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1.
The atomic and electronic structure of mineral surfaces affects many environmentally important processes such as adsorption phenomena. They are however rarely considered relevant to dissimilatory bacterial reduction of iron and manganese minerals. In this regard, surface area and thermodynamics are more commonly considered. Here we take a first step towards understanding the nature of the influence of mineral surface structure upon the rate of electron transfer from Shewanella oneidensis strain MR-1 outer membrane proteins to the mineral surface and the subsequent effect upon cell “activity.” Cell accumulation has been used as a proxy for cell activity at three iron oxide single crystal faces; hematite (001), magnetite (111) and magnetite (100). Clear differences in cell accumulation at, and release from the surfaces are observed, with significantly more cells accumulating at hematite (001) compared to either magnetite face whilst relatively more cells are released into the overlying aqueous phase from the two magnetite faces than hematite. Modeling of the electron transfer process to the different mineral surfaces from a decaheme (protoporphyrin rings containing a central hexacoordinate iron atom), outer membrane-bound cytochrome of S. oneidensis has been accomplished by employing both Marcus and ab initio density functional theories. The resultant model of electron transfer to the three oxide faces predicts that over the entire range of expected electron transfer distances the highest electron transfer rates occur at the hematite (001) surface, mirroring the observed cell accumulation data. Electron transfer rates to either of the two magnetite surfaces are slower, with magnetite (111) slower than hematite (001) by approximately two orders of magnitude. A lack of knowledge regarding the structural details of the heme-mineral interface, especially in regards to atomic distances and relative orientations of hemes and surface iron atoms and the conformation of the protein envelope, precludes a more thorough analysis. However, the results of the modeling concur with the empirical observation that mineral surface structure has a clear influence on mineral surface-associated cell activity. Thus surface structure effects must be accounted for in future studies of cell-mineral interactions.  相似文献   

2.
Mechanisms by which dissimilatory iron-reducing bacteria utilize iron and manganese oxide minerals as terminal electron acceptors for respiration are poorly understood. In the absence of exogenous electron shuttle compounds, extracellular electron transfer is generally thought to occur through the interfacial contact area between mineral surfaces and attached cells. Possible alternative reduction pathways have been proposed based on the discovery of a link between an excreted quinone and dissimilatory reduction. In this study, we utilize a novel experimental approach to demonstrate that Shewanella putrefaciens reduces the surface of crystalline iron oxides at spatial locations that are distinct from points of attachment.  相似文献   

3.
The results of experiments designed to test the hypothesis that near-surface molecular structure of iron oxide minerals influences adhesion of dissimilatory iron reducing bacteria are presented. These experiments involved the measurement, using atomic force microscopy, of interaction forces generated between Shewanella oneidensis MR-1 cells and single crystal growth faces of iron oxide minerals. Significantly different adhesive force was measured between cells and the (001) face of hematite, and the (100) and (111) faces of magnetite. A role for electrostatic interactions is apparent. The trend in relative forces of adhesion generated at the mineral surfaces is in agreement with predicted ferric site densities published previously. These results suggest that near-surface structure does indeed influence initial cell attachment to iron oxide surfaces; whether this is mediated via specific cell surface-mineral surface interactions or by more general interfacial phenomena remains untested.  相似文献   

4.
Bacterial metal reduction is an important biogeochemical process in anaerobic environments. An understanding of electron transfer pathways from dissimilatory metal-reducing bacteria (DMRB) to solid phase metal (hydr)oxides is important for understanding metal redox cycling in soils and sediments, for utilizing DMRB in bioremedation, and for developing technologies such as microbial fuel cells. Here we hypothesize that the outer membrane cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 are the only terminal reductases capable of direct electron transfer to a hematite working electrode. Cyclic voltammetry (CV) was used to study electron transfer between hematite electrodes and protein films, S. oneidensis MR-1 wild-type cell suspensions, and cytochrome deletion mutants. After controlling for hematite electrode dissolution at negative potential, the midpoint potentials of adsorbed OmcA and MtrC were measured (−201 mV and −163 mV vs. Ag/AgCl, respectively). Cell suspensions of wild-type MR-1, deletion mutants deficient in OmcA (ΔomcA), MtrC (ΔmtrC), and both OmcA and MtrC (ΔmtrC–ΔomcA) were also studied; voltammograms for ΔmtrC–ΔomcA were indistinguishable from the control. When the control was subtracted from the single deletion mutant voltammograms, redox peaks were consistent with the present cytochrome (i.e., ΔomcA consistent with MtrC and ΔmtrC consistent with OmcA). The results indicate that OmcA and MtrC are capable of direct electron exchange with hematite electrodes, consistent with a role as terminal reductases in the S. oneidensis MR-1 anaerobic respiratory pathway involving ferric minerals. There was no evidence for other terminal reductases operating under the conditions investigated. A Marcus-based approach to electron transfer kinetics indicated that the rate constant for electron transfer ket varies from 0.025 s−1 in the absence of a barrier to 63.5 s−1 with a 0.2 eV barrier.  相似文献   

5.
Computer simulation of electron transfer at hematite surfaces   总被引:1,自引:0,他引:1  
Molecular dynamics simulations in combination with ab initio calculations were carried out to determine the rate of electron transfer at room temperature in bulk hematite (α-Fe2O3) and at two low-index surfaces, namely the (012) and (001) surfaces. The electron transfer reactions considered here involve the II/III valence interchange between nearest-neighbor iron atoms. Two electron transfer directions were investigated, namely the basal plane and c direction electron transfers. Electron transfer rates obtained in bulk hematite were in good agreement with ab initio electronic structure calculations thus validating the potential model. The surfaces were considered both in vacuum and in contact with an equilibrated aqueous solution. The reorganization energy is found to increase significantly at the first surface layer and this value is little affected by the presence of water. In addition, in the case of the (012) surface, the electronic coupling matrix element for the topmost basal plane transfer was calculated at the Hartree-Fock level and was found to be weak compared to the corresponding electron transfer in the bulk. Therefore, most surfaces show a decrease in the rate of electron transfer at the surface. However, where iron atoms involved in the electron transfer reaction are directly coordinated to water molecules, water lowers the free energy of activation to a great extent and provides a large driving force for electrons to diffuse toward the bulk thus opposing the intrinsic surface effect. The surfaces considered in this work show different electron transfer properties. Hematite has been shown to exhibit anisotropic conductivity and thus different surfaces will show different intra- and inter-layer rates depending on their orientation. Moreover, the calculations of electron transfers at the hydroxyl- and iron-terminated (001) surfaces revealed that surface termination has a significant effect on the electron transfer parameters in the vicinity of the surface. Finally, our findings indicate that undercoordinated terminal iron atoms could act as electron traps at the surface.  相似文献   

6.
The reductive dissolution of FeIII (hydr)oxides by dissimilatory iron-reducing bacteria (DIRB) could have a large impact on sediment genesis and Fe transport. If DIRB are able to reduce FeIII in minerals of high structural order to carry out anaerobic respiration, their range could encompass virtually every O2-free environment containing FeIII and adequate conditions for cell growth. Previous studies have established that Shewanella putrefaciens CN32, a known DIRB, will reduce crystalline Fe oxides when initially grown at high densities in a nutrient-rich broth, conditions that poorly model the environments where CN32 is found. By contrast, we grew CN32 by batch culture solely in a minimal growth medium. The stringent conditions imposed by the growth method better represent the conditions that cells are likely to encounter in their natural habitat. Furthermore, the expression of reductases necessary to carry out dissimilatory Fe reduction depends on the method of growth. It was found that under anaerobic conditions CN32 reduced hydrous ferric oxide (HFO), a poorly crystalline FeIII mineral, and did not reduce suspensions containing 4 mM FeIII in the form of poorly ordered nanometer-sized goethite (α-FeOOH), well-ordered micron-sized goethite, or nanometer-sized hematite (α-Fe2O3) crystallites. Transmission electron microscopy (TEM) showed that all minerals but the micron-sized goethite attached extensively to the bacteria and appeared to penetrate the outer cellular membrane. In the treatment with HFO, new FeII and FeIII minerals formed during reduction of HFO-Fe in culture medium containing 4.0 mmol/L Pi (soluble inorganic P), as observed by TEM with energy-dispersive X-ray spectroscopy, selected area electron diffraction, and X-ray diffraction. The minerals included magnetite (Fe3O4), goethite, green rust, and vivianite [Fe3(PO4)2 · 8H2O]. Vivianite appeared to be the stable end product and the mean coherence length was influenced by the rate of FeIII reduction. When Pi was 0.4 mol/L under otherwise identical conditions, goethite was the only mineral observed to form, and less Fe2+ was produced overall. Hence, the ability of DIRB to reduce Fe (hydr)oxides may be limited when the bacteria are grown under nutrient-limited conditions, and the minerals that result depend on the vigor of FeIII reduction.  相似文献   

7.
Stable Fe isotope fractionations were investigated during exposure of hematite to aqueous Fe(II) under conditions of variable Fe(II)/hematite ratios, the presence/absence of dissolved Si, and neutral versus alkaline pH. When Fe(II) undergoes electron transfer to hematite, Fe(II) is initially oxidized to Fe(III), and structural Fe(III) on the hematite surface is reduced to Fe(II). During this redox reaction, the newly formed reactive Fe(III) layer becomes enriched in heavy Fe isotopes and light Fe isotopes partition into aqueous and sorbed Fe(II). Our results indicate that in most cases the reactive Fe(III) that undergoes isotopic exchange accounts for less than one octahedral layer on the hematite surface. With higher Fe(II)/hematite molar ratios, and the presence of dissolved Si at alkaline pH, stable Fe isotope fractionations move away from those expected for equilibrium between aqueous Fe(II) and hematite, towards those expected for aqueous Fe(II) and goethite. These results point to formation of new phases on the hematite surface as a result of distortion of Fe-O bonds and Si polymerization at high pH. Our findings demonstrate how stable Fe isotope fractionations can be used to investigate changes in surface Fe phases during exposure of Fe(III) oxides to aqueous Fe(II) under different environmental conditions. These results confirm the coupled electron and atom exchange mechanism proposed to explain Fe isotope fractionation during dissimilatory iron reduction (DIR). Although abiologic Fe(II)aq - oxide interaction will produce low δ56Fe values for Fe(II)aq, similar to that produced by Fe(II) oxidation, only small quantities of low-δ56Fe Fe(II)aq are formed by these processes. In contrast, DIR, which continually exposes new surface Fe(III) atoms during reduction, as well as production of Fe(II), remains the most efficient mechanism for generating large quantities of low-δ56Fe aqueous Fe(II) in many natural systems.  相似文献   

8.
We have characterized the outer-membrane decaheme cytochromes OmcA and MtrC from Shewanella oneidensis MR-1 at the single-molecule level using scanning tunneling microscopy (STM) and tunneling spectroscopy (TS). These cytochrome proteins are of great interest because they are thought to mediate bacterial electron transfer reactions in anoxic waters that control the reductive dissolution of oxide minerals. In our study, to characterize the electron transfer properties of these proteins on a model surface, the purified cytochromes were chemically immobilized as molecular monolayers on Au(111) substrates via a recombinant tetra-cysteine sequence as verified by X-ray photoelectron spectroscopy. Atomic force microscopy images confirm the monolayer films were ∼5-8 nm thick which is consistent with the apparent lateral dimensions of individual cytochrome molecules obtained with STM. Current-voltage TS of single cytochrome molecules revealed that OmcA and MtrC have different abilities to mediate tunneling current despite having otherwise very similar molecular and biochemical properties. These observations suggest that, based on their electron tunneling properties, the two cytochromes could have specific roles during bacterial metal reduction. Additionally, this study establishes single-molecule STM/TS as an effective means for revealing insights into biogeochemical redox processes in the environment.  相似文献   

9.
This study documents the first example of in vitro solid-phase mineral oxide reduction by enzyme-containing membrane fractions. Previous in vitro studies have only reported the reduction of aqueous ions. Total membrane (TM) fractions from iron-grown cultures of Shewanella oneidensis MR-1 were isolated and shown to catalyze the reduction of goethite, hematite, birnessite, and ramsdellite/pyrolusite using formate. In contrast, nicotinamide adenine dinucleotide (NADH) and succinate cannot function as electron donors. The significant implications of observations related to this cell-free system are: (i) both iron and manganese mineral oxides are reduced by the TM fraction, but aqueous U(VI) is not; (ii) TM fractions from anaerobically grown, but not aerobically grown, cells can reduce the mineral oxides; (iii) electron shuttles and iron chelators are not needed for this in vitro reduction, documenting conclusively that reduction can occur by direct contact with the mineral oxide; (iv) electron shuttles and EDTA stimulate the in vitro Fe(III) reduction, documenting that exogenous molecules can enhance rates of enzymatic mineral reduction; and (v) multiple membrane components are involved in solid-phase oxide reduction. The membrane fractions, consisting of liposomes of cytoplasmic and outer membrane segments, contain at least 100 proteins including the enzyme that oxidizes formate, formate dehydrogenase. Mineral oxide reduction was inhibited by the addition of detergent Triton X-100, which solubilizes membranes and their associated proteins, consistent with the involvement of multiple electron carriers that are disrupted by detergent addition. In contrast, formate dehydrogenase activity was not inhibited by Triton X-100. The addition of anthraquinone-2,6-disulfonate (AQDS) and menaquinone-4 was unable to restore activity; however, menadione (MD) restored 33% of the activity. The addition of AQDS and MD to reactions without added detergent increased the rate of goethite reduction. The Michaelis-Menten Km values of 71 ± 22 m2/L for hematite and 50 ± 16 m2/L for goethite were calculated as a function of surface area of the two insoluble minerals. Vmax was determined to be 123 ± 14 and 156 ± 13 nmol Fe(II)/min/mg of TM protein for hematite and goethite, respectively. These values are consistent with in vivo rates of reduction reported in the literature. These observations are consistent with our conclusion that the enzymatic reduction of mineral oxides is an effective probe that will allow elucidation of molecular chemistry of the membrane-mineral interface where electron transfer occurs.  相似文献   

10.
Reductive immobilization of uranium by the stimulation of dissimilatory metal-reducing bacteria (DMRB) has been investigated as a remediation strategy for subsurface U(VI) contamination. In those environments, DMRB may utilize a variety of electron acceptors, such as ferric iron which can lead to the formation of reactive biogenic Fe(II) phases. These biogenic phases could potentially mediate abiotic U(VI) reduction. In this work, the DMRB Shewanella putrefaciens strain CN32 was used to synthesize two biogenic Fe(II)-bearing minerals: magnetite (a mixed Fe(II)-Fe(III) oxide) and vivianite (an Fe(II)-phosphate). Analysis of abiotic redox interactions between these biogenic minerals and U(VI) showed that both biogenic minerals reduced U(VI) completely. XAS analysis indicates significant differences in speciation of the reduced uranium after reaction with the two biogenic Fe(II)-bearing minerals. While biogenic magnetite favored the formation of structurally ordered, crystalline UO2, biogenic vivianite led to the formation of a monomeric U(IV) species lacking U-U associations in the corresponding EXAFS spectrum. To investigate the role of phosphate in the formation of monomeric U(IV) such as sorbed U(IV) species complexed by mineral surfaces, versus a U(IV) mineral, uranium was reduced by biogenic magnetite that was pre-sorbed with phosphate. XAS analysis of this sample also revealed the formation of monomeric U(IV) species suggesting that the presence of phosphate hinders formation of UO2. This work shows that U(VI) reduction products formed during in situ biostimulation can be influenced by the mineralogical and geochemical composition of the surrounding environment, as well as by the interfacial solute-solid chemistry of the solid-phase reductant.  相似文献   

11.
Iron-bearing clay minerals are ubiquitous in the environment and have been shown to play important roles in several biogeochemical processes. Previous efforts to characterize the Fe2+–Fe3+ redox couple in clay minerals using electrochemical techniques have been limited by experimental difficulties due to inadequate reactivity between clay minerals and electrodes. The current work overcomes this limitation by utilizing organic electron transfer mediators that rapidly transfer electrons with both the Fe-bearing clay minerals and electrodes. Here, an Fe-rich source clay mineral (ferruginous smectite, SWa-1) is examined with respect to what fraction of structural Fe participates in oxidation/reduction reactions and the relationship between bulk Fe2+/Fe3+ ratios to the reduction potential (Eh).  相似文献   

12.
Microscopic-scale imaging of reduced zones on the surfaces of minerals can be achieved by reaction with dilute Ag(I) solutions and subsequent analysis using synchrotron X-ray microscopy (XRM) above the Ag K-edge (25.5 keV). The principal reductant is Fe(II), but other reductants such as sulfide may contribute. Reduced zones may exist instrinsically, as in the structure of biotite and augite, or may be generated by reaction with chemical agents such as dithionite or treatment with sulfate-reducing bacteria (SRB). We demonstrate the method on flakes of specular hematite and biotite, as well as on thin sections of different rocks (arfvedsonitic granite, oolitic hematite, diabase, and quartz conglomerate) treated with SRB, and discuss possible artifacts that can occur. To our knowledge, this is the only microscopic technique that can image Fe(II) zones on the surface of an Fe-bearing mineral with monolayer sensitivity.  相似文献   

13.
macroscale processes that perturb general groundwater chemistry and therefore mineral–water equilibria; and microscale interactions, where attached organisms locally perturb mineral–water equilibria, potentially releasing limiting trace nutrients from the dissolving mineral. In the contaminated unconfined glacio-fluvial aquifer near Bemidji, Minnesota, USA, carbonate chemistry is influenced primarily at the macroscale. Under oxic conditions, respiration by native aerobic heterotrophs produces excess carbon dioxide that promotes calcite and dolomite dissolution. Aerobic microorganisms do not colonize dolomite surfaces and few occur on calcite. Within the anoxic groundwater, calcite overgrowths form on uncolonized calcite cleavage surfaces, possibly due to the consumption of acidity by dissimilatory iron-reducing bacteria. As molecular oxygen concentration increases downgradient of the oil pool, aerobes again dominate and residual hydrocarbons and ferrous iron are oxidized, resulting in macroscale carbonate-mineral dissolution and iron precipitation. Feldspars, in contrast, weather exclusively at the microscale near attached microorganisms, principally in the anoxic region of the plume. Native organisms preferentially colonize feldspars that contain trace phosphorus as apatite inclusions, apparently as a consequence of the low P concentration in the groundwater. These feldspars weather rapidly, whereas nearby feldspars without trace P are uncolonized and unweathered. Feldspar dissolution is accompanied by the precipitation of secondary minerals, sometimes on the bacterial cell wall itself. These observations suggest a tightly linked biogeochemical system whereby microbial processes control mineral diagenesis at many scales of interaction, and the mineralogy and mineral chemistry influence microbial ecology. Only the macroscale interaction, however, is easily observable by standard geochemical methods, and documentation of the microscale interactions requires microscopic examination of microorganisms on mineral surfaces and the locally intense diagenetic reactions that result. Received, May 1999/Revised, October 1999/Accepted, October 1999  相似文献   

14.
Reduction of U(VI) under iron reducing conditions was studied in a model system containing the dissimilatory metal-reducing bacterium Shewanella putrefaciens and colloidal hematite. We focused on the competition between direct enzymatic uranium reduction and abiotic reduction of U(VI) by Fe(II), catalyzed by the hematite surface, at relatively low U(VI) concentrations (< 0.5 μM) compared to the concentrations of ferric iron (> 10 mM). Under these conditions surface catalyzed reduction by Fe(II), which was produced by dissimilatory iron reduction, was the dominant pathway for uranium reduction. Reduction kinetics of U(VI) were identical to those in abiotic controls to which soluble Fe(II) was added. Strong adsorption of U(VI) at the hematite surface apparently favored the abiotic pathway by reducing the availability of U(VI) to the bacteria. In control experiments, lacking either hematite or bacteria, the addition of 45 mM dissolved bicarbonate markedly slowed down U(VI) reduction. The inhibition of enzymatic U(VI) reduction and abiotic, surface catalyzed U(VI) reduction by the bicarbonate amendments is consistent with the formation of aqueous uranyl-carbonate complexes. Surprisingly, however, more U(VI) was reduced when dissolved bicarbonate was added to experimental systems containing both bacteria and hematite. The enhanced U(VI) reduction was attributed to the formation of magnetite, which was observed in experiments. Biogenic magnetite produced as a result of dissimilatory iron reduction may be an important agent of uranium immobilization in natural environments.  相似文献   

15.
One option for immobilizing uranium present in subsurface contaminated groundwater is in situ bioremediation, whereby dissimilatory metal-reducing bacteria and/or sulfate-reducing bacteria are stimulated to catalyze the reduction of soluble U(VI) and precipitate it as uraninite (UO2). This is typically accomplished by amending groundwater with an organic electron donor. It has been shown, however, that once the electron donor is entirely consumed, Fe(III) (hydr)oxides can reoxidize biogenically produced UO2, thus potentially impeding cleanup efforts. On the basis of published experiments showing that such reoxidation takes place even under highly reducing conditions (e.g., sulfate-reducing conditions), thermodynamic and kinetic constraints affecting this reoxidation are examined using multicomponent biogeochemical simulations, with particular focus on the role of sulfide and Fe(II) in solution. The solubility of UO2 and Fe(III) (hydr)oxides are presented, and the effect of nanoscale particle size on stability is discussed. Thermodynamically, sulfide is preferentially oxidized by Fe(III) (hydr)oxides, compared to biogenic UO2, and for this reason the relative rates of sulfide and UO2 oxidation play a key role on whether or not UO2 reoxidizes. The amount of Fe(II) in solution is another important factor, with the precipitation of Fe(II) minerals lowering the Fe+2 activity in solution and increasing the potential for both sulfide and UO2 reoxidation. The greater (and unintuitive) UO2 reoxidation by hematite compared to ferrihydrite previously reported in some experiments can be explained by the exhaustion of this mineral from reaction with sulfide. Simulations also confirm previous studies suggesting that carbonate produced by the degradation of organic electron donors used for bioreduction may significantly increase the potential for UO2 reoxidation through formation of uranyl carbonate aqueous complexes.  相似文献   

16.
The interaction between minerals and microbes is an important biogeochemical process in the earth surface system, which links the transformation of substances and energy exchange in different earth spheres, and also affects a series of important earth surface processes, including the formation and evolution of secondary minerals, nutrient cycling and environmental behaviors of pollutants. The previous studies on microbe-mineral interaction focused on the extracellular electron transfer, and the microbe-mediated dissolution, precipitation, mineralization of minerals. Because of semiconductor properties of the mineral, it plays a special role in the process of microbial extracellular electron transfer, which can also help to understand the mutual interaction between microbe and mineral from a new angle of view. The unique energy level structures and redox properties of semiconducting mineral lead to a great difference in the mechanism of microbe and mineral interaction. The latest research progresses in the mechanism of microbe-mineral interaction mediated by semiconducting mineral were reviewed from two aspects: driven by thermodynamics and light energy. Finally, the future development trends of the interaction between microbes and semiconductor minerals were prospected.  相似文献   

17.
Computer modelling techniques were used to elucidate the hydration behaviour of three iron (hydr)oxide minerals at the atomic level: white rust, goethite and hematite. A potential model was first adapted and tested against the bulk structures and properties of eight different iron oxides, oxyhydroxides and hydroxides, followed by surface simulations of Fe(OH)2, α-FeO(OH) and α-Fe2O3. The major interaction between the adsorbing water molecules and the surface is through interaction of their oxygen ions with surface iron ions, followed by hydrogen-bonding to surface oxygen ions. The energies released upon the associative adsorption of water range from 1 to 17 kJ mol−1 for Fe(OH)2, 26 to 80 kJ mol−1 for goethite and 40 to 85 kJ mol−1 for hematite, reflecting the increasing oxidation of the iron mineral. Dissociative adsorption at goethite and hematite surfaces releases larger hydration energies, ranging from 120 to 208 kJ mol−1 for goethite and 76 to 190 kJ mol−1 for hematite.The thermodynamic morphologies of the minerals, based on the calculated surface energies, agree well with experimental morphologies, where these are available. When the partial pressures required for adsorption of water from the gas phase are plotted against temperature for the goethite and hematite surfaces, taking into account experimental entropies for water, it appears that these minerals may well be instrumental in the retention of water during the cyclic variations in the atmosphere of Mars.  相似文献   

18.
This paper discusses the selective depression of pyrite from chalcopyrite and arsenopyrite by biomodulation using Acidithiobacillus ferrooxidans under natural conditions of pH. The effect of bacteria–mineral interaction on the surface charge of mineral and bacterial cell was studied by microelectrophoresis. Adhesion experiments were conducted to establish the relationship between cell adhesion to specific minerals and the electrokinetic behaviour of the minerals subsequent to interaction with cells. Effect of bacterial interaction on the xanthate-induced flotation of all the minerals was assessed. Adhesion of A. ferrooxidans on pyrite was rapid and tenacious and subsequent to interaction with cells, pyrite remained hydrophilic even in presence of xanthate collector. The collector, on the other hand, was able to render good flotability to chalcopyrite even after interaction with bacterial cells. Copper activated arsenopyrite was able to retain its hydrophobicity in presence of cells due to poor attachment kinetics of cells to the mineral surface. Thus, by suitably conditioning with the cells and collector, it was possible to effectively depress pyrite from chalcopyrite and arsenopyrite.  相似文献   

19.
Hexavalent uranium [U(VI)] dissolved in a modified lactate-C medium was treated under anoxic conditions with a mixture of an Fe(III)-(hydr)oxide mineral (hematite, goethite, or ferrihydrite) and quartz. The mass of Fe(III)-(hydr)oxide mineral was varied to give equivalent Fe(III)-mineral surface areas. After equilibration, the U(VI)-mineral suspensions were inoculated with sulfate-reducing bacteria, Desulfovibrio desulfuricans G20. Inoculation of the suspensions containing sulfate-limited medium yielded significant G20 growth, along with concomitant reduction of sulfate and U(VI) from solution. With lactate-limited medium, however, some of the uranium that had been removed from solution was resolubilized in the hematite treatments and, to a lesser extent, in the goethite treatments, once the lactate was depleted. No resolubilization was observed in the lactate-limited ferrihydrite treatment even after a prolonged incubation of 4 months. Uranium resolubilization was attributed to reoxidation of the uraninite by Fe(III) present in the (hydr)oxide phases. Analysis by U L3-edge XANES spectroscopy of mineral specimens sampled at the end of the experiments yielded spectra similar to that of uraninite, but having distinct features, notably a much more intense and slightly broader white line consistent with precipitation of nanometer-sized particles. The XANES spectra thus provided strong evidence for SRB-promoted removal of U(VI) from solution by reductive precipitation of uraninite. Consequently, our results suggest that SRB mediate reduction of soluble U(VI) to an insoluble U(IV) oxide, so long as a suitable electron donor is available. Depletion of the electron donor may result in partial reoxidation of the U(IV) to soluble U(VI) species when the surfaces of crystalline Fe(III)-(hydr)oxides are incompletely reduced.  相似文献   

20.
《Geochimica et cosmochimica acta》1999,63(13-14):2019-2023
In vitro enrichment cultures of dissimilatory sulfate-reducing bacteria precipitated FeS and catalyzed its transformation into FeS2 at ambient temperature and pressure under anaerobic conditions. When compared to purely abiotic processes, the bacterially mediated transformation was shown to be more efficient in transforming FeS into FeS2. This occurred due to the large, reactive surface area available for bacterially catalyzed diagenesis, where the biogenic FeS precursor was immobilized as a thin film (∼25 nm thick) on the μm-scale bacteria. The bacteria also contained the source(s) of sulfur for diagenesis to occur. Using a radiolabeled organic-sulfur tracer study, sulfur was released during cell autolysis and was immobilized at the bacterial cell surface forming FeS2. The formation of FeS2 occurred on both the inner and outer surfaces of the cell envelope and represented the first step of bacterial mineral diagenesis. Pyrite crystals, having linear dimensions of ∼1 μm, grew outward from the bacterial cell surfaces. These minerals were several orders of magnitude larger in volume than those originating abiotically.  相似文献   

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