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1.
A <2.0-mm fraction of a mineralogically complex subsurface sediment containing goethite and Fe(II)/Fe(III) phyllosilicates was incubated with Shewanella putrefaciens (strain CN32) and lactate at circumneutral pH under anoxic conditions to investigate electron acceptor preference and the nature of the resulting biogenic Fe(II) fraction. Anthraquinone-2,6-disulfonate (AQDS), an electron shuttle, was included in select treatments to enhance bioreduction and subsequent biomineralization. The sediment was highly aggregated and contained two distinct clast populations: (i) a highly weathered one with “sponge-like” internal porosity, large mineral crystallites, and Fe-containing micas, and (ii) a dense, compact one with fine-textured Fe-containing illite and nano-sized goethite, as revealed by various forms of electron microscopic analyses. Approximately 10-15% of the Fe(III)TOT was bioreduced by CN32 over 60 d in media without AQDS, whereas 24% and 35% of the Fe(III)TOT was bioreduced by CN32 after 40 and 95 d in media with AQDS. Little or no Fe2+, Mn, Si, Al, and Mg were evident in aqueous filtrates after reductive incubation. Mössbauer measurements on the bioreduced sediments indicated that both goethite and phyllosilicate Fe(III) were partly reduced without bacterial preference. Goethite was more extensively reduced in the presence of AQDS whereas phyllosilicate Fe(III) reduction was not influenced by AQDS. Biogenic Fe(II) resulting from phyllosilicate Fe(III) reduction remained in a layer-silicate environment that displayed enhanced solubility in weak acid. The mineralogic nature of the goethite biotransformation product was not determined. Chemical and cryogenic Mössbauer measurements, however, indicated that the transformation product was not siderite, green rust, magnetite, Fe(OH)2, or Fe(II) adsorbed on phyllosilicate or bacterial surfaces. Several lines of evidence suggested that biogenic Fe(II) existed as surface associated phase on the residual goethite, and/or as a Fe(II)-Al coprecipitate. Sediment aggregation and mineral physical and/or chemical factors were demonstrated to play a major role on the nature and location of the biotransformation reaction and its products.  相似文献   

2.
Clay minerals and methanogens are ubiquitous and co-exist in anoxic environments, yet it is unclear whether methanogens are able to reduce structural Fe(III) in clay minerals. In this study, the ability of methanogen Methanosarcina barkeri to reduce structural Fe(III) in iron-rich smectite (nontronite NAu-2) and the relationship between iron reduction and methanogenesis were investigated. Bioreduction experiments were conducted in growth medium using three types of substrate: H2/CO2, methanol, and acetate. Time course methane production and hydrogen consumption were measured by gas chromatography. M. barkeri was able to reduce structural Fe(III) in NAu-2 with H2/CO2 and methanol as substrate, but not with acetate. The extent of bioreduction, as measured by the 1,10-phenanthroline method, was 7-13% with H2/CO2 as substrate, depending on nontronite concentration (5-10 g/L). The extent was higher when methanol was used as a substrate, reaching 25-33%. Methanogenesis was inhibited by Fe(III) reduction in the H2/CO2 culture, but enhanced when methanol was used. High charge smectite and biogenic silica formed as a result of bioreduction. Our results suggest that methanogens may play an important role in biogeochemical cycling of iron in clay minerals and may have important implications for the global methane budget.  相似文献   

3.
Microbial reduction of Fe(III) in clay minerals is an important process that affects properties of clay-rich materials and iron biogeochemical cycling in natural environments. Microbial reduction often ceases before all Fe(III) in clay minerals is exhausted. The factors causing the cessation are, however, not well understood. The objective of this study was to assess the role of biogenic Fe(II) in microbial reduction of Fe(III) in clay minerals nontronite, illite, and chlorite. Bioreduction experiments were performed in batch systems, where lactate was used as the sole electron donor, Fe(III) in clay minerals as the sole electron acceptor, and Shewanella putrefaciens CN32 as the mediator with and without an electron shuttle (AQDS). Our results showed that bioreduction activity ceased within two weeks with variable extents of bioreduction of structural Fe(III) in clay minerals. When fresh CN32 cells were added to old cultures (6 months), bioreduction resumed, and extents increased. Thus, cessation of Fe(III) bioreduction was not necessarily due to exhaustion of bioavailable Fe(III) in the mineral structure, but changes in cell physiology or solution chemistry, such as Fe(II) production during microbial reduction, may have inhibited the extent of bioreduction. To investigate the effect of Fe(II) inhibition on CN 32 reduction activity, a typical bioreduction process (consisting of lactate, clay, cells, and AQDS in a single tube) was separated into two steps: (1) AQDS was reduced by cells in the absence of clay; (2) Fe(III) in clays was reduced by biogenic AH2DS in the absence of cells. With this method, the extent of Fe(III) reduction increased by 45-233%, depending on the clay mineral involved. Transmission electron microscopy observation revealed a thick halo surrounding cell surfaces that most likely resulted from Fe(II) sorption/precipitation. Similarly, the inhibitory effect of Fe(II) sorbed onto clay surfaces was assessed by presorbing a certain amount of Fe(II) onto clay surfaces followed by AH2DS reduction of Fe(III). The reduction extent consistently decreased with an increasing amount of presorbed Fe(II). The relative reduction extent [i.e., the reduction extent normalized to that when the amount of presorbed Fe(II) was zero] was similar for all clay minerals studied and showed a systematic decrease with an increasing clay-presorbed Fe(II) concentration. These results suggest a similar inhibitory effect of clay-sorbed Fe(II) for different clay minerals. An equilibrium thermodynamic model was constructed with independently estimated parameters to evaluate whether the observed cessation of Fe(III) reduction by AH2DS was due to exhaustion of reaction free energy. Model-calculated reduction extents were, however, over 50% higher than experimentally measured, indicating that other factors, such as blockage of the electron transfer chain and mineralogy, restricted the reduction extent. Another important result of this study was the relative reducibility of Fe(III) in different clays: nontronite > chlorite > illite. This order was qualitatively consistent with the differences in the crystal structure and layer charge of these minerals.  相似文献   

4.
To assess the dynamics of microbially mediated U-clay redox reactions, we examined the reduction of iron(III)-rich nontronite NAu-2 and uranium(VI) by Shewanella oneidensis MR-1. Bioreduction experiments were conducted with combinations and varied concentrations of MR-1, nontronite, U(VI) and the electron shuttle anthraquinone-2,6-disulfonate (AQDS). Abiotic experiments were conducted to quantify U(VI) sorption to NAu-2, the reduction of U(VI) by chemically-reduced nontronite-Fe(II), and the oxidation of uraninite, U(IV)O2(s), by nontronite-Fe(III). When we incubated S. oneidensis MR-1 at lower concentration (0.5 × 108 cell mL−1) with nontronite (5.0 g L−1) and U(VI) (1.0 mM), little U(VI) reduction occurred compared to nontronite-free incubations, despite the production of abundant Fe(II). The addition of AQDS to U(VI)- and nontronite-containing incubations enhanced both U(VI) and nontronite-Fe(III) reduction. While U(VI) was completely reduced by S. oneidensis MR-1 at higher concentration (1.0 × 108 cell mL−1) in the presence of nontronite, increasing concentrations of nontronite led to progressively slower rates of U(VI) reduction. U(VI) enhanced nontronite-Fe(III) reduction and uraninite was oxidized by nontronite-Fe(III), demonstrating that U served as an effective electron shuttle from S. oneidensis MR-1 to nontronite-Fe(III). The electron-shuttling activity of U can explain the lack or delay of U(VI) reduction observed in the bulk solution. Little U(VI) reduction was observed in incubations that contained chemically-reduced nontronite-Fe(II), suggesting that biologic U(VI) reduction drove U valence cycling in these systems. Under the conditions used in these experiments, we demonstrate that iron-rich smectite may inhibit or delay U(VI) bioreduction.  相似文献   

5.
99Technetium (99Tc) is a fission product of uranium-235 and plutonium-239 and poses a high environmental hazard due to its long half-life (t1/2 = 2.13 × 105 y), abundance in nuclear wastes, and environmental mobility under oxidizing conditions [i.e., Tc(VII)]. Under reducing conditions, Tc(VII) can be reduced to insoluble Tc(IV). Ferrous iron, either in aqueous form (Fe2+) or in mineral form [Fe(II)], has been used to reduce Tc(VII) to Tc(IV). However, the reactivity of Fe(II) from clay minerals, other than nontronite, toward immobilization of Tc(VII) and its role in retention of reduced Tc(IV) has not been investigated. In this study the reactivity of a suite of clay minerals toward Tc(VII) reduction and immobilization was evaluated. The clay minerals chosen for this study included five members in the smectite-illite (S-I) series, (montmorillonite, nontronite, rectorite, mixed layered I-S, and illite), chlorite, and palygorskite. Surface Fe-oxides were removed from these minerals with a modified dithionite-citrate-bicarbonate (DCB) procedure. The total structural Fe content of these clay minerals, after surface Fe-oxide removal, ranged from 0.7% to 30.4% by weight, and the structural Fe(III)/Fe(total) ratio ranged from 45% to 98%. X-ray diffraction (XRD) and Mössbauer spectroscopy results showed that after Fe oxide removal the clay minerals were free of Fe-oxides. Scanning electron microscopy (SEM) revealed that little dissolution occurred during the DCB treatment. Bioreduction experiments were performed in bicarbonate buffer (pH-7) with structural Fe(III) in the clay minerals as the sole electron acceptor, lactate as the sole electron donor, and Shewanella putrefaciens CN32 cells as a mediator. In select tubes, anthraquinone-2,6-disulfate (AQDS) was added as electron shuttle to facilitate electron transfer. In the S-I series, smectite (montmorillonite) was the most reducible (18% and 41% without and with AQDS, respectively) and illite the least (1% for both without and with AQDS). The extent and initial rate of bioreduction were positively correlated with the percent smectite in the S-I series (i.e., layer expandability). Fe(II) in the bioreduced clay minerals subsequently was used to reduce Tc(VII) to Tc(IV) in PIPES buffer. Similar to the trend of bioreduction, in the S-I series, reduced NAu-2 showed the highest reactivity toward Tc(VII), and reduced illite exhibited the least. The initial rate of Tc(VII) reduction, after normalization to clay and Fe(II) concentrations, was positively correlated with the percent smectite in the S-I series. Fe(II) in chlorite and palygorskite was also reactive toward Tc(VII) reduction. These data demonstrate that crystal chemical parameters (layer expandability, Fe and Fe(II) contents, and surface area, etc.) play important roles in controlling the extent and rate of bioreduction and the reactivity toward Tc(VII) reduction. Reduced Tc(IV) resides within clay mineral matrix, and this association could minimize any potential of reoxidation over long term.  相似文献   

6.
Reaction-based modeling of quinone-mediated bacterial iron(III) reduction   总被引：1，自引：0，他引：1  
This paper presents and validates a new paradigm for modeling complex biogeochemical systems using a diagonalized reaction-based approach. The bioreduction kinetics of hematite (α-Fe2O3) by the dissimilatory metal-reducing bacterium (DMRB) Shewanella putrefaciens strain CN32 in the presence of the soluble electron shuttling compound anthraquinone-2,6-disulfonate (AQDS) is used for presentation/validation purposes. Experiments were conducted under nongrowth conditions with H2 as the electron donor. In the presence of AQDS, both direct biological reduction and indirect chemical reduction of hematite by bioreduced anthrahydroquinone-2,6-disulfonate (AH2DS) can produce Fe(II). Separate experiments were performed to describe the bioreduction of hematite, bioreduction of AQDS, chemical reduction of hematite by AH2DS, Fe(II) sorption to hematite, and Fe(II) biosorption to DMRB. The independently determined rate parameters and equilibrium constants were then used to simulate the parallel kinetic reactions of Fe(II) production in the hematite-with-AQDS experiments. Previously determined rate formulations/parameters for the bioreduction of hematite and Fe(II) sorption to hematite were systematically tested by conducting experiments with different initial conditions. As a result, the rate formulation/parameter for hematite bioreduction was not modified, but the rate parameters for Fe(II) sorption to hematite were modified slightly. The hematite bioreduction rate formulation was first-order with respect to hematite ”free“ surface sites and zero-order with respect to DMRB based on experiments conducted with variable concentrations of hematite and DMRB. The AQDS bioreduction rate formulation was first-order with respect to AQDS and first-order with respect to DMRB based on experiments conducted with variable concentrations of AQDS and DMRB. The chemical reduction of hematite by AH2DS was fast and considered to be an equilibrium reaction. The simulations of hematite-with-AQDS experiments were very sensitive to the equilibrium constant for the hematite-AH2DS reaction. The model simulated the hematite-with-AQDS experiments well if it was assumed that the ferric oxide “surface” phase was more disordered than pure hematite. This is the first reported study where a diagonalized reaction-based model was used to simulate parallel kinetic reactions based on rate formulations/parameters independently obtained from segregated experiments.  相似文献   

7.
Iron-rich clay minerals are abundant in the natural environment and are an important source of iron for microbial metabolism. The objective of this study was to understand the mechanism(s) of enhanced reduction of Fe(III) in iron-rich 2:1 clay minerals under sulfate-reducing conditions. In particular, biogenic reduction of structural Fe(III) in nontronite NAu-2, an Fe-rich smectite-group mineral, was studied using a Desulfovibrio spp. strain G-11 with or without amended sulfate. The microbial production of Fe(II) from NAu-2 is about 10% of total structural Fe(III) (30 mM) when Fe(III) is available as the sole electron acceptor. The measured production of Fe(II), however, can reach 29% of the total structural Fe(III) during sulfate reduction by G-11 when sulfate (50 mM) is concurrently added with NAu-2. In contrast, abiotic production of Fe(II) from the reaction of NAu-2 with Na2S (50 mM) is only ca. 7.5% of the total structural Fe(III). The enhanced reduction of structural Fe(III) by G-11, particularly in the presence of sulfate, is closely related to the growth rate and metabolic activities of the bacteria. Analyses by X-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy reveal significant changes in the structure and composition of NAu-2 during its alteration by bacterial sulfate reduction. G-11 can also derive nutrients from NAu-2 to support its growth in the absence of amended minerals and vitamins. Results of this study suggest that sulfate-reducing bacteria may play a more significant role than previously recognized in the cycling of Fe, S, and other elements during alteration of Fe-rich 2:1 clay minerals and other silicate minerals.  相似文献   

8.
The potential for reduction of 99TcO4−(aq) to poorly soluble 99TcO2 · nH2O(s) by biogenic sediment-associated Fe(II) was investigated with three Fe(III)-oxide containing subsurface materials and the dissimilatory metal-reducing subsurface bacterium Shewanella putrefaciens CN32. Two of the subsurface materials from the U.S. Department of Energy’s Hanford and Oak Ridge sites contained significant amounts of Mn(III,IV) oxides and net bioreduction of Fe(III) to Fe(II) was not observed until essentially all of the hydroxylamine HCl-extractable Mn was reduced. In anoxic, unreduced sediment or where Mn oxide bioreduction was incomplete, exogenous biogenic TcO2 · nH2O(s) was slowly oxidized over a period of weeks. Subsurface materials that were bioreduced to varying degrees and then pasteurized to eliminate biological activity, reduced TcO4−(aq) at rates that generally increased with increasing concentrations of 0.5 N HCl-extractable Fe(II). Two of the sediments showed a common relationship between extractable Fe(II) concentration (in mM) and the first-order reduction rate (in h−1), whereas the third demonstrated a markedly different trend. A combination of chemical extractions and 57Fe Mössbauer spectroscopy were used to characterize the Fe(III) and Fe(II) phases. There was little evidence of the formation of secondary Fe(II) biominerals as a result of bioreduction, suggesting that the reactive forms of Fe(II) were predominantly surface complexes of different forms. The reduction rates of Tc(VII)O4− were slowest in the sediment that contained plentiful layer silicates (illite, vermiculite, and smectite), suggesting that Fe(II) sorption complexes on these phases were least reactive toward pertechnetate. These results suggest that the in situ microbial reduction of sediment-associated Fe(III), either naturally or via redox manipulation, may be effective at immobilizing TcO4−(aq) associated with groundwater contaminant plumes.  相似文献   

9.
The sorption of 57Fe(II) onto an Fe-free, mineralogically pure and Ca-saturated synthetic montmorillonite sample (structural formula: Ca0.15(Al1.4Mg0.6)(Si4)O10(OH,F)2), was studied as a function of pH under strictly anoxic conditions (N2 glove box atmosphere, O2 content <1 ppm), using wet chemistry and cryogenic (T = 77 K) 57Fe Mössbauer spectrometry. No Fe(III) was detected in solution at any pH. However, in pH conditions where Fe(II) is removed from solution, a significant amount of surface-bound Fe(III) was produced, which increased with pH from 0% to 3% of total Fe in a pre-sorption edge region (i.e. at pH < 7.5 where about 15% of total Fe is sorbed) to 7% of total Fe when all Fe is sorbed. At low pH, where the pre-sorption edge plateau occurs (2 < pH < 7.5), the total sorbed-Fe amount remained constant but, within this sorbed-Fe pool, the Fe(III)/Fe(II) ratio increased with pH, from 0.14 at pH 2 up to 0.74 at pH 7. The pre-sorption edge plateau is interpreted as cation exchange on interlayer surfaces together with a sorption phenomenon occurring on highly reactive (i.e. high affinity) surface sites. As pH increases and protons are removed from the clay edge surface, we propose that more and more of these highly reactive sites acquire a steric configuration that stabilizes Fe(III) relative to Fe(II), thereby inducing a Fe to clay particle electron transfer. A sorption model based on cation exchange combined with surface complexation and electron transfers reproduces both wet chemical as well as the Mössbauer spectrometric results. The mechanism is fully reversible: sorbed-Fe is reduced as pH decreases (Mössbauer solid-state analyses) and all Fe returned to solution is returned as Fe(II) (solution analyses). This would not be the case if the observed oxidations were due to contaminant oxidizing agents in solution. The present work shows that alternating pH may induce surface redox phenomena in the absence of an electron acceptor in solution other than H2O.  相似文献   

10.
The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of FeTOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.  相似文献   

11.
Characterization of Fe(III) (hydr)oxides in soils near the Ichinokawa mine was conducted using X-ray absorption fine structure (XAFS) and Mössbauer spectroscopies, and the structural changes were correlated with the release of As into pore-water. The Eh values decreased monotonically with depth. Iron is mainly present as poorly-ordered Fe(III) (hydr)oxides, such as ferrihydrite, over a wide redox range (from Eh = 360 to −140 mV). Structural details of the short-range order of these Fe(III) (hydr)oxides were examined using Mössbauer spectroscopy by comparing the soil phases with synthesized ferrihydrite samples having varying crystallinities. The crystallinity of the soil Fe (hydr)oxides decreased slightly with depth and Eh. Thus, within the redox range of this soil profile, ferrihydrite dominated, even under very reducing conditions, but the crystalline domain size, and, potentially, particle size, changed with the variation in Eh. In the soil–water system examined here, where As concentration and the As(III)/As(V) ratio in soil water increased with depth, ferrihydrite persisted and maintained or even enhanced its capacity for As retention with increased reducing conditions. Therefore, it is concluded that As release from these soils largely depends on the transformation of As(V) to As(III) rather than reductive dissolution of Fe(III) (hydr)oxide.  相似文献   

12.
Mössbauer spectra of glauconite and nontronite recorded at temperatures down to 1.3K and in applied fields up to 4.5 T show that Fe III spin configurations are respectively ferromagnetic and antiferromagnetic. It is shown that in a particular material depending on the distribution and concentration of Fe III in the silicate sheet either mode might occur. A new model of competing nearest-neighbour (J 1) and next-nearest-neighbour (J 2) magnetic exchange interactions in the triangular lattice is introduced to account for the results. From available magnetic susceptibilities we estimate ∣J 1∣～6∣J 2∣. The results lead to the conclusion that the Fe III cations are highly ordered in glauconite and occupy cis sites so as to maximize their mutual separations.  相似文献   

13.
In the first known kinetic application of the technique, synchrotron 57Fe-Mössbauer spectroscopy was used to follow the rate of heterogeneous electron transfer between aqueous reagents and a solid phase containing Fe. The solid, a synthetic 57Fe-enriched Fe(III)-bearing pyroaurite-like phase having terephthalate (TA) in the interlayer [Mg3Fe(OH)8(TA)0.5 · 2H2O], was reduced by Na2S2O4 and then reoxidized by K2Cr2O7 by means of a novel flow-through cell. Synchrotron Mössbauer spectra were collected in the time domain at 30-s intervals. Integration of the intensity obtained during a selected time interval in the spectra allowed sensitive determination of Fe(II) content as a function of reaction time. Analysis of reaction end member specimens by both the synchrotron technique and conventional Mössbauer spectroscopy yielded comparable values for Mössbauer parameters such as center shift and Fe(II)/Fe(III) area ratios. Slight differences in quadrupole splitting values were observed, however. A reactive diffusion model was developed that fit the experimental Fe(II) kinetic data well and allowed the extraction of second-order rate constants for each reaction. Thus, in addition to rapidly collecting high quality Mössbauer data, the synchrotron technique seems well suited for aqueous rate experiments as a result of the penetrating power of 14.4 keV X-rays and high sensitivity to Fe valence state.  相似文献   

14.
The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.  相似文献   

15.
Sorption of contaminants such as arsenic (As) to natural Fe(III) (oxyhydr)oxides is very common and has been demonstrated to occur during abiotic and biotic Fe(II) oxidation. The molecular mechanism of adsorption- and co-precipitation of As has been studied extensively for synthetic Fe(III) (oxyhydr)oxide minerals but is less documented for biogenic ones. In the present study, we used Fe and As K-edge X-ray Absorption Near Edge Structure (XANES), extended X-ray Absorption Fine Structure (EXAFS) spectroscopy, Mössbauer spectroscopy, XRD, and TEM in order to investigate the interactions of As(V) and As(III) with biogenic Fe(III) (oxyhydr)oxide minerals formed by the nitrate-reducing Fe(II)-oxidizing bacterium Acidovorax sp. strain BoFeN1. The present results show the As immobilization potential of strain BoFeN1 as well as the influence of As(III) and As(V) on biogenic Fe(III) (oxyhydr)oxide formation. In the absence of As, and at low As loading (As:Fe ≤ 0.008 mol/mol), goethite (Gt) formed exclusively. In contrast, at higher As/Fe ratios (As:Fe = 0.020-0.067), a ferrihydrite (Fh) phase also formed, and its relative amount systematically increased with increasing As:Fe ratio, this effect being stronger for As(V) than for As(III). Therefore, we conclude that the presence of As influences the type of biogenic Fe(III) (oxyhydr)oxide minerals formed during microbial Fe(II) oxidation. Arsenic-K-edge EXAFS analysis of biogenic As-Fe-mineral co-precipitates indicates that both As(V) and As(III) form inner-sphere surface complexes at the surface of the biogenic Fe(III) (oxyhydr)oxides. Differences observed between As-surface complexes in BoFeN1-produced Fe(III) (oxyhydr)oxide samples and in abiotic model compounds suggest that associated organic exopolymers in our biogenic samples may compete with As oxoanions for sorption on Fe(III) (oxyhydr)oxides surfaces. In addition HRTEM-EDXS analysis suggests that As(V) preferentially binds to poorly crystalline phases, such as ferrihydrite, while As(III) did not show any preferential association regarding Fh or Gt.  相似文献   

16.
Phosphorus is one of the nutrients most commonly limiting net primary production in soils of humid tropical forests, mainly because insoluble Al and Fe phosphates and strong sorption to Fe(III) (hydr)oxides remove P from the bioavailable pool. Recent field studies have suggested, however, that this loss may be balanced by organic P accumulation under a wet moisture regime (>3350 mm annual precipitation). It has been hypothesized that, as the moisture regime changes from dry to mesic to wet, periods of anoxic soil conditions increase in intensity and duration, depleting Fe(III) (hydr)oxides and releasing sorbed P, but also slowing organic matter turnover, thus shifting the repository of soil P from minerals to humus. Almost no quantitative information is available concerning the coupled biogeochemical behavior of Fe and P in highly weathered forest soils that would allow examination of this hypothesis. In this paper, we report a laboratory incubation study of the effects of biotic Fe(III) (hydr)oxide reduction on P solubilization in a humid tropical forest soil (Ultisol) under a wet moisture regime (3000-4000 mm annual rainfall). The objectives of our study were: (1) to quantify Fe(III) reduction and P solubilization processes in a highly weathered forest soil expected to typify the hypothesized mineral dissolution-organic matter accumulation balance; (2) to examine the influence of electron shuttling on these processes using anthraquinone-2,6-disulfonate (AQDS), a well-known surrogate for the semiquinone electron shuttles in humic substances, as an experimental probe; and (3) to characterize the chemical forms of Fe(II) and P produced under anoxic conditions, both with and without AQDS. Two series of short-term incubation experiments were carried out, one without AQDS and another with an initial AQDS concentration of 150 μM. We measured pH, pE, and the production of Fe(II), total Fe [Fe(II) + Fe(III)], inorganic P, total P (inorganic P + organic P), and biogenic gases (CO2, H2 and CH4). The same positive correlation was found between soluble P release and soluble Fe(II) production throughout incubation, implying that reduction of Fe(III) solubilized P. The Fe(II) produced was mainly particulate, evidently due to the formation of Fe(II) solid phases. Thermodynamic calculations indicated that precipitation of siderite and, in the presence of AQDS, vivianite was favored under the anoxic conditions that developed rapidly in the soil suspensions. Inorganic soluble P released during incubation was very small, indicating that the soluble P produced was mainly in organic form, which is consistent with the hypothesis that P accumulates in soil humus. Our net CO2 production, H2 consumption, and Fe(II) production data all suggested that reductive dissolution of Fe(III) (hydr)oxides was a terminal electron-accepting process coupled both to H2 consumption and organic C oxidation by the native population of microorganisms in the soil. Addition of AQDS accelerated the production of Fe(II) and the release of soluble P, while hastening the decline in H2 gas levels and suppressing CH4 production. However, throughout incubation, the same quantitative relationships between soluble Fe(II) and P, and between pE and pH, were found, irrespective of AQDS addition. Thus we conclude that, in our soil incubation experiments, added AQDS functioned with the native microbial population solely as an electron shuttle catalyzing Fe(III) reduction. Whether humic substances in the soil also can act as electron shuttles in this way is a matter for future investigation.  相似文献   

17.
Experiments were performed herein to investigate the rates and products of heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to hematite and goethite, and by Fe(II) associated with a dithionite-citrate-bicarbonate (DCB) reduced natural phyllosilicate mixture [structural, ion-exchangeable, and edge-complexed Fe(II)] containing vermiculite, illite, and muscovite. The heterogeneous reduction of Tc(VII) by Fe(II) adsorbed to the Fe(III) oxides increased with increasing pH and was coincident with a second event of adsorption. The reaction was almost instantaneous above pH 7. In contrast, the reduction rates of Tc(VII) by DCB-reduced phyllosilicates were not sensitive to pH or to added that adsorbed to the clay. The reduction kinetics were orders of magnitude slower than observed for the Fe(III) oxides, and appeared to be controlled by structural Fe(II). The following affinity series for heterogeneous Tc(VII) reduction by Fe(II) was suggested by the experimental results: aqueous Fe(II) ∼ adsorbed Fe(II) in phyllosilicates [ion-exchangeable and some edge-complexed Fe(II)] ? structural Fe(II) in phyllosilicates ? Fe(II) adsorbed on Fe(III) oxides. Tc-EXAFS spectroscopy revealed that the reduction products were virtually identical on hematite and goethite that were comprised primarily of sorbed octahedral TcO2 monomers and dimers with significant Fe(III) in the second coordination shell. The nature of heterogeneous Fe(III) resulting from the redox reaction was ambiguous as probed by Tc-EXAFS spectroscopy, although Mössbauer spectroscopy applied to an experiment with 56Fe-goethite with adsorbed 57Fe(II) implied that redox product Fe(III) was goethite-like. The Tc(IV) reduction product formed on the DCB-reduced phyllosilicates was different from the Fe(III) oxides, and was more similar to Tc(IV) oxyhydroxide in its second coordination shell. The heterogeneous reduction of Tc(VII) to less soluble forms by Fe(III) oxide-adsorbed Fe(II) and structural Fe(II) in phyllosilicates may be an important geochemical process that will proceed at very different rates and that will yield different surface species depending on subsurface pH and mineralogy.  相似文献   

18.
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19.
The toxicity and mobility of the redox-active metalloid As strongly depends on its oxidation state, with As(III) (arsenite) being more toxic and mobile than As(V) (arsenate). It is, therefore, necessary to know the biogeochemical processes potentially influencing As redox state to understand and predict its environmental behavior. The first part of this presentation will discuss the quantification of As redox changes by pH-neutral mineral suspensions of goethite [α-FeIIIOOH] amended with Fe(II) using wet-chemical and synchrotron X-ray absorption (XANES) analysis (Amstaetter et al., 2010). First, it was found that goethite itself did not oxidize As(III). Second, in contrast to thermodynamic predictions, Fe(II)–goethite systems did not reduce As(V). However, surprisingly, rapid oxidation of As(III) to As(V) was observed in Fe(II)–goethite systems. Iron speciation and mineral analysis by Mössbauer spectroscopy showed rapid formation of 57Fe–goethite after 57Fe(II) addition and the formation of a so far unidentified additional Fe(II) phase. No other Fe(III) phase could be detected by Mössbauer spectroscopy, EXAFS, scanning electron microscopy, X-ray diffraction or high-resolution transmission electron microscopy. This suggests that reactive Fe(III) species form as an intermediate Fe(III) phase upon Fe(II) addition and electron transfer into bulk goethite but before crystallization of the newly formed Fe(III) as goethite.The second part of the presentation will show that semiquinone radicals produced during microbial or chemical reduction of a humic substance model quinone (AQDS, 9,10-anthraquinone-2,6-disulfonic acid) can react with As and change its redox state (Jiang et al., 2009). The results of these experiments showed that these semiquinone radicals are strong oxidants and oxidize arsenite to arsenate, thus decreasing As toxicity and mobility. The oxidation of As(III) depended strongly on pH. More arsenite (up to 67.3%) was oxidized at pH 11 compared to pH 7 (12.6% oxidation) and pH 3 (0.5% oxidation). In addition to As(III) oxidation by semiquinone radicals, hydroquinones that were also produced during quinone reduction, reduced As(V) to As(III) at neutral and acidic pH values (less than 12%) but not at alkaline pH. In an attempt to understand the observed redox reactions between As and reduced/oxidized quinones present in humic substances, the radical content in reduced AQDS solutions was quantified and Eh-pH diagrams were constructed. Both the radical quantification and the Eh-pH diagram allowed explaining the observed redox reactions between the reduced AQDS solutions and the As.In summary these studies indicate that in the simultaneous presence of Fe(III) oxyhydroxides, Fe(II), and humic substances as commonly observed in environments inhabited by Fe-reducing microorganisms, As(III) oxidation can occur. This potentially explains the presence of As(V) in reduced groundwater aquifers.  相似文献   

20.
Structural Fe(II) has been shown to reduce several oxidized environmental contaminants, including NO3, chlorinated solvents, Cr(VI), and U(VI). Studies investigating reduction of U(VI) by soils and sediments, however, suggest that abiotic reduction of U(VI) by Fe(II) is not significant, and that direct enzymatic reduction of U(VI) by metal-reducing bacteria is required for U(VI) immobilization as U(IV). Here evidence is presented for abiotic reduction and immobilization of U(VI) by structural Fe(II) in a redoximorphic soil collected from a hillside spring in Iowa. Oxidation of Fe(II) in the soil after reaction with U(VI) was demonstrated by Mössbauer spectroscopy and reduction of U(VI) by the pasteurized soil using U LIII-edge X-ray absorption spectroscopy (XAS). XAS indicates that both reduced U(IV) and oxidized U(VI) or U(V) are present after U(VI) interaction with the Fe(II) containing soil. The EXAFS data show the presence of a non-uraninite U(IV) phase and evidence of the oxidized U(V) or U(VI) fraction being present as a non-uranyl species. Little U(VI) reduction is observed by soil that has been exposed to air and oxidation of Fe(II) to goethite has occurred. Soil characterization based on chemical extractions, Mössbauer spectroscopy, and Fe K-edge XAS indicate that the majority of Fe(II) in the soil is structural in nature, existing in clay minerals and possibly a green rust-like phase. These data provide compelling evidence for abiotic reduction of U(VI) by structural Fe(II) from soil near Fe-rich oxic–anoxic boundaries in natural environments. The work highlights the potential for abiotic reduction of U(VI) by Fe(II) in reduced, Fe-rich environments.  相似文献   

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