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1.
The mobility and toxicity of Cr within surface and subsurface environments is diminished by the reduction of Cr(VI) to Cr(III). The reduction of hexavalent chromium can proceed via chemical or biological means. Coupled processes may also occur including reduction via the production of microbial metabolites, including aqueous Fe(II). The ultimate pathway of Cr(VI) reduction will dictate the reaction products and hence the solubility of Cr(III). Here, we investigate the fate of Cr following a coupled biotic-abiotic reduction pathway of chromate under iron-reducing conditions. Dissimilatory bacterial reduction of two-line ferrihydrite indirectly stimulates reduction of Cr(VI) by producing aqueous Fe(II). The product of this reaction is a mixed Fe(III)-Cr(III) hydroxide of the general formula Fe1−xCrx(OH)3 · nH2O, having an α/β-FeOOH local order. As the reaction proceeds, Fe within the system is cycled (i.e., Fe(III) within the hydroxide reaction product is further reduced by dissimilatory iron-reducing bacteria to Fe(II) and available for continued Cr reduction) and the hydroxide products become enriched in Cr relative to Fe, ultimately approaching a pure Cr(OH)3 · nH2O phase. This Cr purification process appreciably increases the solubility of the hydroxide phases, although even the pure-phase chromium hydroxide is relatively insoluble.  相似文献   

2.
The subsurface behaviour of 99Tc, a contaminant resulting from nuclear fuels reprocessing, is dependent on its valence (e.g., IV or VII). Abiotic reduction of soluble Tc(VII) by Fe(II)(aq) in pH 6-8 solutions was investigated under strictly anoxic conditions using an oxygen trap (<7.5 × 10−9 atm O2). The reduction kinetics were strongly pH dependent. Complete and rapid reduction of Tc(VII) to a precipitated Fe/Tc(IV) form was observed when 11 μmol/L of Tc(VII) was reacted with 0.4 mmol/L Fe(II) at pH 7.0 and 8.0, while no significant reduction was observed over 1 month at pH 6.0. Experiments conducted at pH 7.0 with Fe(II)(aq) = 0.05-0.8 mmol/L further revealed that Tc(VII) reduction was a combination of homogeneous and heterogeneous reaction. Heterogeneous reduction predominated after approximately 0.01 mmol/L of Fe(II) was oxidized. The heterogeneous reaction was more rapid, and was catalyzed by Fe(II) that adsorbed to the Fe/Tc(IV) redox product. Wet chemical and Fe-X-ray absorption near edge spectroscopy measurements (XANES) showed that Fe(II) and Fe(III) were present in the Fe/Tc(IV) redox products after reaction termination. 57Fe-Mössbauer, extended X-ray adsorption fine structure (EXAFS), and transmission electron microscopy (TEM) measurements revealed that the Fe/Tc(IV) solid phase was poorly ordered and dominated by Fe(II)-containing ferrihydrite with minor magnetite. Tc(IV) exhibited homogeneous spatial distribution within the precipitates. According to Tc-EXAFS measurements and structural modeling, its molecular environment was consistent with an octahedral Tc(IV) dimer bound in bidentate edge-sharing mode to octahedral Fe(III) associated with surface or vacancy sites in ferrihydrite. The precipitate maintained Tc(IV)aq concentrations that were slightly below those in equilibrium with amorphous Tc(IV)O2·nH2O(s). The oxidation rate of sorbed Tc(IV) in the Fe/Tc precipitate was considerably slower than Tc(IV)O2·nH2O(s) as a result of its intraparticle/intragrain residence. Precipitates of this nature may form in anoxic sediments or groundwaters, and the intraparticle residence of sorbed/precipitated Tc(IV) may limit 99Tc remobilization upon the return of oxidizing conditions.  相似文献   

3.
The potential for Mn oxides to modify the biogeochemical behavior of U during reduction by the subsurface bacterium Shewanella putrefaciens strain CN32 was investigated using synthetic Mn(III/IV) oxides (pyrolusite [β-MnO2], bixbyite [Mn2O3] and K+-birnessite [K4Mn14O27 · 8H2O]). In the absence of bacteria, pyrolusite and bixbyite oxidized biogenic uraninite (UO2[s]) to soluble U(VI) species, with bixbyite being the most rapid oxidant. The Mn(III/IV) oxides lowered the bioreduction rate of U(VI) relative to rates in their absence or in the presence of gibbsite (Al[OH]3) added as a non-redox-reactive surface. Evolved Mn(II) increased with increasing initial U(VI) concentration in the biotic experiments, indicating that valence cycling of U facilitated the reduction of Mn(III/IV). Despite an excess of the Mn oxide, 43 to 100% of the initial U was bioreduced after extended incubation. Analysis of thin sections of bacterial Mn oxide suspensions revealed that the reduced U resided in the periplasmic space of the bacterial cells. However, in the absence of Mn(III/IV) oxides, UO2(s) accumulated as copious fine-grained particles external to the cell. These results indicate that the presence of Mn(III/IV) oxides may impede the biological reduction of U(VI) in subsoils and sediments. However, the accumulation of U(IV) in the cell periplasm may physically protect reduced U from oxidation, promoting at least a temporal state of redox disequilibria.  相似文献   

4.
Data from studies of dissimilatory bacterial (108 cells mL−1 of Shewanella putrefaciens strain CN32, pH 6.8) and ascorbate (10 mM, pH 3.0) reduction of two synthetic Fe(III) oxide coated sands and three natural Fe(III) oxide-bearing subsurface materials (all at ca. 10 mmol Fe(III) L−1) were analyzed in relation to a generalized rate law for mineral dissolution (Jt/m0 = k′(m/m0)γ, where Jt is the rate of dissolution and/or reduction at time t, m0 is the initial mass of oxide, and m/m0 is the unreduced or undissolved mineral fraction) in order to evaluate changes in the apparent reactivity of Fe(III) oxides during long-term biological vs. chemical reduction. The natural Fe(III) oxide assemblages demonstrated larger changes in reactivity (higher γ values in the generalized rate law) compared to the synthetic oxides during long-term abiotic reductive dissolution. No such relationship was evident in the bacterial reduction experiments, in which temporal changes in the apparent reactivity of the natural and synthetic oxides were far greater (5-10 fold higher γ values) than in the abiotic reduction experiments. Kinetic and thermodynamic considerations indicated that neither the abundance of electron donor (lactate) nor the accumulation of aqueous end-products of oxide reduction (Fe(II), acetate, dissolved inorganic carbon) are likely to have posed significant limitations on the long-term kinetics of oxide reduction. Rather, accumulation of biogenic Fe(II) on residual oxide surfaces appeared to play a dominant role in governing the long-term kinetics of bacterial crystalline Fe(III) oxide reduction. The experimental findings together with numerical simulations support a conceptual model of bacterial Fe(III) oxide reduction kinetics that differs fundamentally from established models of abiotic Fe(III) oxide reductive dissolution, and indicate that information on Fe(III) oxide reactivity gained through abiotic reductive dissolution techniques cannot be used to predict long-term patterns of reactivity toward enzymatic reduction at circumneutral pH.  相似文献   

5.
Technetium-99 (Tc) is an important fission product contaminant associated with sites of nuclear fuels reprocessing and geologic nuclear waste disposal. Tc is highly mobile in its most oxidized state and less mobile in the reduced form [Tc(IV)O2·nH2O]. Here we investigate the potential for oxidation of Tc(IV) that was heterogeneously reduced by reaction with biogenic Fe(II) in two sediments differing in mineralogy and aggregation state; unconsolidated Pliocene-age fluvial sediment from the upper Ringold (RG) Formation at the Hanford Site and a clay-rich saprolite from the Field Research Center (FRC) background site on the Oak Ridge Site. Both sediments contained Fe(III) and Mn(III/IV) as redox active phases, but FRC also contained mass-dominant Fe-phyllosilicates of different types. Shewanella putrefaciens CN32 reduced Mn(III/IV) oxides and generated Fe(II) that was reactive with Tc(VII) in heat-killed, bioreduced sediment. After bioreduction and heat-killing, biogenic Fe(II) in the FRC exceeded that in RG by a factor of two. More rapid reduction rates were observed in the RG that had lower biogenic Fe(II), and less particle aggregation. EXAFS measurements indicated that the primary reduction product was a TcO2-like phase in both sediments. The biogenic redox product Tc(IV) oxidized rapidly and completely in RG when contacted with air. Oxidation, in contrast, was slow and incomplete in the FRC, in spite of similar molecular scale speciation of Tc compared to RG. X-ray microprobe, electron microprobe, X-ray absorption spectroscopy, and micro X-ray diffraction were applied to the whole sediment and isolated Tc-containing particles. These analyses revealed that non-oxidizable Tc(IV) in the FRC existed as complexes with octahedral Fe(III) within intra-grain domains of 50-100 μm-sized, Fe-containing micas presumptively identified as celadonite. The markedly slower oxidation rates in FRC as compared to RG were attributed to mass-transfer-limited migration of O2 into intra-aggregate and intraparticle domains where Tc(IV) existed; and the formation of unique, oxidation-resistant, intragrain Tc(IV)-Fe(III) molecular species.  相似文献   

6.
Schwertmannite (Fe8O8(OH)6SO4) is a common Fe(III)-oxyhydroxysulfate mineral in acid-sulfate systems, where its formation and fate strongly influence water quality. The present study examines transformation of schwertmannite to goethite (FeOOH), as catalyzed by interactions with Fe(II) in anoxic aquatic environments. This study also evaluates the role of the Fe(II) pathway in influencing the formation of iron-sulfide minerals in such environments. At pH > 5, the rates of Fe(II)-catalyzed schwertmannite transformation were several orders of magnitude faster than transformation in the absence of Fe(II). Complete transformation of schwertmannite occurred within only 3-5 h at pH > 6 and Fe(II)(aq) ? 5 mmol L−1. Model calculations indicate that the Fe(II)-catalyzed transformation of schwertmannite to goethite greatly decreases the reactivity of the Fe(III) pool, thereby favoring SO4-reduction and facilitating the formation of iron-sulfide minerals (particularly mackinawite, tetragonal FeS). Examination of in situ sediment geochemistry in an acid-sulfate system revealed that the rapid Fe(II)-catalyzed transformation was consistent with an abrupt shift from an acidic Fe(III)-reducing regime with abundant schwertmannite near the sediment surface, to a near-neutral mackinawite-forming regime where goethite was dominant. This study demonstrates that the Fe(II) pathway exerts a major influence on schwertmannite transformation and iron-sulfide formation in anoxic acid-sulfate systems. These findings have important implications for understanding acidity dynamics and trace element mobility in such systems.  相似文献   

7.
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   

8.
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   

9.
The reductive biotransformation of two Si-ferrihydrite coprecipitates (1 and 5 mole % Si) by Shewanella putrefaciens, strain CN32, was investigated in 1,4-piperazinediethanesulfonic acid-buffered media (pH ∼7) with lactate as the electron donor. Anthraquinone-2,6-disulfonate, an electron shuttle, was present in the media. Experiments were performed without and with PO43− (P) (1 to 20 mmol/L) in media containing 50 mmol/L Fe. Our objectives were to define the combined effects of SiO44− (Si) and P on the bioreducibility and biomineralization of ferrihydrites under anoxic conditions. Iron reduction was measured as a function of time, solids were characterized by powder X-ray diffraction and Mössbauer spectroscopy, and aqueous solutions were analyzed for Si, P, Cl− and inorganic carbon. Both of the ferrihydrites were rapidly reduced regardless of the Si and P content. Si concentration had no effect on the reduction rate or mineralization products. Magnetite was formed in the absence of P whereas carbonate green rust GR(CO32−) ([Fe(6−x)IIFeIIIx(OH)12]x+(CO32−)0.5x · yH2O) and vivianite [Fe3(PO4)2 · 8H2O], were formed when P was present. GR(CO32−) dominated as a mineral product in samples with <4 mmol/L P. The Fe(II)/Fe(III) ratio of GR(CO32−) varied with P concentration; the ratio was 2 in 1 mmol/L P and approached 1 with 4- and 10 mmol/L P. Green rust appeared to form by solid-state transformation of ferrihydrite. Media P and Si concentration dictated the mechanism of transformation. In the 1 mole % Si coprecipitate with 1 mmol/L P, an intermediate Fe(II)/Fe(III) phase with structural Fe(II) slowly transformed to GR with time. In contrast, when ferrihydrite contained more Si (5 mole %) and/or contained higher P (4 mmol/L), sorbed Fe(II) and residual ferrihydrite together transformed to GR. Despite similar chemistries, P was shown to have a profound effect on extent of ferrihydrite reduction and biotransformations while that of Si was minimal.  相似文献   

10.
Pyrite dissolution and interaction with Fe(II), Co(II), Eu(III) and U(VI) have been studied under anoxic conditions by solution chemistry and spectroscopic techniques. Aqueous data show a maximal cation uptake above pH 5.5. Iron (II) uptake can explain the non-stoichiometric [S]aq/[Fe]aq ratios often observed during dissolution experiments. Protonation data corrected for pyrite dissolution resulted in a proton site density of 9 ± 3 sites nm−2. Concentration isotherms for Eu(III) and U(VI) sorption on pyrite indicate two different behaviours which can be related to the contrasted redox properties of these elements. For Eu(III), sorption can be explained by the existence of a unique site with a saturation concentration of 1.25 × 10−6 mol g−1. In the U(VI) case, sorption seems to occur on two different sites with a total saturation concentration of 4.5 × 10−8 mol g−1. At lower concentration, uranium reduction occurs, limiting the concentration of dissolved uranium to the solubility of UO2(s).Scanning electron microscopy and micro-Raman spectrometry of U(VI)-sorbed pyrite indicate a heterogeneous distribution of U at the pyrite surface and a close association with oxidized S. X-ray photoelectron spectroscopy confirms the partial reduction of U and the formation of a hyperstoichiometric UO2+x(s). Our results are consistent with a chemistry of the pyrite surface governed not by Fe(II)-bound hydroxyl groups, but by S groups which can either sorb cations and protons, or sorb and reduce redox-sensitive elements such as U(VI).  相似文献   

11.
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   

12.
The solubility of the albite-paragonite-quartz mineral assemblage was measured as a function of NaCl and fluorine concentration at 400°C, 500 bars and at 450°C, 500 and 1000 bars. Decreasing Al concentrations with increasing NaCl molality in F-free fluids of low salinity (mNaCl < 0.01) demonstrates that Al(OH)4− dominates Al speciation and is formed according to the reaction 0.5 NaAl3Si3O12H2(cr)+2 H2O = 0.5 NaAlSi3O8(cr)+Al(OH)4−+H+. Log K results for this reaction are −11.28 ± 0.10 and −10.59 ± 0.10 at 400°C, 500 bars and 450°C, 1000 bars, respectively. Upon further salinity increase, Al concentration becomes constant (at 400°C, 500 bars) or even rises (at 450°C, 1000 bars). The observed Al behavior can be explained by the formation of NaAl(OH)40(aq) or NaAl(OH)3Cl(aq)0. The calculated constant for the reaction Al(OH)4−+Na+=NaAl(OH)40(aq) expressed in log units is equal to 2.46 and 2.04 at 400°C, 500 bars and 450°C, 1000 bars, respectively. These values are in good agreement with the predictions given in Diakonov et al. (1996). Addition of fluoride at m(NaCl) = const = 0.5 caused a sharp increase in Al concentration in equilibrium with the albite-paragonite-quartz mineral assemblage. As fluid pH was also constant, this solubility increase indicates strong aluminum-fluoride complexation with the formation of NaAl(OH)3F(aq)0 and NaAl(OH)2F20(aq), according to 0.5 NaAl3Si3O12H2(cr)+Na++HF(aq)0+H2O = 0.5 NaAlSi3O8(cr)+ NaAl(OH)3F(aq)0+H+, log K = −5.17 and −5.23 at 400°C and 450°C, 500 bars, respectively, and 0.5 NaAl3Si3O12H2(cr)+Na++2 HF(aq)0 = 0.5 NaAlSi3O8(cr)+NaAl(OH)2F20(aq)+H+, log K = −2.19 and −1.64 at the same P-T conditions. It was found that temperature increase and pressure decrease promote the formation of Na-Al-OH-F species. Stability of NaAl(OH)2F20(aq) in low-density fluids also increases relative to NaAl(OH)3F(aq)0. These complexes, together with Al(OH)2F(aq)0 and AlOHF20(aq), whose stability constants were calculated from the corundum solubility measured by Soboleva and Zaraisky (1990) and Zaraisky (1994), are likely to dominate Al speciation in metamorphic fluids containing several ppm of fluorine.  相似文献   

13.
To examine the pathways that form Mn(III) and Mn(IV) in the Mn(II)-oxidizing bacterial strains Pseudomonas putida GB-1 and MnB1, and to test whether the siderophore pyoverdine (PVD) inhibits Mn(IV)O2 formation, cultures were subjected to various protocols at known concentrations of iron and PVD. Depending on growth conditions, P. putida produced one of two oxidized Mn species - either soluble PVD-Mn(III) complex or insoluble Mn(IV)O2 minerals - but not both simultaneously. PVD-Mn(III) was present, and MnO2 precipitation was inhibited, both in iron-limited cultures that had synthesized 26-50 μM PVD and in iron-replete (non-PVD-producing) cultures that were supplemented with 10-550 μM purified PVD. PVD-Mn(III) arose by predominantly ligand-mediated air oxidation of Mn(II) in the presence of PVD, based on the following evidence: (a) yields and rates of this reaction were similar in sterile media and in cultures, and (b) GB-1 mutants deficient in enzymatic Mn oxidation produced PVD-Mn(III) as efficiently as wild type. Only wild type, however, could degrade PVD-Mn(III), a process linked to the production of both MnO2 and an altered PVD with absorbance and fluorescence spectra markedly different from those of either PVD or PVD-Mn(III). Two conditions, the presence of bioavailable iron and the absence of PVD at concentrations exceeding those of Mn, both had to be satisfied for MnO2 to appear. These results suggest that P. putida cultures produce soluble Mn(III) or MnO2 by different and mutually inhibitory pathways: enzymatic catalysis yielding MnO2 under iron sufficiency or PVD-promoted oxidation yielding PVD-Mn(III) under iron limitation. Since PVD-producing Pseudomonas species are environmentally prevalent Mn oxidizers, these data predict influences of iron (via PVD-Mn(III) versus MnO2) on the global oxidation/reduction cycling of various pollutants, recalcitrant organic matter, and elements such as C, S, N, Cr, U, and Mn.  相似文献   

14.
The reductive biotransformation of 6-line ferrihydrite located within porous silica (intragrain ferrihydrite) by Shewanella oneidensis MR-1 was investigated and compared to the behavior of 6-line ferrihydrite in suspension (free ferrihydrite). The effect of buffer type (PIPES and NaHCO3), phosphate (P), and an electron shuttle (AQDS) on the extent of reduction and formation of Fe(II) secondary phases was investigated under anoxic conditions. Electron microscopy and micro X-ray diffraction were applied to evaluate the morphology and mineralogy of the biogenic precipitates and to study the distribution of microorganisms on the surface of porous silica after bioreduction. Kinetic reduction experiments with free and intragrain ferrihydrite revealed contrasting behavior with respect to the buffer and presence of P. The overall amount of intragrain ferrihydrite reduction was less than that of free ferrihydrite [at 5 mmol L−1 Fe(III)T]. Reductive mineralization was not observed in the intragrain ferrihydrite incubations without P, and all biogenic Fe(II) concentrated in the aqueous phase. Irrespective of buffer and AQDS addition, rosettes of Fe(II) phosphate of approximate 20-30 μm size were observed on porous silica when P was present. The rosettes grew not only on the silica surface but also within it, forming a coherent spherical structure. These precipitates were well colonized by microorganisms and contained extracellular materials at the end of incubation. Microbial extracellular polymeric substances may have adsorbed Fe(II) promoting Fe(II) phosphate nucleation with subsequent crystal growth proceeding in different directions from a common center.  相似文献   

15.
The oxidation of Fe(II) with H2O2 at nanomolar levels in seawater have been studied using an UV-Vis spectrophotometric system equipped with a long liquid waveguide capillary flow cell. The effect of pH (6.5 to 8.2), H2O2 (7.2 × 10−8 M to 5.2 × 10−7 M), HCO3− (2.05 mM to 4.05 mM) and Fe(II) (5 nM to 500 nM) as a function of temperature (3 to 35 °C) on the oxidation of Fe(II) are presented. The oxidation rate is linearly related to the pH with a slope of 0.89 ± 0.01 independent of the concentration of HCO3−. A kinetic model for the reaction has been developed to consider the interactions of Fe(II) with the major ions in seawater. The model has been used to examine the effect of pH, concentrations of Fe(II), H2O2 and HCO3− as a function of temperature. FeOH+ is the most important contributing species to the overall rate of oxidation from pH 6 to pH 8. At a pH higher than 8, the Fe(OH)2 and Fe(CO3)22− species contribute over 20% to the rates. Model results show that when the concentration of O2 is two orders of magnitude higher than the concentration of H2O2, the oxidation with O2 also needs to be considered. The rate constants for the five most kinetically active species (Fe2+, FeOH+, Fe(OH)2, FeCO3, Fe(CO3)22−) in seawater as a function of temperature have been determined. The kinetic model is also valid in pure water with different concentrations of HCO3− and the conditions found in fresh waters.  相似文献   

16.
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   

17.
Methylmercury can accumulate in fish to concentrations unhealthy for humans and other predatory mammals. Most sources of mercury (Hg) emit inorganic species to the environment. Therefore, ecological harm occurs when inorganic Hg is converted to methylmercury. Sulfate- and iron-reducing bacteria (SRB and FeRB) methylate Hg, but the effects of processes involving oxidized and reduced forms of sulfur and iron on the reactivity of Hg, including the propensity of inorganic Hg to be methylated, are poorly understood. Under abiotic conditions, using a laboratory flow reactor, bisulfide (HS−) was added at 40 to 250 μM h−1 to 5 g L−1 goethite (α-FeOOH) suspensions to which Hg(II) was adsorbed (30-100 nmol m−2) at pH 7.5. Dissolved Hg initially decreased from 103 or 104 nM (depending on initial conditions) to 10−1 nM, during which the concentration of Hg(II) adsorbed to goethite decreased by 80% and metacinnabar (β-HgS(s)) formed, based on identification using Hg LIII-edge extended X-ray absorption fine structure (EXAFS) spectroscopic analysis. The apparent coordination of oxygens surrounding Hg(II), measured with EXAFS spectroscopy, increased during one flow experiment, suggesting desorption of monodentate-bound Hg(II) while bidentate-bound Hg(II) persisted on the goethite surface. Further sulfidation increased dissolved Hg concentrations by one to two orders of magnitude (0.5 to 10 nM or 30 nM), suggesting that byproducts of bisulfide oxidation and Fe(III) reduction, primarily polysulfide and potentially Fe(II), enhanced the dissolution of β-HgS(s) and/or desorption of Hg(II). Rapid accumulation of Fe(II) in the solid phase (up to 40 μmol g−1) coincided with faster elevation of dissolved Hg concentrations. Fe(II) served as a proxy for elemental sulfur [S(0)], as S(0) was the dominant bisulfide oxidation product coupled to Fe(III) reduction, based on sulfur K-edge X-ray absorption near edge structure (XANES) spectroscopy. In one experiment, dissolved Hg concentrations tracked those of all sulfide species [S(-II)]. These results suggest that S(-II) reacted with S(0) to form polysulfide, which then caused the dissolution of β-HgS(s). A secondary Fe-bearing phase resembling poorly formed green rust was observed in sulfidized solids with scanning electron microscopy, although there was no clear evidence that either surface-bound or mineralized Fe(II) strongly affected Hg speciation. Examination of interrelated processes involving S(-II) and Fe(III) revealed new modes of Hg solubilization previously not considered in Hg reactivity models.  相似文献   

18.
Iron isotope fractionation between aqueous Fe(II) and biogenic magnetite and Fe carbonates produced during reduction of hydrous ferric oxide (HFO) by Shewanella putrefaciens, Shewanella algae, and Geobacter sulfurreducens in laboratory experiments is a function of Fe(III) reduction rates and pathways by which biogenic minerals are formed. High Fe(III) reduction rates produced 56Fe/54Fe ratios for Fe(II)aq that are 2-3‰ lower than the HFO substrate, reflecting a kinetic isotope fractionation that was associated with rapid sorption of Fe(II) to HFO. In long-term experiments at low Fe(III) reduction rates, the Fe(II)aq-magnetite fractionation is −1.3‰, and this is interpreted to be the equilibrium fractionation factor at 22°C in the biologic reduction systems studied here. In experiments where Fe carbonate was the major ferrous product of HFO reduction, the estimated equilibrium Fe(II)aq-Fe carbonate fractionations were ca. 0.0‰ for siderite (FeCO3) and ca. +0.9‰ for Ca-substituted siderite (Ca0.15Fe0.85CO3) at 22°C. Formation of precursor phases such as amorphous nonmagnetic, noncarbonate Fe(II) solids are important in the pathways to formation of biogenic magnetite or siderite, particularly at high Fe(III) reduction rates, and these solids may have 56Fe/54Fe ratios that are up to 1‰ lower than Fe(II)aq. Under low Fe(III) reduction rates, where equilibrium is likely to be attained, it appears that both sorbed Fe(II) and amorphous Fe(II)(s) components have isotopic compositions that are similar to those of Fe(II)aq.The relative order of δ56Fe values for these biogenic minerals and aqueous Fe(II) is: magnetite > siderite ≈ Fe(II)aq > Ca-bearing Fe carbonate, and this is similar to that observed for minerals from natural samples such as Banded Iron Formations (BIFs). Where magnetite from BIFs has δ56Fe >0‰, the calculated δ56Fe value for aqueous Fe(II) suggests a source from midocean ridge (MOR) hydrothermal fluids. In contrast, magnetite from BIFs that has δ56Fe ≤0‰ apparently requires formation from aqueous Fe(II) that had very low δ56Fe values. Based on this experimental study, formation of low-δ56Fe Fe(II)aq in nonsulfidic systems seems most likely to have been produced by dissimilatory reduction of ferric oxides by Fe(III)-reducing bacteria.  相似文献   

19.
《Applied Geochemistry》2002,17(4):431-443
A steady state geochemical model has been developed to assist in understanding surface-catalysed oxidation of aqueous Fe(II) by O2(aq), which occurs rapidly at circumneutral pH. The model has been applied to assess the possible abiotic removal of Fe(II)(aq) from alkaline ferruginous mine water discharges using engineered reactors with high specific-surface area filter media. The model includes solution and surface speciation equilibrium, oxidation kinetics of dissolved and adsorbed Fe(II) species and mass transfer of O2(g). Limited field data for such treatment of a mine water discharge were available for model development and assessment of possible parameter values. Model results indicate that an adsorption capacity between 10−6 and 10−5 mol l−1 is sufficient for complete removal, by oxidation, of the Fe(II)(aq) load at the discharge. This capacity corresponds approximately to that afforded by surface precipitation of Fe(III) oxide onto plastic trickling filter media typically used for biological treatment of wastewater. Extrapolated literature values for microbial oxidation of Fe(II)(aq) by neutrophilic microbial populations to the simulated reactor conditions suggested that the microbially-mediated rate may be several orders-of-magnitude slower than the surface-catalysed oxidation. Application of the model across a range of mine water discharge qualities shows that high Fe(II)(aq) loadings can be removed if the discharge is sufficiently alkaline. Additional reactor simulations indicate that reactor efficiency decreases dramatically with pH in the near acid region, coinciding with the adsorption edge for Fe2+ on Fe oxyhydroxide. Alkaline discharges thus buffer pH within the range where Fe(II)(aq) adsorbs onto the accreting Fe hydroxide mineral surface, and undergoes rapid catalytic oxidation. The results suggest that the proposed treatment technology may be appropriate for highly ferruginous alkaline discharges, typically associated with abandoned deep coal mines.  相似文献   

20.
The oxidation of Mn(II) by O2 to Mn(III) or Mn(IV) is thermodynamically favored under the pH and pO2 conditions present in most near surface waters, but the kinetics of this reaction are extremely slow. This work investigated whether reactive oxygen species, produced through illumination of humic substances, could oxidize Mn at an environmentally relavent rate. The simulated sunlight illumination of a solution containing 200 μM Mn(II) and 5 mg/L Aldrich humic acid buffered at pH 8.1 produced ∼19 μM of oxidized Mn (MnOx where x is between one and two) after 45 minutes. The major oxidants reponsible for this reaction appear to be photoproduced superoxide radical anion, O2−, and singlet molecular oxygen, 1O2. The dependencies of MnOx formation on Mn(II), humic acid, and H+ concentration were characterized. A kinetic model based largely on published rate constants was established and fit to the experimental data. As expected, analysis of the model indicates that the key reaction rate controlling MnOx production is the rate of decomposition of a MnO2+ complex formed from the reaction of Mn(II) with O2−. This rate is strongly dependent on the Mn(II) complexing ligands in solution. The MnOx production in the seawater sample taken from Bodega Bay, USA and spiked with 200 μM Mn(II) was well reproduced by the model. Extrapolations from the model imply that Mn photo-oxidation should be a significant reaction in typical surface seawaters. Calculated rates, 5.8 to 55 pM h−1, are comparable to reported rates of biological Mn oxidation, 0.07 to 89 pM h−1. Four fresh water samples that were spiked with 200 μM Mn(II) also showed significant MnOx production. Based on these results, it appears that Mn photo-oxidation could constitute a significant, and apparently unrecognized geochemical pathway in natural waters.  相似文献   

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