fluid.

Iron Atom Exchange between Hematite and Aqueous Fe(II).

Aqueous Fe(II) has been shown to exchange with structural Fe(III) in goethite without any significant phase transformation. It remains unclear, however, whether aqueous Fe(II) undergoes similar exchange reactions with structural Fe(III) in hematite, a ubiquitous iron oxide mineral. Here, we use an enriched (57)Fe tracer to show that aqueous Fe(II) exchanges with structural Fe(III) in hematite at room temperature, and that the amount of exchange is influenced by particle size, pH, and Fe(II) concentration. Reaction of 80 nm-hematite (27 m(2) g(-1)) with aqueous Fe(II) at pH 7.0 for 30 days results in ∼5% of its structural Fe(III) atoms exchanging with Fe(II) in solution, which equates to about one surface iron layer. Smaller, 50 nm-hematite particles (54 m(2) g(-1)) undergo about 25% exchange (∼3× surface iron) with aqueous Fe(II), demonstrating that structural Fe(III) in hematite is accessible to the fluid in the presence of Fe(II). The extent of exchange in hematite increases with pH up to 7.5 and then begins to decrease as the pH progresses to 8.0, likely due to surface site saturation by sorbed Fe(II). Similarly, when we vary the initial amount of added Fe(II), we observe decreasing amounts of exchange when aqueous Fe(II) is increased beyond surface saturation. This work shows that Fe(II) can catalyze iron atom exchange between bulk hematite and aqueous Fe(II), despite hematite being the most thermodynamically stable iron oxide.

Atom exchange between aqueous Fe(II) and structural Fe in clay minerals.

Due to their stability toward reductive dissolution, Fe-bearing clay minerals are viewed as a renewable source of Fe redox activity in diverse environments. Recent findings of interfacial electron transfer between aqueous Fe(II) and structural Fe in clay minerals and electron conduction in octahedral sheets of nontronite, however, raise the question whether Fe interaction with clay minerals is more dynamic than previously thought. Here, we use an enriched isotope tracer approach to simultaneously trace Fe atom movement from the aqueous phase to the solid ((57)Fe) and from the solid into the aqueous phase ((56)Fe). Over 6 months, we observed a significant decrease in aqueous (57)Fe isotope fraction, with a fast initial decrease which slowed after 3 days and stabilized after about 50 days. For the aqueous (56)Fe isotope fraction, we observed a similar but opposite trend, indicating that Fe atom movement had occurred in both directions: from the aqueous phase into the solid and from the solid into aqueous phase. We calculated that 5-20% of structural Fe in clay minerals NAu-1, NAu-2, and SWa-1 exchanged with aqueous Fe(II), which significantly exceeds the Fe atom layer exposed directly to solution. Calculations based on electron-hopping rates in nontronite suggest that the bulk conduction mechanism previously demonstrated for hematite1 and suggested as an explanation for the significant Fe atom exchange observed in goethite2 may be a plausible mechanism for Fe atom exchange in Fe-bearing clay minerals. Our finding of 5-20% Fe atom exchange in clay minerals indicates that we need to rethink how Fe mobility affects the macroscopic properties of Fe-bearing phyllosilicates and its role in Fe biogeochemical cycling, as well as its use in a variety of engineered applications, such as landfill liners and nuclear repositories.

Fe(II)-catalyzed recrystallization of goethite revisited.

Results from enriched (57)Fe isotope tracer experiments have shown that atom exchange can occur between structural Fe in Fe(III) oxides and aqueous Fe(II) with no formation of secondary minerals or change in particle size or shape. Here we derive a mass balance model to quantify the extent of Fe atom exchange between goethite and aqueous Fe(II) that accounts for different Fe pool sizes. We use this model to reinterpret our previous work and to quantify the influence of particle size and pH on extent of goethite exchange with aqueous Fe(II). Consistent with our previous interpretation, substantial exchange of goethite occurred at pH 7.5 (≈ 90%) and we observed little effect of particle size between nanogoethite (average size of 81 × 11 nm; ≈ 110 m(2)/g) and microgoethite (average size of 590 × 42 nm; ≈ 40 m(2)/g). Despite ≈ 90% of the bulk goethite exchanging at pH 7.5, we found no change in mineral phase, average particle size, crystallinity, or reactivity after reaction with aqueous Fe(II). At a lower pH of 5.0, no net sorption of Fe(II) was observed and significantly less exchange occurred accounting for less than the estimated proportion of surface Fe atoms in the particles. Particle size appears to influence the amount of exchange at pH 5.0 and we suggest that aggregation and surface area may play a role. Results from sequential chemical extractions indicate that (57)Fe accumulates in extracted Fe(III) goethite components. Isotopic compositions of the extracts indicate that a gradient of (57)Fe develops within the goethite with more accumulation of (57)Fe occurring in the more easily extracted Fe(III) that may be nearer to the surface.

Spectroscopic evidence for Fe(II)-Fe(III) electron transfer at clay mineral edge and basal sites.

Despite the importance of Fe redox cycling in clay minerals, the mechanism and location of electron transfer remain unclear. More specifically, there is some controversy whether electron transfer can occur through both basal and edge surfaces. Here we used Mössbauer spectroscopy combined with selective chemical extractions to study electron transfer from Fe(II) sorbed to basal planes and edge OH-groups of clay mineral NAu-1. Fe(II) sorbed predominantly to basal planes at pH values below 6.0 and to edge OH-groups at pH value 7.5. Significant electron transfer occurred from edge OH-group bound Fe(II) at pH 7.5, whereas electron transfer from basal plane-sorbed Fe(II) to structural Fe(III) in clay mineral NAu-1 at pH 4.0 and 6.0 occurred but to a much lower extent than from edge-bound Fe(II). Mössbauer hyperfine parameters for Fe(II)-reacted NAu-1 at pH 7.5 were consistent with structural Fe(II), whereas values found at pH 4.0 and 6.0 were indicative of binding environments similar to basal plane-sorbed Fe(II). Reference experiments with Fe-free synthetic montmorillonite SYn-1 provided supporting evidence for the assignment of the hyperfine parameters to Fe(II) bound to basal planes and edge OH-groups. Our findings demonstrate that electron transfer to structural Fe in clay minerals can occur from Fe(II) sorbed to both basal planes and edge OH-groups. These findings require us to reassess the mechanisms of abiotic and microbial Fe reduction in clay minerals as well as the importance of Fe-bearing clay minerals as a renewable source of redox equivalents in subsurface environments.

Influence of chloride and Fe(II) content on the reduction of Hg(II) by magnetite.

Abiotic reduction of inorganic mercury by natural organic matter and native soils is well-known, and recently there is evidence that reduced iron (Fe) species, such as magnetite, green rust, and Fe sulfides, can also reduce Hg(II). Here, we evaluated the reduction of Hg(II) by magnetites with varying Fe(II) content in both the absence and presence of chloride. Specifically, we evaluated whether magnetite stoichiometry (x = Fe(II)/Fe(III)) influences the rate of Hg(II) reduction and formation of products. In the absence of chloride, reduction of Hg(II) to Hg(0) is observed over a range of magnetite stoichiometries (0.29 < x < 0.50) in purged headspace reactors and unpurged low headspace reactors, as evidenced by Hg recovery in a volatile product trap solution and Hg L(III)-edge X-ray absorption near edge spectroscopy (XANES). In the presence of chloride, however, XANES spectra indicate the formation of a metastable Hg(I) calomel species (Hg2Cl2) from the reduction of Hg(II). Interestingly, Hg(I) species are only observed for the more oxidized magnetite particles that contain lower Fe(II) content (x < 0.42). For the more reduced magnetite particles (x ≥ 0.42), Hg(II) is reduced to Hg(0) even in the presence of high chloride concentrations. As previously observed for nitroaromatic compounds and uranium, magnetite stoichiometry appears to influence the rate of Hg(II) reduction (both in the presence and absence of chloride) confirming that it is important to consider magnetite stoichiometry when assessing the fate of contaminants in Fe-rich subsurface environments.

Effects of bound phosphate on the bioreduction of lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3) and formation of secondary minerals.

Natural Fe(III) oxides typically contain a range of trace elements including P. Although solution phase and adsorbed P (as phosphate) have been shown to impact the bioreduction of Fe(III) oxides and the formation of "biogenic" secondary minerals, little is known about the potential effects of occluded/incorporated phosphate. We have examined the bioreduction of Fe(III) oxides (lepidocrocite (γ-FeOOH) and maghemite (γ-Fe2O3)) containing 0-3 mass% P as "bound" (a term we use to include both adsorbed and occluded/incorporated) phosphate. Kinetic dissolution studies showed congruent release of Fe and P, suggesting that the phosphate in these materials was incorporated within the particles; however, 53% or 86% of the total phosphate associated with the lepidocrocites containing 0.7 or 3 mass% P, respectively, was extracted with 0.1 M NaOH and can be considered to be adsorbed, both to exterior surfaces and within micropores. In the absence of phosphate, lepidocrocite was rapidly reduced to magnetite by Shewanella putrefaciens CN32, and over time the magnetite was partially transformed to ferrous hydroxy carbonate (FHC). The presence of 0.2-0.7 mass% P significantly inhibited the initial reduction of lepidocrocite but ultimately resulted in greater Fe(II) production and the formation of carbonate green rust. The bioreduction of maghemite with and without bound phosphate resulted in solid-state conversion to magnetite, with subsequent formation of FHC. We also examined the potential redox cycling of green rust under alternating Fe(III)-reducing and oxic conditions. Oxidation of biogenic green rust by O2 resulted in conversion to ferric green rust, which was readily reduced back to green rust by S. putrefaciens CN32. These results indicate the potential for cycling of green rust between reduced and oxidized forms under redox dynamics similar to those encountered in environments that alternate between iron-reducing and oxic conditions, and they are consistent with the identification of green rust in soils/sediments with seasonal redox cycling.

Simulated atmospheric processing of iron oxyhydroxide minerals at low pH: roles of particle size and acid anion in iron dissolution.

A number of recent studies have shown that iron dissolution in Fe-containing dust aerosol can be linked to source material (mineral or anthropogenic), mineralogy, and iron speciation. All of these factors need to be incorporated into atmospheric chemistry models if these models are to accurately predict the impact of Fe-containing dusts into open ocean waters. In this report, we combine dissolution measurements along with spectroscopy and microscopy to focus on nanoscale size effects in the dissolution of Fe-containing minerals in low-pH environments and the importance of acid type, including HNO(3), H(2)SO(4), and HCl, on dissolution. All of these acids are present in the atmosphere, and dust particles have been shown to be associated with nitrate, sulfate, and/or chloride. These measurements are done under light and dark conditions so as to simulate and distinguish between daytime and nighttime atmospheric chemical processing. Both size (nano- versus micron-sized particles) and anion (nitrate, sulfate, and chloride) are found to play significant roles in the dissolution of alpha-FeOOH under both light and dark conditions. The current study highlights these important, yet unconsidered, factors in the atmospheric processing of iron-containing mineral dust aerosol.

Tracking Initial Fe(II)-Driven Ferrihydrite Transformations: A Mössbauer Spectroscopy and Isotope Investigation.

Transformation of nanocrystalline ferrihydrite to more stable microcrystalline Fe(III) oxides is rapidly accelerated under reducing conditions with aqueous Fe(II) present. While the major steps of Fe(II)-catalyzed ferrihydrite transformation are known, processes in the initial phase that lead to nucleation and the growth of product minerals remain unclear. To track ferrihydrite-Fe(II) interactions during this initial phase, we used Fe isotopes, Mössbauer spectroscopy, and extractions to monitor the structural, magnetic, and isotope composition changes of ferrihydrite within ∼30 min of Fe(II) exposure. We observed rapid isotope mixing between aqueous Fe(II) and ferrihydrite during this initial lag phase. Our findings from Mössbauer spectroscopy indicate that a more magnetically ordered Fe(III) phase initially forms that is distinct from ferrihydrite and bulk crystalline transformation products. The signature of this phase is consistent with the early stage emergence of lepidocrocite-like lamellae observed in previous transmission electron microscopy studies. Its signature is furthermore removed by xylenol extraction of Fe(III), the same approach used to identify a chemically labile form of Fe(III) resulting from Fe(II) contact that is correlated to the ultimate emergence of crystalline product phases detectable by X-ray diffraction. Our work indicates that the mineralogical changes in the initial lag phase of Fh transformation initiated by Fe(II)-Fh electron transfer are critical to understanding ferrihydrite behavior in soils and sediments, particularly with regard to metal uptake and release.

Influence of Fe(2+)-catalysed iron oxide recrystallization on metal cycling.

Recent work has indicated that iron (oxyhydr-)oxides are capable of structurally incorporating and releasing metals and nutrients as a result of Fe2+-induced iron oxide recrystallization. In the present paper, we briefly review the current literature examining the mechanisms by which iron oxides recrystallize and summarize how recrystallization affects metal incorporation and release. We also provide new experimental evidence for the Fe2+-induced release of structural manganese from manganese-doped goethite. Currently, the exact mechanism(s) for Fe2+-induced recrystallization remain elusive, although they are likely to be both oxide-and metal-dependent. We conclude by discussing some future research directions for Fe2+-catalysed iron oxide recrystallization.

Fe electron transfer and atom exchange in goethite: influence of Al-substitution and anion sorption.

The reaction of Fe(II) with Fe(III) oxides and hydroxides is complex and includes sorption of Fe(II) to the oxide, electron transfer between sorbed Fe(II) and structural Fe(III), reductive dissolution coupled to Fe atom exchange, and, in some cases mineral phase transformation. Much of the work investigating electron transfer and atom exchange between aqueous Fe(II) and Fe(III) oxides has been done under relatively simple aqueous conditions in organic buffers to control pH and background electrolytes to control ionic strength. Here, we investigate whether electron transfer is influenced by cation substitution of Al(III) in goethite and the presence of anions such as phosphate, carbonate, silicate, and natural organic matter. Results from (57)Fe Mössbauer spectroscopy indicate that both Al-substitution (up to 9%) and the presence of common anions (PO(4)(3-), CO(3)(2-), SiO(4)(4-), and humic acid) does not inhibit electron transfer between aqueous Fe(II) and Fe(III) in goethite under the conditions we studied. In contrast, sorption of a long-chain phospholipid completely shuts down electron transfer. Using an enriched isotope tracer method, we found that Al-substitution in goethite (10%), does, however, significantly decrease the extent of atom exchange between Fe(II) and goethite (from 43 to 12%) over a month's time. Phosphate, somewhat surprisingly, appears to have little effect on the rate and extent of atom exchange between aqueous Fe(II) and goethite. Our results show that electron transfer between aqueous Fe(II) and solid Fe(III) in goethite can occur under wide range of geochemical conditions, but that the extent of redox-driven Fe atom exchange may be dependent on the presence of substituting cations such as Al.

Coal fly ash as a source of iron in atmospheric dust.

Anthropogenic coal fly ash (FA) aerosol may represent a significant source of bioavailable iron in the open ocean. Few measurements have been made that compare the solubility of atmospheric iron from anthropogenic aerosols and other sources. We report here an investigation of iron dissolution for three FA samples in acidic aqueous solutions and compare the solubilities with that of Arizona test dust (AZTD), a reference material for mineral dust. The effects of pH, simulated cloud processing, and solar radiation on iron solubility have been explored. Similar to previously reported results on mineral dust, iron in aluminosilicate phases provides the predominant component of dissolved iron. Iron solubility of FA is substantially higher than of the crystalline minerals comprising AZTD. Simulated atmospheric processing elevates iron solubility due to significant changes in the morphology of aluminosilicate glass, a dominant material in FA particles. Iron is continuously released into the aqueous solution as FA particles break up into smaller fragments. These results suggest that the assessment of dissolved atmospheric iron deposition fluxes and their effect on the biogeochemistry at the ocean surface should be constrained by the source, environmental pH, iron speciation, and solar radiation.

Influence of magnetite stoichiometry on U(VI) reduction.

Hexavalent uranium (U(VI)) can be reduced enzymatically by various microbes and abiotically by Fe(2+)-bearing minerals, including magnetite, of interest because of its formation from Fe(3+) (oxy)hydroxides via dissimilatory iron reduction. Magnetite is also a corrosion product of iron metal in suboxic and anoxic conditions and is likely to form during corrosion of steel waste containers holding uranium-containing spent nuclear fuel. Previous work indicated discrepancies in the extent of U(VI) reduction by magnetite. Here, we demonstrate that the stoichiometry (the bulk Fe(2+)/Fe(3+) ratio, x) of magnetite can, in part, explain the observed discrepancies. In our studies, magnetite stoichiometry significantly influenced the extent of U(VI) reduction by magnetite. Stoichiometric and partially oxidized magnetites with x ≥ 0.38 reduced U(VI) to U(IV) in UO(2) (uraninite) nanoparticles, whereas with more oxidized magnetites (x < 0.38) and maghemite (x = 0), sorbed U(VI) was the dominant phase observed. Furthermore, as with our chemically synthesized magnetites (x ≥ 0.38), nanoparticulate UO(2) was formed from reduction of U(VI) in a heat-killed suspension of biogenic magnetite (x = 0.43). X-ray absorption and Mössbauer spectroscopy results indicate that reduction of U(VI) to U(IV) is coupled to oxidation of Fe(2+) in magnetite. The addition of aqueous Fe(2+) to suspensions of oxidized magnetite resulted in reduction of U(VI) to UO(2), consistent with our previous finding that Fe(2+) taken up from solution increased the magnetite stoichiometry. Our results suggest that magnetite stoichiometry and the ability of aqueous Fe(2+) to recharge magnetite are important factors in reduction of U(VI) in the subsurface.

Inhibition of trace element release during Fe(II)-activated recrystallization of Al-, Cr-, and Sn-substituted goethite and hematite.

Aqueous Fe(II) reacts with Fe(III) oxides by coupled electron transfer and atom exchange (ETAE) resulting in mineral recrystallization, contaminant reduction, and trace element cycling. Previous studies of Fe(II)-Fe(III) ETAE have explored the reactivity of either pure iron oxide phases or those containing small quantities of soluble trace elements. Naturally occurring iron oxides, however, contain substantial quantities of insoluble impurities (e.g., Al) which are known to affect the chemical properties of such minerals. Here we explore the effect of Al(III), Cr(III), and Sn(IV) substitution (1-8 mol %) on trace element release from Ni(II)-substituted goethite and Zn(II)-substituted hematite during reaction with aqueous Fe(II). Fe(II)-activated trace element release is substantially inhibited from both minerals when an insoluble element is cosubstituted into the structure, and the total amount of release decreases exponentially with increasing cosubstituent. The limited changes in surface composition that occur following reaction with Fe(II) indicate that Al, Cr, and Sn do not exsolve from the structure and that Ni and Zn released to solution originate primarily from the bulk rather than the particle exterior (upper ~3 nm). Incorporation of Al into goethite substantially decreases the amount of iron atom exchange with aqueous Fe(II) and, consequently, the amount of Ni release from the structure. This implies that trace element release inhibition caused by substituting insoluble elements results from a decrease in the amount of mineral recrystallization. These results suggest that naturally occurring iron oxides containing insoluble elements are less susceptible to Fe(II)-activated recrystallization and exhibit a greater retention of trace elements and contaminants than pure mineral phases.