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There remains a lack of knowledge regarding ecosystem transfer, transport processes, and mechanisms, which influence the long-term mobility of Pu-239 and Cs-137 in natural environments. Monitoring the distribution and migration of trace radioisotopes as ecosystem tracers has the potential to provide insight into the underlying mechanisms of geochemical cycles. This study investigated the distribution of anthropogenic radionuclides Pu-239 and Cs-137 along with total organic carbon, iron, and trace element in contaminated sediments of Pond B at the Savannah River Site (SRS). Pond B received reactor cooling water from 1961 to 1964, and trace amounts of Pu-239 and Cs-137 during operations. Our study collected sediment cores to determine concentrations of Pu-239, Cs-137, and major and minor elements in solid phase, pore water and an electrochemical method was used on wet cores to determine dissolved elemental concentrations. More than 50 years after deposition, Pu-239 and Cs-137 in sediments are primarily located in the upper 5 cm in area where deposition of particulate-bound contaminants was prevalent and located between 5 and 10 cm in areas of high sedimentation, showing a limited migration of Pu-239 and Cs-137. A Factor analysis demonstrated different sediment facies across the pond resulting in a range of geochemical processes controlling accumulation of Pu and Cs. Highest concentrations appear to be controlled by particulate input from the influent canal, dominated by clay, silt, and sand minerals bearing Fe. Elevated Pu-239 in the sediments were observed in areas with high organic matter and higher deposition rate relative to the Pond B system near the outlet indicating strong association of Pu with OM and particulates. Therefore, organic matter cycling likely plays a role in Pu redistribution between sediment and overlying pond water, and deposition in organic rich sediments accumulating near the outlet. Though Pu appears to have been distributed throughout the pond, Cs-137 concentrations remained the highest near the influent canal.

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.

Exploration of oxygen-depleted marine environments has consistently revealed novel microbial taxa and metabolic capabilities that expand our understanding of microbial evolution and ecology. Marine blue holes are shallow karst formations characterized by low oxygen and high organic matter content. They are logistically challenging to sample, and thus our understanding of their biogeochemistry and microbial ecology is limited. We present a metagenomic characterization of Amberjack Hole on the Florida continental shelf (Gulf of Mexico). Dissolved oxygen became depleted at the hole’s rim (32 m water depth), remained low but detectable in an intermediate hypoxic zone (40-75 m), and then increased to a secondary peak before falling below detection in the bottom layer (80-110 m), concomitant with increases in nutrients, dissolved iron, and a series of sequentially more reduced sulfur species. Microbial communities in the bottom layer contained heretofore undocumented levels of the recently discovered phylum Woesearchaeota (up to 58% of the community), along with lineages in the bacterial Candidate Phyla Radiation (CPR). Thirty-one high-quality metagenome-assembled genomes (MAGs) showed extensive biochemical capabilities for sulfur and nitrogen cycling, as well as for resisting and respiring arsenic. One uncharacterized gene associated with a CPR lineage differentiated hypoxic from anoxic zone communities. Overall, microbial communities and geochemical profiles were stable across two sampling dates in the spring and fall of 2019. The blue hole habitat is a natural marine laboratory that provides opportunities for sampling taxa with under-characterized but potentially important roles in redox-stratified microbial processes.

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.

Estuarine regions are generally considered a major source of atmospheric CO2, as a result of the high organic carbon (OC) mineralization rates in their water column and sediments. Despite this, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites near the sediment–water interface controls the flux of benthic alkalinity. This alkalinity may partially buffer metabolic CO2 generated by benthic OC respiration in sediments. Thus, sediments with high anaerobic respiration rates could contribute less to local acidification than previously thought. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lion, northwestern Mediterranean) in late summer to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH micro-profiles, voltammetric profiles and pore water composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. Benthic TA and DIC fluxes to the water column, ranging between 14 and 74 and 18 and 78 mmol m−2 d−1, respectively, were up to 8 times higher than dissolved oxygen uptake (DOU) rates (10.4±0.9 mmol m−2 d−1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. In the zone close to the river mouth, pore water redox species indicated that TA and DIC were mainly produced by microbial sulfate and iron reduction. Despite the complete removal of sulfate from pore waters, dissolved sulfide concentrations were low and significant concentrations of FeS were found, indicating the precipitation and burial of iron sulfide minerals with an estimated burial flux of 12.5 mmol m−2 d−1 near the river mouth. By preventing reduced iron and sulfide reoxidation, the precipitation and burial of iron sulfide increases the alkalinity release from the sediments during the spring and summer months. Under these conditions, the sediment provides a net source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters and weakens the partial pressure of CO2 increase in the bottom waters that would occur if only DIC was produced.

International audience; Carbon and silicon cycles at the Earth surface are linked to long-term variations of atmospheric CO2 and oceanic primary production. In these cycles, the river-sea interface is considered a biogeochemical hotspot, and deltas presently receive and preserve a major fraction of riverine particles in shallow water sediments. In contrast, periods of glacial maximum lowstand were characterized by massive exports of sediments to the deep-sea via submarine canyons and accumulation in deep-sea fans. Here, we calculate present-day mass balances for organic carbon (OC) and amorphous silica (aSi) in the terminal lobe complex of the Congo River deep-sea fan as an analogue for glacial periods. We show that this lobe complex constitutes a megasink with the current accumulation of 18 and 35% of the OC and aSi river input, respectively. This increases the estimates of organic carbon burial by 19% in the South Atlantic Ocean in a zone representing less than 0.01% of the basin. These megasinks might have played a role in carbon trapping in oceanic sediments during glacial times.

Estuarine regions are generally considered a net source of atmospheric CO2 as a result of the high organic carbon (OC) mineralization rates in the water column and their sediments. Yet, the intensity of anaerobic respiration processes in the sediments tempered by the reoxidation of reduced metabolites controls the net production of alkalinity from sediments that may partially buffer the metabolic CO2 generated by OC respiration. In this study, a benthic chamber was deployed in the Rhône River prodelta and the adjacent continental shelf (Gulf of Lions, NW Mediterranean) to assess the fluxes of total alkalinity (TA) and dissolved inorganic carbon (DIC) from the sediment. Concurrently, in situ O2 and pH microprofiles, electrochemical profiles, pore water and solid composition were measured in surface sediments to identify the main biogeochemical processes controlling the net production of alkalinity in these sediments. The benthic fluxes of TA and DIC, ranging between 14 and 74 mmol m−2 d−1 and 18 and 78 mmol m−2 d−1, respectively, were up to 8 times higher than the DOU fluxes (10.4 ± 0.9 mmol m−2 d−1) close to the river mouth, but their intensity decreased offshore, as a result of the decline in OC inputs. Low nitrate concentrations and strong pore water sulfate gradients indicated that the majority of the TA and DIC was produced by sulfate and iron reduction. Despite the complete removal of sulfate from the pore waters, dissolved sulfide concentrations were low due to the precipitation and burial of iron sulfide minerals (12.5 mmol m−2 d−1 near the river mouth), while soluble organic-Fe(III) complexes were concurrently found throughout the sediment column. The presence of organic-Fe(III) complexes together with low sulfide concentrations and high sulfate consumption suggests a dynamic system driven by the variability of the organic and inorganic particulate input originating from the river. By preventing reduced substances from being reoxidized, the precipitation and burial of iron sulfide decouples the iron and sulfur cycles from oxygen, therefore allowing a flux of alkalinity out of the sediments. In these conditions, the sediment provides a source of alkalinity to the bottom waters which mitigates the effect of the benthic DIC flux on the carbonate chemistry of coastal waters.

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.

Despite the undeniable effect of iron on shaping patterns of ocean productivity, the relative importance of the different sources of this limiting nutrient to the ocean is still under debate. Although global estimates indicate that the benthic input of iron to the oceans is significant, most studies have investigated continental margins exposed to either upwelling or large riverine inputs, environments that are not representative of the majority of the oceans. Additionally, the number of studies that report dissolved iron concentrations in continental slope sediments is limited, despite the fact that these regions between the shelf edge and the continental rise make up >5% of the sedimentary surface area of the global ocean. The sedimentary flux of iron has traditionally been considered negligible due to the rapid oxidation of Fe2+ in oxic waters and poor solubility of the Fe(III) product. The recent realization that ferric iron may be stabilized in solution by organic ligands during oxidation near the sediment-water interface suggests that a significant fraction of the dissolved iron pool may be present under the form organic-Fe(III) complexes that could eventually reach the overlying waters. In this study, the speciation and biogeochemical importance of iron was determined in intact sediment cores along a transect across the entire continental margin near Cape Lookout, North Carolina, a region not dominated by upwelling or riverine inputs that is representative of most passive continental margins. Rates of diffusive oxygen uptake (DOU) and maximum diffusive fluxes of both dissolved Fe2+and organic-Fe(III) complexes decreased from the coastal zone to the continental shelf, remained low on the shelf and the upper continental slope, but rebounded to reach a maximum in mid-slope sediments where concentrations of Fe(III) oxides were the highest along the transect. In turn, DOU decreased and dissolved iron was below detection in lower-slope sediments, indicating that mid-slope sediments represent depocenters where Fe(III) oxides and organic matter may accumulate. Pore water sulfate and sulfide concentrations as well as separate sediment incubations confirmed that sulfate reduction does not greatly influence the cycling of iron in these sediments. The production of dissolved organic-Fe(III) in these continental margin sediments is likely regulated by a combination of aerobic oxidation in the presence of natural organic ligands near the sediment-water interface, dissimilatory iron reduction, or chemical oxidation of Fe(II) complexed to natural organic ligands. Fluxes of Fe2+ and organic-Fe(III) complexes across the sediment-water interface were not observed. However, diffusive fluxes of Fe2+ and organic-Fe(III) complexes into the oxic zone of these sediments (

Controlled laboratory experiments were combined with field measurements to better understand the interactions between dissolved organic matter (DOM) and reduced iron in organic-rich peatlands. Addition of peat-derived humic acid extract (HA) to Sideroxydans lithotrophicus ES-1 liquid cultures led to higher cell numbers and up to 1.4 times higher Fe(II) oxidation rates compared to chemical controls. This effect was positively correlated with increasing HA concentrations. Similar Fe(III) (oxyhydr)oxide mineralogies were formed both abiotically and biotically irrespective of HA amendment, but minerals formed in the presence of ES-1 and HA were smaller. ES-1 growth with HA promoted aggregation of Fe(III) products in agarose-stabilized gradient tubes as shown by voltammetric profiling. In situ voltammetry in an acidic, iron-rich peatland revealed a gap between oxygen penetration and iron reduction that may reflect active Fe(II)-oxidizing microorganisms. The highest abundance of Fe(II) oxidizers Sideroxydans (4.9 × 107 gene copies gww-1) and Gallionella (1.5 × 107 gene copies gww-1) in the upper peat layer coincided with small-sized minerals resembling nanoparticulate ferrihydrite or goethite. Our results suggest that microbially mediated Fe(II) oxidation dominates in the presence of DOM leading to the formation of nano-sized biogenic Fe(III) (oxyhydr)oxides that might be readily bioavailable and likely important to iron and carbon cycling.

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 redox chemistry and speciation of Fe in both solid and dissolved phases were characterized in the organic- and Fe-rich sediments of the Satilla River estuary in South-East Georgia (USA) on a series of four cruises between July 2007 and January 2008. Results indicate that dissolved Fe is present in relatively high concentration in the overlying waters at the freshwater end of the estuary and flocculates along the river as the salinity increases downstream. Soluble organic–Fe(III) complexes comprise the majority of dissolved Fe (

The presently active region of the Congo deep-sea fan (around 330,000 km(2)), called the terminal lobes or lobe complex, covers an area of 2500 km(2) at 4700-5100 m water depth and 750-800 km offshore. It is a unique sedimentary area in the world ocean fed by a submarine canyon and a channel-levee system which presently deliver large amounts of organic carbon originating from the Congo River by turbidity currents. This particularity is due to the deep incision of the shelf by the Congo canyon, up to 30 km into the estuary, which funnels the Congo River sediments into the deep-sea. The connection between the river and the canyon is unique for major world rivers. In 2011, two cruises (WACS leg 2 and Congolobe) were conducted to simultaneously investigate the geology, organic and inorganic geochemistry, and micro- and macro-biology of the terminal lobes of the Congo deep-sea fan. Using this multidisciplinary approach, the morpho-sedimentary features of the lobes were characterized along with the origin and reactivity of organic matter, the recycling and burial of biogenic compounds, the diversity and function of bacterial and archaeal communities within the sediment, and the biodiversity and functioning of the faunal assemblages on the seafloor. Six different sites were selected for this study: Four distributed along the active channel from the lobe complex entrance to the outer rim of the sediment deposition zone, and two positioned cross-axis and at increasing distance from the active channel, thus providing a gradient in turbidite particle delivery and sediment age. This paper aims to provide the general context of this multidisciplinary study. It describes the general features of the site and the overall sampling strategy and provides the initial habitat observations to guide the other in-depth investigations presented in this special issue. Detailed bathymetry of each sampling site using 0.1-1 m resolution multibeam obtained with a remotely operated vehicle (ROV) shows progressive widening and smoothing of the channel-levees with increasing depth and reveals a complex morphology with channel bifurcations, erosional features and massive deposits. Dense ecosystems surveyed in the study area gather high density clusters of two large-sized species of symbiotic Vesicomyidae bivalves and microbial mats. These assemblages, which are rarely observed in sedimentary zones, resemble those based on chemosynthesis at cold-seep sites, such as the active pockmarks encountered along the Congo margin, and share with these sites the dominant vesicomyid species Christineconcha regab. Sedimentation rates estimated in the lobe complex range between 0.5 and 10 cm yr(-1), which is 2-3 orders of magnitude higher than values generally encountered at abyssal depths. The bathymetry, faunal assemblages and sedimentation rates make the Congo lobe complex a highly peculiar deep-sea habitat driven by high inputs of terrigenous material delivered by the Congo channel-levee system. (c) 2016 Elsevier Ltd. All rights reserved. ZAIANGO ANR Congolobe (ANR Blanc SIMI5-6) [11 BS56 030] IFREMER CEA through LSCE U.S. National Science Foundation [OCE-0831156] info:eu-repo/semantics/acceptedVersion

Although a number of techniques exist to measure the major and minor inorganic anions Cl-, NO2-, Br-, NO3-, or SO42- in marine waters and sediment porewaters, a single method that can quantify all five anions in a single step with a sufficiently low detection limit has yet to be developed. In this work, a novel ion-chromatographic separation procedure was developed that exploits the UV-absorbing properties of Br-, NO3-, and NO2-, as well as the suppression of eluent absorbance by high concentrations of Cl- and SO42- to quantify all these anions simultaneously in marine waters. If additional sensitivity for the minor anions Br-, NO3-, and NO2- is needed, NaCl can be used as eluent in a matrix elimination method that no longer allows for Cl- and SO42- determination. These methods are isocratic, require no chemical or electronic suppression, are not subject to interferences, and can resolve the anions in less than 18 min. The decrease in analysis time and the number of analyses required compared with conventional methods lowers the costs associated with laboratory analysis of marine samples. Last, the simplicity and good limits of detection make this separation method suitable for in situ analyses of marine waters and porewaters, and an in situ liquid chromatograph is currently under development for these applications.

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.

Geochemical profiles (SO 4 2- , H 2 S, CH 4 , δ 13 CH 4 ) and phylogenetic diversity of Archaea and Bacteria from two oceanographic cruises dedicated to the lobes sediments of the Congo deep-sea fan are presented in this paper. In this area, organic-rich turbidites reach 5000 m and allow the establishment of patchy cold-seep-like habitats including microbial mats, reduced sediments, and vesicomyid bivalves assemblages. These bivalves live in endosymbiosis with sulfur-oxidizing bacteria and use sulfides to perform chemosynthesis. In these habitats, unlike classical abyssal sediments, anoxic processes are dominant. Total oxygen uptake fluxes and methane fluxes measured with benthic chambers are in the same range as those of active cold-seep environments, and oxygen is mainly used for reoxidation of reduced compounds, especially in bacterial mats and reduced sediments. High concentrations of methane and sulfate co-exist in the upper 20 cm of sediments, and evidence indicates that sulfate-reducing microorganisms and methanogens co-occur in the shallow layers of these sediments. Simultaneously, anaerobic oxidation of methane (AOM) with sulfate as the electron acceptor is evidenced by the presence of ANMEs (ANaerobic MEthanotroph). Dissolved sulfide produced through the reduction of sulfate is reoxidized through several pathways depending on the habitat. These pathways include vesicomyid bivalves uptake (adults or juveniles in the bacterial mats habitats), reoxidation by oxygen or iron phases within the reduced sediment, or reoxidation by microbial mats. Sulfide uptake rates by vesicomyids measured in sulfide-rich sea water (90±18 mmol S m -2 d -1 ) were similar to sulfide production rates obtained by modelling the sulfate profile with different bioirrigation constants, highlighting the major control of vesicomyids on sulfur cycle in their habitats.

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.

Improper disposal of 1,4-dioxane and the chlorinated organic solvents trichloroethylene (TCE) and tetrachloroethylene (also known as perchloroethylene [PCE]) has resulted in widespread contamination of soil and groundwater. In the present study, a previously designed microbially driven Fenton reaction system was reconfigured to generate hydroxyl (HO˙) radicals for simultaneous transformation of source zone levels of single, binary, and ternary mixtures of TCE, PCE, and 1,4-dioxane. The reconfigured Fenton reaction system was driven by fed batch cultures of the Fe(III)-reducing facultative anaerobe Shewanella oneidensis amended with lactate, Fe(III), and contaminants and exposed to alternating anaerobic and aerobic conditions. To avoid contaminant loss due to volatility, the Fe(II)-generating, hydrogen peroxide-generating, and contaminant transformation phases of the microbially driven Fenton reaction system were separated. The reconfigured Fenton reaction system transformed TCE, PCE, and 1,4-dioxane either as single contaminants or as binary and ternary mixtures. In the presence of equimolar concentrations of PCE and TCE, the ratio of the experimentally derived rates of PCE and TCE transformation was nearly identical to the ratio of the corresponding HO˙ radical reaction rate constants. The reconfigured Fenton reaction system may be applied as an ex situ platform for simultaneous degradation of commingled TCE, PCE, and 1,4-dioxane and provides valuable information for future development of in situ remediation technologies. IMPORTANCE A microbially driven Fenton reaction system [driven by the Fe(III)-reducing facultative anaerobe S. oneidensis ] was reconfigured to transform source zone levels of TCE, PCE, and 1,4-dioxane as single contaminants or as binary and ternary mixtures. The microbially driven Fenton reaction may thus be applied as an ex situ platform for simultaneous degradation of at least three (and potentially more) commingled contaminants. Additional targets for ex situ and in situ degradation by the microbially driven Fenton reaction developed in the present study include multiple combinations of environmental contaminants susceptible to attack by Fenton reaction-generated HO˙ radicals, including commingled plumes of 1,4-dioxane, pentachlorophenol (PCP), PCE, TCE, 1,1,2-trichloroethane (TCA), and perfluoroalkylated substances (PFAS).

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.

Iron speciation in the Satilla River Estuary was investigated using competitive ligand equilibration–adsorptive cathodic stripping voltammetry (CLE-ACSV) with the ligand 1-nitroso-2-naphthol (1N2N). The blackwater Satilla River contains high concentrations of dissolved organic matter and iron, suggesting that it could provide a source of dissolved iron to the continental shelf. Total dissolved iron in the water column decreases along the estuary, likely due to flocculation and precipitation processes associated with the increase in salinity. Simultaneously, the percentage of dissolved organic-Fe(III) complexes measured by CLE-ACSV in overlying waters of sediment cores increases with salinity. The speciation of dissolved iron in the pore waters indicates that these complexes originate in the underlying sediments. Diffusive fluxes calculated from depth profiles in the sediments indicate that only 8% of the sedimentary flux of Fe(III) is delivered to the continental shelf during low riverine discharge. During normal flow conditions, however, the sediment flux of Fe(III) represents 63% of the total riverine flux of Fe(III). These findings suggest that the flux of dissolved iron to the continental shelf is controlled by the sedimentation of iron in the estuary and the remobilization of soluble organic-Fe(III) complexes produced either during iron reduction deep in the sediment or oxidation of Fe(II) close to the sediment–water interface. The Satilla River Estuary generates five to eight times higher concentrations of dissolved Fe(III) than the average major world rivers, suggesting that it is, along with other small blackwater rivers, currently underrepresented in world average river flux calculations. The importance of iron for primary productivity in the open ocean is well documented, and iron fertilization experiments have shown that iron additions can enhance primary productivity in high nutrient, low chlorophyll (HNLC) zones (Breitbarth et al. 2010). Iron is considered a limiting nutrient in marine waters, as the low solubility of Fe(III) limits the concentration of dissolved iron (, 0.4 mm)

A recently developed autonomous benthic lander equipped with an underwater potentiostat and a micromanipulator for in situ voltammetric depth profiling of main redox species in pore waters was deployed for 3 yr at multiple stations along the Satilla River estuary (Georgia, U.S.A.). These measurements revealed that biogeochemical processes in estuarine sediments vary seasonally and are influenced by riverine discharge. A prolonged drought decreased river discharge, altered the salinity gradient in the estuary, and profoundly affected anaerobic respiratory processes in the underlying sediments. Under normal hydrologic conditions, iron reduction was the dominant anaerobic respiratory process across the estuary, likely due to the significant supply of iron from the coastal plane and low salinity of the estuary. Under drought conditions, the salinity of the estuary increased to full seawater strength and carbon remineralization was enhanced significantly. Yet, sulfate reduction was only observed near the mouth of the estuary, whereas a substantial increase in iron reduction was distinctive upriver. Evidence indicates that the increase in iron-reducing activity during the drought resulted mainly from the deposition of mineral particles in the upper estuary when the salinity gradient increased. Altogether, this study demonstrates that the biogeochemical response of estuarine sediments to natural perturbations is rapid and that respiration processes are controlled by a combination of temperature, supply of inorganic and organic substrates, and hydrological processes. These findings also suggest that an increase in the frequency of droughts as a result of climate change may enhance the resiliency of iron-reducing bacteria in river-fed estuarine sediments.

Shewanella oneidensis MR-1 respires a wide range of anaerobic electron acceptors, including sparingly soluble Fe(III) oxides. In the present study, S. oneidensis was found to produce Fe(III)-solubilizing organic ligands during anaerobic Fe(III) oxide respiration, a respiratory strategy postulated to destabilize Fe(III) and produce more readily reducible soluble organic Fe(III). In-frame gene deletion mutagenesis, siderophore detection assays, and voltammetric techniques were combined to determine (i) if the Fe(III)-solubilizing organic ligands produced by S. oneidensis during anaerobic Fe(III) oxide respiration were synthesized via siderophore biosynthesis systems and (ii) if the Fe(III)-siderophore reductase was required for respiration of soluble organic Fe(III) as an anaerobic electron acceptor. Genes predicted to encode the siderophore (hydroxamate) biosynthesis system (SO3030 to SO3032), the Fe(III)-hydroxamate receptor (SO3033), and the Fe(III)-hydroxamate reductase (SO3034) were identified in the S. oneidensis genome, and corresponding in-frame gene deletion mutants were constructed. ΔSO3031 was unable to synthesize siderophores or produce soluble organic Fe(III) during aerobic respiration yet retained the ability to solubilize and respire Fe(III) at wild-type rates during anaerobic Fe(III) oxide respiration. ΔSO3034 retained the ability to synthesize siderophores during aerobic respiration and to solubilize and respire Fe(III) at wild-type rates during anaerobic Fe(III) oxide respiration. These findings indicate that the Fe(III)-solubilizing organic ligands produced by S. oneidensis during anaerobic Fe(III) oxide respiration are not synthesized via the hydroxamate biosynthesis system and that the Fe(III)-hydroxamate reductase is not essential for respiration of Fe(III)-citrate or Fe(III)-nitrilotriacetic acid (NTA) as an anaerobic electron acceptor.

Recent voltammetric analyses indicate that Shewanella putrefaciens strain 200 produces soluble organic-Fe(III) complexes during anaerobic respiration of sparingly soluble Fe(III) oxides. Results of the present study expand the range of Shewanella species capable of producing soluble organic-Fe(III) complexes to include Shewanella oneidensis MR-1. Soluble organic-Fe(III) was produced by S. oneidensis cultures incubated anaerobically with Fe(III) oxides, or with Fe(III) oxides and the alternate electron acceptor fumarate, but not in the presence of O(2), nitrate or trimethylamine-N-oxide. Chemical mutagenesis procedures were combined with a novel MicroElectrode Screening Array (MESA) to identify four (designated Sol) mutants with impaired ability to produce soluble organic-Fe(III) during anaerobic respiration of Fe(III) oxides. Two of the Sol mutants were deficient in anaerobic growth on both soluble Fe(III)-citrate and Fe(III) oxide, yet retained the ability to grow on a suite of seven alternate electron acceptors. The rates of soluble organic-Fe(III) production were proportional to the rates of iron reduction by the S. oneidensis wild-type and Sol mutant strains, and all four Sol mutants retained wild-type siderophore production capability. Results of this study indicate that the production of soluble organic-Fe(III) may be an important intermediate step in the anaerobic respiration of both soluble and sparingly soluble forms of Fe(III) by S. oneidensis.

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 situ capping has recently emerged as a remedial method for contaminated sediments and involves placing a layer of clean material at the sediment-water interface. The biogeochemical response of native sediment following capping, as well as the redoxenvironmentsthatdevelopwithinthe cap, are currently unknown. Column experiments were performed using voltammetric microelectrodes to characterize spatial and temporal distributions of biogeochemical processes in capped sediments under stagnant and upflow conditions. Oxygen penetration into sand caps extended only a few centimeters, thus maintaining underlying sediment anaerobic. Chemical species indicative of heterotrophic organic matter degradation (Mn2+, Fe2+, organic--FeIII(aq), FexSy(aq), sigmaH2S) were observed in stratified zones below the oxic layer. The majority of the overlying cap was subject to iron-reducing conditions under stagnant flow, while upflow conditions led to a compression of the redox zones toward the cap-water interface. Controls confirmed that sediment capping induced an upward, vertical shift of biogeochemical processes into the overlying cap, with redox stratification conserved. The redox conditions within the cap, specifically the predominance of iron reduction, should allow for reductive contaminant attenuation processes to extend into the overlying cap. These findings improve our understanding of the dynamics of biogeochemical processes following capping of contaminated sediments.

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.

Research investigating geochemical changes accompanying subsurface mixing of fresh and saline water has primarily focused on cation exchange and mineral dissolution/precipitation reactions. In this study, we report on redox species zonation at the boundaries of a freshwater lens confined beneath a small, permeable island surrounded by saline marshes and tidal creeks and located on the estuary side of Sapelo Island, Georgia. The spatial and temporal distribution of the chemical species in the aquifer implies that the freshwater lens resists saline intrusion by maintaining constant advection across the salinity gradient. As a result, the biogeochemical processes in this aquifer seem to have reached a quasi steady-state very close to equilibrium. Redox reactions associated with natural organic matter oxidation may also play an important role at the salinity transition. Surprisingly, aerobic respiration and microbial iron reduction seem to be the main pathways for natural organic matter oxidation. Sulfate reduction is not significant despite the high concentration of sulfate available, and manganese oxides are probably chemically reduced by dissolved sulfide and Fe 2+ . This study is the first to demonstrate that iron and manganese reduction takes place at the salinity transitions bounding both sides of an island freshwater lens and that microbial iron reduction accounts for most of anaerobic respiration of natural organic matter at these transitions.

Sediment and water can potentially be altered, chemically, physically and biologically as they are sampled at the seafloor, brought to the surface, processed and analysed. As a result, in situ observations of relatively undisturbed systems have become the goal of a growing body of scientists. Our understanding of sediment biogeochemistry and exchange fluxes was revolutionized by the introduction of benthic chambers and in situ micro-electrode profilers that allow for the direct measurement of chemical fluxes between sediment and water at the sea floor and for porewater composition. Since then, rapid progress in the technology of in situ sensors and benthic chambers (such as the introduction of gel probes, voltammetric electrodes or one- and two-dimensional optodes) have yielded major breakthroughs in the scientific understanding of benthic biogeochemistry. This paper is a synthesis of discussions held during the workshop on sediment biogeochemistry at the "Benthic Dynamics: in situ surveillance of the sediment-water interface" international conference (Aberdeen, UK--March 25-29, 2002). We present a review of existing in situ technologies for the study of benthic biogeochemistry dynamics and related scientific applications. Limitations and possible improvement (e.g., technology coupling) of these technologies and future development of new sensors are discussed. There are countless important scientific and technical issues that lend themselves to investigation using in situ benthic biogeochemical assessment. While the increasing availability of these tools will lead research in yet unanticipated directions, a few emerging issues include greater insight into the controls on organic matter (OM) mineralization, better models for the understanding of benthic fluxes to reconcile microelectrode and larger-scale chamber measurements, insight into the impacts of redox changes on trace metal behavior, new insights into geochemical reaction pathways in surface sediments, and a better understanding of contaminant fate in nearshore sediments.

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.