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Mn oxides are among the most ubiquitous minerals on Earth and play critical roles in numerous elemental cycles in biotic/abiotic loops as the key redox center. Yet, it has long puzzled geochemists why the laboratory synthesis of todorokite, a tunnel-structured Mn oxide, is extremely difficult while it is the dominant form over other tunneled phases in low-temperature natural environments. This study employs a novel electrochemical method to mimic the cyclic redox reactions occurring over long geological time scales in an accelerated manner. The results revealed that the kinetics and electron flux of the cyclic redox reaction are key to the layer-to-tunnel structure transformation of Mn oxides, provided new insights for natural biotic and abiotic redox reactions, and explained the dominance of todorokite in nature.

Arsenite (As(III)), may be rapidly oxidized to arsenate (As(V)) by manganese oxides over a wide range of pH. Interestingly, pseudo-first order rate constants for Mn(IV) oxides (MnO2) reported in the literature differ by orders of magnitude, mainly due to the fact that experimental conditions have not been normalized and surface passivation may hinder the reaction rate. As a result, a formal kinetic rate law for the oxidation of As(III) by MnO2 does not exist. In this study, a comprehensive rate law that describes the abiotic oxidation of As(III) by vernadite (δ-MnO2) was developed by systematically varying pH and the concentrations of δ-MnO2 and As(III). Experiments were performed with excess δ-MnO2 compared to As(III) in buffered solutions with an ionic strength typical of freshwater environments to reflect the geochemical conditions of most environments. The half-life of the pseudo-first order reaction is less than three minutes in all experiments. Results show the initial reaction rate is proportional to the concentrations of δ-MnO2 and As(III) and independent of pH in the pH range 4–9. However, below pH 6 and above pH 8 the pseudo-first order rate constant is slightly lower due to the protonation of the surface δ-MnO2 and the deprotonation of As(III). Overall, the reaction follows a first order rate law with respect to As(III) and effective surface sites of δ-MnO2 and zeroth order with respect to pH. The overall second order rate constant, k, was calculated to be 0.36 ± 0.11 L h−1 m−2. This rate constant is comparable to the vast majority of rate constants derived from previously published data when using the effective surface sites of MnO2 as reactive species only, indicating the most influential factors of As(III) oxidation by MnO2 are constrained in the developed rate law. Based on the present experiments, the oxidation of As(III) by MnO2 is proposed to proceed as one two-electron transfer reaction between As(III) and Mn(IV) to eventually form As(V) and Mn2+ species. Two steps of one-electron transfer, however, may be possible though it is likely that both Mn(IV) and Mn(III) species are ultimately reduced to Mn2+. Comproportionation of Mn2+ and Mn(IV) to Mn(III) does not seem to be important on the time scale of these experiments.

As oxidation state is often a primary determinant of the mobility of uranium in subsurface environments, a comprehensive understanding of the redox cycling of uranium is essential to predict the fate of this contaminant. The potential of iron to serve as both a reductant and an oxidant of uranium suggests that remediation strategies which primarily rely on the reduction of the uranyl ion (U(VI)) to the poorly soluble uranous ion (U(IV)) to immobilize uranium in the solid phase may be either enhanced or hindered depending on the biogeochemical transformations of iron. To identify the geochemical controls of both uranium and iron redox cycling, batch incubations with the model metal-reducing bacterium Shewanella putrefaciens were conducted with either U(VI), ferrihydrite, or both as terminal electron acceptors, and concentrations of dissolved inorganic carbon (DIC), calcium, and silica were varied to alter aqueous uranyl speciation and secondary mineralization pathways of ferrihydrite. The presence of ferrihydrite increased the pseudo-first order rate constant of initial uranium removal from solution in nearly all conditions compared to uranium-only controls due to a combination of abiotic U(VI) reduction by Fe(II) and solid-phase association of uranium with secondary mineralization products of ferrihydrite. Following an initial period of uranium reduction, U(IV) was oxidized by ferrihydrite which led to a rebound in dissolved uranium. Once ferrihydrite was completely consumed by microbial respiration and secondary mineralization, uranium was again removed from solution via reductive precipitation and association with secondary mineralization products. DIC and calcium enhanced the oxidative dissolution of U(IV) solids but did not affect the redox potential of the U(VI)/U(IV) redox couple despite the formation of aqueous uranyl carbonate and calcium-uranyl carbonate species. Instead, removal of dissolved Fe(II) from solution and the accompanied shift in the redox potential of the Fe(III)/Fe(II) redox couple was responsible for the abrupt shift in iron acting as a reductant of U(VI) to an oxidant of U(IV). The removal of dissolved Fe(II) via siderite precipitation at the highest DIC concentration and in the presence of calcium enhanced the oxidation of U(IV), and the presence of silica limited the conversion of ferrihydrite to magnetite and sustained U(IV) oxidation. A kinetic model was developed which could reproduce incubation time series of uranium and iron speciation provided the thermodynamic favorability of abiotic uranium-iron redox cycling was accounted for. The modeling exercise revealed that the non-uraninite U(IV) solids formed in the incubations have a redox potential approximately 84 mV lower than that of amorphous uraninite, highlighting the need for a thermodynamic characterization of non-uraninite U(IV) solids. The results of this study identify dissolved Fe(II) concentration as the primary geochemical control of the role of iron in uranium redox cycling at moderate to high DIC concentrations and emphasize the importance of considering this parameter when designing site-specific, in situ bioremediation strategies.

This study characterized the kinetics of abiotic production of the greenhouse gas nitrous oxide (N 2 O) by chemical oxidation of the nitrification intermediate hydroxylamine (NH 2 OH) in seawater at circumneutral pH (6.2–8.3). The oxidant was birnessite , a ubiquitous manganese oxide mineral in a variety of marine environments. Experiments using microsensor electrodes for high-resolution measurements of N 2O production combined with the simultaneous measurements of the removal of NH2OH using spectrophotometric techniques revealed that the reaction was overall first order with the rate law d[N2O]/dt = k[NH2OH]0.9[MnO2]0.3[H+]0 where k is 0.01 s−1. Birnessite consistently oxidized 80–100% of NH2OH to N2O within 3 min. Mass balance on nitrogen indicated rapid formation and disappearance of an intermediate species that was evidently involved in the formation of N2 O. In the presence of a nitroxyl (HNO) scavenger, N 2O production rates and yield were suppressed by 17–59% and ~50%, respectively, suggesting that HNO is an intermediate in NH2OH oxidation to N2 O. These results support a mechanism whereby Mn(IV) is reduced to Mn(III) with the formation of an aminoxyl radical as the first product of NH 2OH oxidation, which donates a second electron to another Mn(IV) center, or reduces the same Mn(III), to release Mn2+ and HNO in solution. The final step is predicted to be HNO dimerization to N 2O given the complete oxidation of NH2OH to N2O at steady-state. The experimentally-derived second-order rate constant for the dimerization step suggests that adsorption of HNO onto the excess solid surface controls the rate of N2O formation. Our findings suggest that abiotic NH2OH oxidation could be an important source of N2 O in coastal ecosystems such as open oceans and oxygen minimum zones as well as sediment ecosystems wherever nitrification occurs in the presence of particulate metal oxides .

Low molecular weight organic sulfur species, often referred to as thiols, are known to be ubiquitous in aquatic environments and represent important chemical reductants of Fe(III) oxides. Thiols are excellent electron shuttles used during dissimilatory iron reduction, and in this capacity could indirectly affect the redox state of sediments, release adsorbed contaminants via reductive dissolution, and influence the carbon cycle through alteration of bacterial respiration processes. Interestingly, the reduction of Fe(III) oxides by thiols has not been previously investigated in environmentally relevant conditions, likely due to analytical limitations associated with the detection of thiols and their oxidized products. In this study, a novel electrochemical method was developed to simultaneously determine thiol/disulfide pair concentrations in situ during the reduction of ferrihydrite in batch reactors. First order rate laws with respect to initial thiol concentration were confirmed for Fe(III) oxyhydroxide reduction by four common thiols: cysteine, homocysteine, cysteamine, and glutathione. Zero order was determined for both Fe(III) oxyhydroxide and proton concentration at circumneutral pH. A kinetic model detailing the molecular mechanism of the reaction was optimized with proposed intermediate surface structures. Although metal oxide overall reduction rate constants were inversely proportional to the complexity of the thiol structure, the extent of metal reduction increased with structure complexity, indicating that surface complexes play a significant role in the ability of these thiols to reduce iron. Taken together, these results demonstrate the importance of considering the molecular reaction mechanism at the iron oxide surface when investigating the potential for thiols to act as electron shuttles during dissimilatory iron reduction in natural environments.

Soluble manganese in the intermediate +III oxidation state (Mn3+ ) is a newly identified oxidant in anoxic environments, whereas acetate is a naturally abundant substrate that fuels microbial activity. Microbial populations coupling anaerobic acetate oxidation to Mn3+ reduction, however, have yet to be identified. We isolated a Shewanella strain capable of oxidizing acetate anaerobically with Mn3+ as the electron acceptor, and confirmed this phenotype in other strains. This metabolic connection between acetate and soluble Mn3+ represents a new biogeochemical link between carbon and manganese cycles. Genomic analyses uncovered four distinct genes that allow for pathway variations in the complete dehydrogenase-driven TCA cycle that could support anaerobic acetate oxidation coupled to metal reduction in Shewanella and other Gammaproteobacteria. An oxygen-tolerant TCA cycle supporting anaerobic manganese reduction is thus a new connection in the manganese-driven carbon cycle, and a new variable for models that use manganese as a proxy to infer oxygenation events on early Earth.

International audience; Pore water and solid phase geochemical profiles of sediment cores collected along two transects on the western and eastern sides of the Mississippi River mouth in the northern Gulf of Mexico were incorporated into a reactive transport model to determine the role of manganese and iron in the remineralization of carbon. Reactive transport model calculations indicate that sedimentation rates control the intensity of anaerobic carbon remineralization and select for the dominant anaerobic carbon remineralization pathways. Although sulfate reduction dominates the shelf station (65 m water depth), denitrification and microbial manganese reduction appear equally significant anaerobic respiration processes along the continental slope the closest to the Mississippi River, whereas microbial iron reduction does not represent an important process in these sediments. These findings suggest that the differential kinetics of manganese and iron redox transformations influence carbon remineralization processes on the continental slope. The fast kinetics of Fe2+ oxidation near the sediment-water interface and high sedimentation rates maintain Fe under the form of Fe(III) oxides and thermodynamically prevent sulfate reduction from dominating carbon remineralization processes on the slope, whereas the much slower Mn2+ oxygenation kinetics allows diffusion of Mn2+ across the sediment-water interface of the shelf station closest to the river mouth. Exposure to oxygenated bottom waters and entrainment within mobile muds typical of deltaic sediments during high riverine discharge likely promote the formation and downslope transport of Mn(III/IV) oxides within the nepheloid layer. This phenomenon appears to form a manganese ‘conveyor belt’ that selectively enriches Mn(III/IV) oxides relative to Fe(III) oxides in the deep sediment. In contrast, the intensity of anaerobic carbon remineralization processes along the eastern continental slope the farthest from the Mississippi River plume is much lower due to the low organic and lithogenic inputs, and denitrification dominates anaerobic respiration. Overall, these findings suggest that manganese cycling and its role in carbon remineralization processes in continental slope sediments exposed to large riverine inputs may be more important than previously considered.

The bioreduction of uranium may immobilize a significant fraction of this toxic contaminant in reduced environments at circumneutral pH. In oxic and low pH environments, however, the low solubility of U(VI)-phosphate minerals also makes them good candidates for the immobilization of U(VI) in the solid phase. As inorganic phosphate is generally scarce in soils, the biomineralization of U(VI)-phosphate minerals via microbially-mediated organophosphate hydrolysis may represent the main immobilization process of uranium in these environments. In this study, contaminated sediments were incubated aerobically in two pH conditions to examine whether phytate, a naturally-occurring and abundant organophosphate in soils, could represent a potential phosphorous source to promote U(VI)-phosphate biomineralization by natural microbial communities. While phytate hydrolysis was not evident at pH 7.0, nearly complete hydrolysis was observed both with and without electron donor at pH 5.5, suggesting indigenous microorganisms express acidic phytases in these sediments. While the rate of hydrolysis of phytate generally increased in the presence of uranium, the net rate of inorganic phosphate production in solution was decreased and inositol phosphate intermediates were generated in contrast to similar incubations conducted without uranium. These findings suggest uranium stress enhanced the phytate-metabolism of the microbial community, while simultaneously inhibiting phosphatase production and/or activity by the indigenous population. Finally, phytate hydrolysis drastically decreased uranium solubility, likely due to formation of ternary sorption complexes, U(VI)-phytate precipitates, and U(VI)-phosphate minerals. Overall, the results of this study provide evidence for the ability of natural microbial communities to liberate phosphate from phytate in acidic sediments, possibly as a detoxification mechanism, and demonstrate the potential utility of phytate-promoted uranium immobilization in subsurface environments. These processes should be investigated in more detail with pure cultures isolated from these sediments.

The kinetics and mechanism of thiol oxidation by Mn oxides undergoing dynamic structural transformation under environmentally relevant conditions remain poorly understood. In this study, thiol/disulfide pair concentrations were simultaneously determined in situ using voltammetric microelectrodes during the interaction of four common thiols (cysteine, homocysteine, cysteamine, and glutathione) with fresh and aged δ-MnO2 at pH 7.0. The reaction kinetics was first order with respect to thiol and zero order with respect to Mn oxides. A transient intermediate sulfur surface species observed during the reaction provides evidence for a mechanism involving two successive one-electron transfer steps. The reaction kinetics of fresh and aged δ-MnO2 was investigated with cysteine and compared to that of manganite, a Mn(III) oxyhydroxide phase. The reactivity of aged δ-MnO2 decreased as a result of structural transformation to cryptomelane but remained higher than that of manganite, suggesting the potential roles of transient Mn(III) surface intermediate in promoting the reduction of Mn(IV) in δ-MnO2 and cryptomelane (compared to Mn(III) in manganite). This study demonstrates the importance of correlating Mn oxide mineral structure and redox reactivity and extends the potential for thiols commonly found in sedimentary environments to be utilized as electron shuttles during dissimilatory Mn reduction.

The ability to predict the success of the microbial reduction of soluble U(VI) to highly insoluble U(IV) as an in situ bioremediation strategy is complicated by the wide range of geochemical conditions at contaminated sites and the strong influence of aqueous uranyl speciation on the bioavailability and toxicity of U(VI) to metal-reducing bacteria. In order to determine the effects of aqueous uranyl speciation on uranium bioreduction kinetics, incubations and viability assays with Shewanella putrefaciens strain 200 were conducted over a range of pH and dissolved inorganic carbon (DIC), Ca2+, and Mg2+ concentrations. A speciation-dependent kinetic model was developed to reproduce the observed time series of total dissolved uranium concentration over the range of geochemical conditions tested. The kinetic model yielded the highest rate constant for the reduction of uranyl non-carbonate species (i.e., the ‘free’ hydrated uranyl ion, uranyl hydroxides, and other minor uranyl complexes), indicating that they represent the most readily reducible fraction of U(VI) despite being the least abundant uranyl species in solution. In the presence of DIC, Ca2+, and Mg2+ is suppressed during the formation of more bioavailable uranyl non-carbonate species and resulted in slower bioreduction rates. At high concentrations of bioavailable U(VI), however, uranium toxicity to S.more » putrefaciens inhibited bioreduction, and viability assays confirmed that the concentration of non-carbonate uranyl species best predicts the degree of toxicity. The effect of uranium toxicity was accounted for by incorporating the free ion activity model of metal toxicity into the bioreduction rate law. These results demonstrate that, in the absence of competing terminal electron acceptors, uranium bioreduction kinetics can be predicted over a wide range of geochemical conditions based on the bioavailability and toxicity imparted on U(VI) by solution composition. Finally, these findings also imply that the concentration of uranyl non-carbonate species, despite being extremely low, is a determining factor controlling uranium bioreduction at contaminated sites.« less

The reduction of Mn(IV) oxides coupled to the anaerobic oxidation of NH 4 + has been proposed for more than a decade to contribute to the fixed nitrogen pool in marine sediments, yet the existence of this process is still under debate. In this study, surface sediments from an intertidal salt marsh were incubated with MnO2 in the presence of elevated concentrations of NH 4 + to test the hypothesis that the reduction of Mn(IV) oxides catalyzes anaerobic NH 4 + oxidation to NO 2 - or NO 3 - . Geochemical factors such as the ratio of Mn(IV) to NH 4 + , the type of Mn(IV) oxides (amorphous or colloidal MnO2), and the redox potential of the sediment significantly affect the activity of anaerobic nitrification. Incubations show that the net production of NO 3 - is stimulated under anaerobic conditions with external addition of colloidal but not amorphous MnO2 and is facilitated by the presence of high concentrations of NH 4 + . Mass balance calculations demonstrate that anaerobic NH 4 + oxidation contributes to the net consumption of NH 4 + , providing another piece of evidence for the occurrence of Mn(IV)-catalyzed anaerobic nitrification in coastal marine sediments. Finally, anaerobic nitrification is stimulated by the amendment of small concentrations of NO 3 - or the absence of sulfate reduction, suggesting that moderately reducing conditions favor anaerobic NH 4 + oxidation. Overall, these findings suggest that Mn(IV)-catalyzed anaerobic nitrification in suboxic sediments with high N/Mn concentration ratios and highly reactive manganese oxides may be an important source of NO 2 - and NO 3 - for subsequent marine nitrogen loss via denitrification or anammox.

Although bioreduction of uranyl ions (U(VI)) and biomineralization of U(VI)–phosphate minerals are both able to immobilize uranium in contaminated sediments, the competition between these processes and the role of anaerobic respiration in the biomineralization of U(VI)–phosphate minerals has yet to be investigated. In this study, contaminated sediments incubated anaerobically in static microcosms at pH 5.5 and 7.0 were amended with the organophosphate glycerol-2-phosphate (G2P) as sole phosphorus and external carbon source and iron oxides, sulfate, or nitrate as terminal electron acceptors to determine the most favorable geochemical conditions to these two processes. While sulfate reduction was not observed even in the presence of G2P at both pHs, iron reduction was more significant at circumneutral pH irrespective of the addition of G2P. In turn, nitrate reduction was stimulated by G2P at both pH 5.5 and 7.0, suggesting nitrate-reducing bacteria provided the main source of inorganic phosphate in these sediments. U(VI) was rapidly removed from solution in all treatments but was not reduced as determined by X-ray absorption near edge structure (XANES) spectroscopy. Simultaneously, wet chemical extractions and extended X-ray absorption fine structure (EXAFS) spectroscopy of these sediments indicated the presence of U–P species in reactors amended with G2P at both pHs. The rapid removal of dissolved U(VI), the simultaneous production of inorganic phosphate, and the existence of U–P species in the solid phase indicate that uranium was precipitated as U(VI)–phosphate minerals in sediments amended with G2P. Thus, under reducing conditions and in the presence of G2P, bioreduction of U(VI) was outcompeted by the biomineralization of U(VI)–phosphate minerals and U(VI) sorption at both pHs.

WOS:000408783500011; International audience; Deep-sea fans are well known depot centers for organic carbon that should promote sulfate reduction. At the same time, the high rates of deposition of unconsolidated metal oxides from terrigenous origin may also promote metal-reducing microbial activity. To investigate the eventual coupling between the iron and sulfur cycles in these environments, shallow sediment cores ( \textless 50 cm) across various channels and levees in the Congo River deep-sea fan (similar to 5000 m) were profiled using a combination of geochemical methods. Interestingly, metal reduction dominated suboxic carbon remineralization processes in most of these sediments, while dissolved sulfide was absent. In some 'hotspot' patches, however, sulfate reduction produced large sulfide concentrations which supported chemosynthetic-based benthic megafauna. These environments were characterized by sharp geochemical boundaries compared to the iron-rich background environment, suggesting that FeS precipitation efficiently titrated iron and sulfide from the pore waters. A companion study demonstrated that methanogenesis was active in the deep sediment layers of these patchy ecosystems, suggesting that sulfate reduction was promoted by alternative anaerobic processes. These highly reduced habitats could be fueled by discrete, excess inputs of highly labile natural organic matter from Congo River turbidites or by exhumation of buried sulfide during channel flank erosion and slumping. Sulfidic conditions may be maintained by the mineralization of decomposition products from local benthic macrofauna or bacterial symbionts or by the production of more crystalline Fe(III) oxide phases that are less thermodynamically favorable than sulfate reduction in these bio-turbated sediments. Overall, the iron and sulfur biogeochemical cycling in this environment is unique and much more similar to a coastal ecosystem than a deep-sea environment.

Mn(IV) and Mn(II) are the most stable and prevalent forms of manganese in natural environments. The occurrence of Mn(III) in minerals and the detection of soluble Mn(III) in natural waters, however, suggest that Mn(III) is an intermediate in both the oxidation of Mn(II) and the reduction of Mn(IV). Mn(III) has recently been proposed as an intermediate during the oxidation of Mn(II) by Mn-oxidizing bacteria but has never been considered as an intermediate during the bio-reduction of Mn(IV). Here we show for the first time that microbial Mn(IV) reduction proceeds step-wise via two successive one-electron transfer reactions with production of soluble Mn(III) as transient intermediate. Incubations with mutant strains demonstrate that the reduction of both solid Mn(IV) and soluble Mn(III) occurs at the outer membrane of the cell. In addition, pseudo-first order rate constants obtained from these incubations indicate that Mn(IV) respiration involves only one of the two potential terminal reductases (c-type cytochrome MtrC and OmcA) involved in Fe(III) respiration. More importantly, only the second electron transfer step is coupled to production of dissolved inorganic carbon, suggesting that the first electron transfer reaction is a reductive solubilization step that increases Mn bioavailability. These findings oppose the long-standing paradigm that microbial Mn(IV) reduction proceeds via a single two-electron transfer reaction coupled to organic carbon oxidation, and suggest that diagenetic models should be revised to correctly account for the impact of manganese reduction in the global carbon cycle.

The biomineralization of U(VI) phosphate as a result of microbial phosphatase activity is a promising new bioremediation approach to immobilize uranium in both aerobic and anaerobic conditions. In contrast to reduced uranium minerals such as uraninite, uranium phosphate precipitates are not susceptible to changes in oxidation conditions and may represent a long-term sink for uranium in contaminated environments. So far, the biomineralization of U(VI) phosphate has been demonstrated with pure cultures only. In this study, two uranium contaminated soils from the Department of Energy Oak Ridge Field Research Center (ORFRC) were amended with glycerol phosphate as model organophosphate source in small flow-through columns under aerobic conditions to determine whether natural phosphatase activity of indigenous soil bacteria was able to promote the precipitation of uranium(VI) at pH 5.5 and 7.0. High concentrations of phosphate (1–3 mM) were detected in the effluent of these columns at both pH compared to control columns amended with U(VI) only, suggesting that phosphatase-liberating microorganisms were readily stimulated by the organophosphate substrate. Net phosphate production rates were higher in the low pH soil (0.73 ± 0.17 mM d−1) compared to the circumneutral pH soil (0.43 ± 0.31 mM d−1), suggesting that non-specific acid phosphatase activity was expressed constitutively in these soils. A sequential solid-phase extraction scheme and X-ray absorption spectroscopy measurements were combined to demonstrate that U(VI) was primarily precipitated as uranyl phosphate minerals at low pH, whereas it was mainly adsorbed to iron oxides and partially precipitated as uranyl phosphate at circumneutral pH. These findings suggest that, in the presence of organophosphates, microbial phosphatase activity can contribute to uranium immobilization in both low and circumneutral pH soils through the formation of stable uranyl phosphate minerals.

Depth profiles in the sediment porewaters of the Chattahoochee River (Georgia, USA) show that iron oxides scavenge arsenate in the water column and settle to the sediment–water interface (SWI) where they are reduced by iron-reducing bacteria. During their reduction, these particles seem to release arsenic to the porewaters in the form of arsenate only. Sediment slurry incubations were conducted to determine the effect of low concentrations of arsenic (⩽10 μM) on biogeochemical processes in these sediments. Experiments confirm that any arsenate (As(V)) added to these sediments is immediately adsorbed in oxic conditions and released in anoxic conditions during the microbial reduction of authigenic iron oxides. Incubations in the presence of ⩽1 μM As(V) reveal that arsenate is released but not concomitantly reduced during this process. Simultaneously, microbial iron reduction is enhanced significantly, spurring the simultaneous release of arsenate into porewaters and secondary formation of crystalline iron oxides. Above 1 μM As(V), however, the microbial reductive dissolution of iron oxides appears inhibited by arsenate, and arsenite is produced in excess in the porewaters. These incubations show that even low inputs of arsenic to riverine sediments may affect microbial processes, the stability of iron oxides and, indirectly, the cycling of arsenic. Possible mechanisms for such effects on iron reduction are proposed.

In this project, inter-disciplinary research activities were conducted in collaboration among investigators at The University of Alabama (UA), Georgia Institute of Technology (GT), Lawrence Berkeley National Laboratory (LBNL), Brookhaven National Laboratory (BNL), the DOE Joint Genome Institute (JGI), and the Stanford Synchrotron Radiation Light source (SSRL) to: (i) confirm that phosphatase activities of subsurface bacteria in Area 2 and 3 from the Oak Ridge Field Research Center result in solid U-phosphate precipitation in aerobic and anaerobic conditions; (ii) investigate the eventual competition between uranium biomineralization via U-phosphate precipitation and uranium bioreduction; (iii) determine subsurface microbial community structure changes of Area 2 soils following organophosphate amendments; (iv) obtain the complete genome sequences of the Rahnella sp. Y9-602 and the type-strain Rahnella aquatilis ATCC 33071 isolated from these soils; (v) determine if polyphosphate accumulation and phytate hydrolysis can be used to promote U(VI) biomineralization in subsurface sediments; (vi) characterize the effect of uranium on phytate hydrolysis by a new microorganism isolated from uranium-contaminated sediments; (vii) utilize positron-emission tomography to label and track metabolically-active bacteria in soil columns, and (viii) study the stability of the uranium phosphate mineral product. Microarray analyses and mineral precipitation characterizations were conducted in collaboration with DOE SBR-funded investigatorsmore » at LBNL. Thus, microbial phosphorus metabolism has been shown to have a contributing role to uranium immobilization in the subsurface.« less

In marine sediments, Fe(III) is found predominantly as a solid. Recently, however, soluble species of Fe3+ complexed by natural organic ligands have been detected in coastal marine sediments with voltammetric microelectrodes. The role of soluble Fe3+ complexes in diagenesis is unknown. In anoxic conditions, soluble Fe3+ can effectively oxidize FeS2 and recycle iron and sulfur for use as terminal electron acceptors during natural organic matter (NOM) degradation. Alternatively, soluble Fe3+ complexes can catalyze the formation of FeS and FeS2 through the rapid chemical reduction of Fe3+ by dissolved sulfide. To better understand the role of soluble Fe3+ in the transformation of iron and sulfur in marine sediments, we incubated the first few centimeters of unvegetated salt marsh sediment in plug-flow reactors. Microbial iron reduction seemed to prevail in suboxic conditions, but sulfate reduction outcompeted microbial iron reduction in the presence of reactive organic metabolites. The dominance of sulfate reduction led to the complete removal of reactive iron oxides by precipitation of FeS. Experiments mimicking the enrichment of soluble Fe3+ complexes in reduced sediments show that soluble Fe3+ does not reoxidize FeS and pyrite; rather, it promotes pyrite precipitation by enhancing sulfate reduction via complex bacterial interactions. The rate of pyrite formation in the presence of soluble Fe3+ is much higher than previously reported in the literature, suggesting that soluble Fe3+ might promote alternative pathways for microbial degradation of NOM that ultimately results in the immobilization of Fe and S as reduced iron sulfide minerals.

Solid and colloidal iron oxides are commonly involved in early diagenesis. More readily available soluble Fe(III) should accelerate the cycling of iron (Fe) and sulfur (S) in sediments. Experiments with synthetic solutions (Taillefert et al. 2000) showed that soluble Fe(III) (i.e.

We conducted a study to determine the seasonal relationship between iron, sulfur, and phosphorus in the upper sediments and pore waters of a shallow intercoastal bay. From April 1999 to September 2000, sediment cores were collected from Rehoboth Bay, Delaware. Analyses of the sediments in the upper 4 cm revealed that redox conditions controlled Fe-S-P concentrations in the sediments, pore waters, and overlying water. Monthly sampling showed a marked decrease in the reactive solid phase P pool (ascorbate leachable fraction, ASC-P) and sharp increases in soluble P (measured as PO ) in pore waters and overlying waters, as the conditions became more reducing through32 4 out the summer months. These changes were paralleled by decreases in the amorphous Fe(III) (ascorbate leachable fraction, ASC-Fe) and total Fe(III)oxyhydroxide pools [dithionite extracted fraction, Fe(III) oxide] and increases in solid FeS/FeS2. The release of soluble P from sulfidic sediments to oxygenated overlying waters only occurred during periods of solid FeS/FeS2 production, which indicates that Fe(III) oxides act as a barrier to diffusive P flux. During these anoxic conditions, the regenerative P appears to induce secondary benthic algal blooms and promotes eutrophication in these inland bays through late summer. By the late fall and into early spring, sulfide production diminished and oxic conditions were reestablished as indicated by increases in solid amorphous and crystalline Fe(III) oxides and decreases in FeS/FeS2 concentrations. During this period, increasing ASC-Fe concentrations correlated with increases in ASC-P concentrations and decreases in pore-water PO . The seasonal correlations 32 4 between Fe-S-P indicate that Fe redox chemistry controls sediment P flux to the overlying water column.

The geochemical behavior of Co in aquatic systems has often been related to the presence of Fe and Mn particles. A few studies have shown that Co is exclusively associated with particulate Mn, but the dynamics of Co and Mn cycling have never been determined in real time under natural conditions. In this study, we used a combination of analytical techniques to study the temporal and spatial evolution of Mn microparticles (MnOx) over 2 weeks in the water column of a shallow stratified lake (Paul Lake, MI). We report a temporal accumulation of dissolved Mn at the oxic-anoxic transition, and we show that this accumulation is due to the reductive dissolution of Mn particles. The reductant has not been identified, but abiotic reduction by sigmaH2S and ferrous iron is excluded because they are produced below the zone of MnOx reduction. Hybridization of RNA isolated from Paul Lake with oligonucleotide probes targeting the delta proteobacteria, which include metal-reducing species, suggests that their activity is greatest at and just below the oxic-anoxic transition, so that Mn reduction may be influenced by bacterial activity. Mn-oxidizing bacteria were isolated from this zone as well. We also demonstrate that the dynamic evolution of MnOx has a direct influence on the distribution of Co in the water column of this lake: dissolved Co is released during the reductive dissolution of MnOx and accumulates at the redox interface.

Sulfur speciation was determined in real time in salt marsh microbial mats, subtidal sediments and hydrothermal vent diffuse flow waters using solid state gold-amalgam voltammetric microelectrodes. Chemical species were measured in situ without any sample manipulation or processing. The partially oxidized sulfur species detected were polysulfides, thiosulfate, elemental sulfur and tetrathionate. Fe(III) oxidation of hydrogen sulfide does not occur within the mats where microbially mediated processes are responsible for oxidation of H2S. In sediments and diffuse flow vent waters, Fe(III) phases are the direct oxidant of H2S. Sulfur speciation determined in this work is due to in situ biogeochemical processes and is not due to artefacts of sample manipulation. The voltammetric data show that polysulfides are the first detectable intermediate during sulfide oxidation which is consistent with previous laboratory studies.

The distributions of cobalt and manganese in the water column of Paul Lake, a small meromictic lake located in the upper Michigan peninsula, follow remarkably Similar patterns. At the oxycline, these elements show pronounced concentration gradients. In May 1994, Co and Mn increase from detection limits to 6 nM and 3 μM, respectively. The association between Co and Mn can be attributed to the sorption of cobalt to manganese hydrous oxides, and the redox-driven interconversion between dissolved Mn and particulate Mn-oxides species, which is often mediated by micro-organisms. In this paper, we have used a multi-method approach to the study of Co:Mn association in an aquatic system. First, using equilibrium calculations, we discuss the chemical speciation of dissolved Co and Mn in the water column. Second, we present a Transmission Electron Microscopic (TEM) characterization of individual Mn-rich micro-particles. These particles were primarily observed at the oxic/anoxic transition. Micrographs confirm the biological origin of the hydrous manganese oxides. Analytical Electron Microscopy clearly establishes that Co and Fe are scavenged by micro-organisms bearing a Mn-oxide crust. Co:Mn ratios were determined on individual particles by Energy Dispersive Spectrometry (EDS). The comparison of the average Co:Mn ratio in particles to the one in solution shows that Co is enriched in the Mn-oxides overgrowths. High resolution TEM-EDS analyses of environmental particles proves to be a powerful tool to unveil chemical associations that are difficult to deduce from changes in the water chemistry.

[1] The upper basin of Effingham Inlet possesses permanently anoxic bottom waters, with a water column redox transition zone typically occurring at least 40 m above the sediment-water interface. During our sampling campaign in April and July 2007, this redox transition zone was associated with sharp peaks in a variety of parameters, including soluble reactive phosphorus (SRP) and total particulate phosphorus (TPP). Based on sequential extraction results, TPP maxima exhibited preferential accumulation of an operationally defined class of loosely adsorbed organic phosphorus (P), which may contain a substantial fraction of polyphosphate (poly-P). This poly-P may furthermore be involved in the redox-dependent remobilization of SRP. For example, direct fluorometric analysis of poly-P content revealed that particulate inorganic poly-P was present at concentrations ranging from 1 to 9 nM P within and several meters above the TPP maximum. Below the depth of 1% oxygen saturation, however, particulate inorganic poly-P was undetectable (

International audience; The speciation of metal species extracted by diffusion gradient in thin films (DGT) devices during experimental deployments in simple metal-ligand synthetic solutions was numerically modeled, analyzed at steady state, and simulated in the dynamic regime. The modeled speciation of two well-known complexes (Cu-citrate and Cu-EDTA) are in good agreement with experimental data obtained in NaNO3 solutions. For any metal complex, the rate at which the metal accumulates on the chelating resin is proportional to the concentration of free metal in solution plus a fraction of the metal complex concentration in solution equivalent to zetaD(ML)/D-M. D-M and D-ML are the diffusion coefficients of the free and metal complex, respectively, and zeta characterizes the complex lability: it is defined as the fraction of metal complex lost when diffusing from the bulk solution to the chelating resin. Numerical simulations were used to explore the variations of zeta as a function of several operational and chemical parameters. Lability increases when the dissociation rate constant or the residence time of the metal complex within the hydrogel increase (i.e., by either increasing the thickness of the hydrogel or decreasing DML). Overall, the fraction of metal complex extracted by the DGT decreases when DML decreases, which confirms the ability of diffusion-restrictive hydrogels to separate the free metal fraction from complex solutions. Although the DGT model does not exactly comply with the voltammetric formalism, the lability criteria ATtau(1/2) used with voltammetric macroelectrodes is similar to the lability criteria zeta, except that it is valid for high metal ligand ratio. To determine free metal concentrations in aquatic systems using DGT, it is necessary to account for the presence of numerous ligands with different complexing properties. Soon, the numerical model will be improved to include additional ligands competing for the metal, and new experiments will be designed to discriminate between different labile complexes. Experimental results obtained with different DGT devices (of different hydrogel thicknesses, for example) could be interpreted in terms of conditional kinetic characteristics of the dominant metal-ligand complex in solution.

Gold/mercury amalgam (Au/Hg) microelectrodes with a diameter of 25 microm were developed for the detection of environmentally relevant analytes such as manganese and iron by scanning electrochemical microscopy (SECM), and applied to investigate the controlled dissolution of manganese carbonate (MnCO(3); rhodochrosite) in acidic conditions. Characterization of the amalgam electrode geometry via approach curves recorded during SECM experiments revealed Au/Hg microelectrodes with sphere cap geometry. Quantitative determination of Mn(2+) has been achieved by calibration of the Au/Hg microelectrode in bulk solution experiments. Subsequent SECM imaging experiments confirm the applicability of amalgam microelectrodes for imaging of Mn(2+) production during dissolution of MnCO(3) at pH 3.9. This study confirms feasibility and provides the fundamental basis of SECM imaging with amalgam microelectrodes to address biogeochemically relevant questions.

We report a laboratory and field study that demonstrates that soluble Fe(III) complexed to organic ligands exists in sediment porewaters. Synthetic solutions of Fe(III) with the ligand Tris were used to simulate organic complexation of Fe(III) in natural waters. Size fractionation using gel filtration chromatography shows that at least three different molecular mass species coexist. The molecular masses of FeIIIx−Trisy complexes increase with time, suggesting that aggregation occurs in solution. Soluble Fe(III) is detected by voltammetry at a mercury drop electrode when it is complexed by an organic ligand. Depending on the age of Fe(III), two voltammetric waves can be observed: at ca. −0.3 V for “freshly” formed Fe(III) and at a more negative potential for “aged” Fe(III). A mathematical model was successfully developed to assess a mechanism for this aging process. This model involves oxidation and adsorption of Fe(II), aggregation, and precipitation of Fe(III) complexes. The species formed are extremely...