Influence of soil minerals on chromium(VI) reduction by sulfide under anoxic conditions     

Yeqing Lan  Baolin Deng  Chulsung Kim  Edward C Thornton 《Geochemical transactions》2007,8(1):4

The effects of soil minerals on chromate (Cr^VIO₄ ^2-, noted as Cr(VI)) reduction by sulfide were investigated in the pH range of 7.67 to 9.07 under the anoxic condition. The examined minerals included montmorillonite (Swy-2), illite (IMt-2), kaolinite (KGa-2), aluminum oxide (γ-Al₂O₃), titanium oxide (TiO₂, P-25, primarily anatase), and silica (SiO₂). Based on their effects on Cr(VI) reduction, these minerals were categorized into three groups: (i) minerals catalyzing Cr(VI) reduction – illite; (ii) minerals with no effect – Al₂O₃; and (iii) minerals inhibiting Cr(VI) reduction- kaolinite, montmorillonite, SiO₂ and TiO₂ . The catalysis of illite was attributed primarily to the low concentration of iron solubilized from the mineral, which could accelerate Cr(VI) reduction by shuttling electrons from sulfide to Cr(VI). Additionally, elemental sulfur produced as the primary product of sulfide oxidation could further catalyze Cr(VI) reduction in the heterogeneous system. Previous studies have shown that adsorption of sulfide onto elemental sulfur nanoparticles could greatly increase sulfide reactivity towards Cr(VI) reduction. Consequently, the observed rate constant, k _obs, increased with increasing amounts of both iron solubilized from illite and elemental sulfur produced during the reaction. The catalysis of iron, however, was found to be blocked by phenanthroline, a strong complexing agent for ferrous iron. In this case, the overall reaction rate at the initial stage of reaction was pseudo first order with respect to Cr(VI), i.e., the reaction kinetics was similar to that in the homogeneous system, because elemental sulfur exerted no effect at the initial stage prior to accumulation of elemental sulfur nanoparticles. In the suspension of kaolinite, which belonged to group (iii), an inhibitive effect to Cr(VI) reduction was observed and subsequently examined in more details. The inhibition was due to the sorption of elemental sulfur onto kaolinite, which reduced or completely eliminated the catalytic effect of elemental sulfur, depending on kaolinite concentration. This was consistent with the observation that the catalysis of externally added elemental sulfur (50 μM) on Cr(VI) reduction would disappear with a kaolinite concentration of more than 5.0 g/L. In kaolinite suspension, the overall reaction rate law was:

相似文献    7. Iron in a post-glacial lake sediment core; a Mössbauer effect study      J.M.D. Coey 《Geochimica et cosmochimica acta》1975,39(4):401-415 The distribution of iron in a 6-m core of post-glacial sediment from an oligotrophic lake (Connistonwater, England) was determined, principally by Mossbauer spectroscopy on dried samples. The immediate post-glacial deposits contain 4.8 wt. % of iron, with a Fe2+; Fe3+ ratio ～- 4. The iron there is predominantly in the form of chlorite, but there are small amounts in hematite and illite. The distribution of iron is different, and very variable in the recent sediments (~ < 13,000 BP), which contain 25–35 per cent organic matter and 5.2 wt. % of iron relative to the inorganic fraction. Typically half the iron is present there as chlorite, and the rest is ferric, mostly in the form of an amorphous gel which is also present in undried samples. To explain the observed ferrous:ferric profile, it is proposed that the latter includes iron which was once mobile, having been leached from the Fe2+-bearing clays under reducing conditions in the soils of the drainage basin, or in the sediment itself. It was subsequently precipitated as ferric hydroxide on contact with the oxic lake water. In contrast, the ferrous iron in the sediments is immobile iron, which remained locked in the chlorite phase of the clay particles as they were carried from soil to sediment intact.All the sediments are rather inhomogeneous. Chlorite, and especially hematite, are mechanically concentrated in pink varves in the immediate post-glacial deposits. In the partly inorganic sediments, the concentration of ferrous iron (chlorite) is approximately uniform, but the ferric content may differ by a factor of five between regions only a few millimeters apart.  相似文献    8. Biogeochemistry of sulfur and iron in Thioploca-colonized surface sediments in the upwelling area off central chile      Jakob Zopfi  Bo Barker Jørgensen 《Geochimica et cosmochimica acta》2008,72(3):827-843 The biogeochemistry of sedimentary sulfur was investigated on the continental shelf off central Chile at water depths between 24 and 88 m under partial influence of an oxygen minimum zone. Dissolved and solid iron and sulfur species, including the sulfur intermediates sulfite, thiosulfate, and elemental sulfur, were analyzed at high resolution in the top 20 cm. All stations were characterized by high rates of sulfate reduction, but only the sediments within the Bay of Concepción contained dissolved sulfide. Due to advection and/or in-situ reoxidation of sulfide, dissolved sulfate was close to bottom water values. Whereas the concentrations of sulfite and thiosulfate were mostly in the submicromolar range, elemental sulfur was by far the dominant sulfur intermediate. Although the large nitrate- and sulfur-storing bacteria Thioploca were abundant, the major part of S0 was located extracellularly. The distribution of sulfur species and dissolved iron suggests the reaction of sulfide with FeOOH as an important pathway for sulfide oxidation and sulfur intermediate formation. This is in agreement with the sulfur isotope composition of co-existing elemental sulfur and iron monosulfides. In the Bay of Concepción, sulfur isotope data suggest that pyrite formation proceeds via the reaction of FeS with polysulfides or H2S. At the shelf stations, on the other hand, pyrite was significantly depleted in 34S relative to its potential precursors FeS and S0. Isotope mass balance considerations suggest further that pyritization at depth includes light sulfide, potentially originating from bacterial sulfur disproportionation. The δ34S-values of pyrite down to −38‰ vs. V-CDT are among the lightest found in organic-rich marine sediments. Seasonal variations in the sulfur isotope composition of dissolved sulfate indicated a dynamic non-steady-state sulfur cycle in the surface sediments. The 18O content of porewater sulfate increased with depth at all sites compared to the bottom water composition due to intracellular isotope exchange reactions during microbial sulfur transformations.  相似文献    9. Weathering of phlogopite in simulated bioleaching solutions      Tariq M. Bhatti  Jerry M. Bigham  Antti Vuorinen  Olli H. Tuovinen 《International Journal of Mineral Processing》2011,98(1-2):30-34 The purpose of this study was to examine structural alterations of finely ground phlogopite, a trioctahedral mica, when exposed to acid, iron- and sulfate-rich solutions typical of bioleaching systems. Phlogopite suspensions were supplemented with ferrous sulfate and incubated with iron- and sulfur-oxidizing bacteria (Acidithiobacillus ferrooxidans) at 22 °C. As bacteria oxidized ferrous iron, ferric iron thus formed partially precipitated as K-jarosite. K-jarosite precipitation was contingent on the preceding ferrous iron oxidation by bacteria and the release of interlayer-K from phlogopite. This chemically and microbially induced weathering involved alteration of phlogopite to a mixed layer structure that included expansible vermiculite. The extent of phlogopite weathering and structure expansion varied with duration of the contact, concentration of ferrous iron and phlogopite, and the presence of monovalent cations (NH4+, K+, or Na+) in the culture solution. NH4+ and K+ ions (100 mM) added to culture suspensions precipitated as jarosite and thereby effectively prevented the loss of interlayer-K and structural alteration of phlogopite. Additional Na+ (100 mM) was insufficient to precipitate ferric iron as natrojarosite and therefore the precipitation was coupled with interlayer-K released from phlogopite. When ferrous iron was replaced with elemental sulfur as the substrate for A. ferrooxidans, the weathering of phlogopite was based on chemical dissolution without structural interstratification. The results demonstrate that iron oxidation and the concentration and composition of monovalent ions can have an effect on mineral weathering in leaching systems that involve contact of phlogopite and other mica minerals with acid leach solutions.  相似文献    10. Pyrite oxidation by Acidithiobacillus ferrooxidans at various concentrations of dissolved oxygen   总被引：1，自引：0，他引：1   《Chemical Geology》2006,225(1-2):16-29 Pyrite oxidation rates were examined at various concentrations of dissolved oxygen (DO) in the presence of the sulfur and iron oxidizer Acidithiobacillus ferrooxidans. Five different batch experiments were performed at room temperature for 75 days under various DO levels (273, 129, 64.8, 13.2, and ≤ 0.006 μM), containing pyrite grains (particle size 63–250 μm) and a modified 9K nutrient medium at pH 3. The reactors were inoculated with A. ferrooxidans. In all experiments, pH decreased with time and sulfur and iron were released to the solution, indicating pyrite oxidation at all DO levels. Pyrite oxidation rates (ca. 5 × 10− 10 mol m− 2 s− 1 at 273 μM DO) from all experiments showed positive correlation with DO, Fe(III), and bacterial concentration. These rates were significantly slower than rates presented in other published studies, but this is probably due to the significantly greater Fe(III) concentration at lower pH in these previous studies. The results obtained in this study suggest that ferric iron reduction at the pyrite surface is the primarily mechanism for microbial pyrite oxidation in the presence of DO. The results from our study support the indirect mechanism of sulfide oxidation, where A. ferrooxidans oxidizes ferrous iron in the presence of DO, which then oxidizes pyrite.  相似文献    11. Annual fluctuations in sulfur isotope fractionation in the water column of a euxinic marine basin      Ketil B Sørensen  Donald E Canfield 《Geochimica et cosmochimica acta》2004,68(3):503-515 The sulfur cycle of Mariager Fjord was studied by following the pool of sulfide in the anoxic water and its isotopic composition during a period of 3 yr. Though most of the sulfide accumulating in the fjord was formed in the sediment, the isotopic composition of sulfide in the water was different from the isotopic composition of sulfide diffusing into the water from the sediment. The mean isotopic composition of the water column sulfide (δ34S) varied during the year between −13‰ and −21‰ with the most negative values reached during winter/early spring, while the sulfide diffusing into the water from the sediment had a mean isotope composition of −11.3‰. This annual pattern suggested that processes in the oxidative part of the sulfur cycle were responsible for the excess fractionation, and mass-balance considerations indicated that the excess fractionation of the sulfur isotopes could be accounted for by disproportionation of S0 or S2O32− in the water column, but not by water column sulfate reduction or sulfide oxidation alone. MPN counts demonstrated that a population of more than 3 × 104 cells mL−1 capable of growing by disproportionation of these two substrates was present in all depths of the fjord. The results presented in this communication demonstrate that the isotopic depletion of sulfide in anoxic systems may vary between periods of net sulfate reduction versus periods of net sulfide oxidation and indicate that disproportionation of sulfur compounds may be an important step in the sulfur cycle of euxinic basins.  相似文献    12. 液液萃取电感耦合等离子体光谱法测定碳酸盐岩中的单质硫      全洗强  陶鑫  杜文越  秦愫妮  俞建国 《中国岩溶》2017,36(3):415-418 建立了碳酸盐岩样品中单质硫的分析方法,此法以正己烷为萃取剂,在180.7 nm和182.0 nm波长下用电感耦合等离子体光谱法(ICP-AES)测定国家标准物质GBW(E)07108和碳酸盐岩样品。正己烷萃取碳酸盐岩中单质硫的回收率在90%～110%之间;每个样品测定7次,相对标准偏差(RSD)<5.0%。结果表明,此法满足实验要求,可用于大批量碳酸盐岩样品中单质硫的测定。   相似文献    13. Quantitative determination of elemental sulfur at the arsenopyrite surface after oxidation by ferric iron: mechanistic implications      Molly M McGuire  Jillian F Banfield  Robert J Hamers 《Geochemical transactions》2001,2(1):25-5   相似文献    14. The effect of As, Co, and Ni impurities on pyrite oxidation kinetics: Batch and flow-through reactor experiments with synthetic pyrite      Stephen Lehner 《Geochimica et cosmochimica acta》2008,72(7):1788-1800 Pyrite samples synthesized with As, Co, or Ni impurities and without added impurities were oxidized in batch and mixed flow-through reactors in the presence of 1 mM ferric iron, at pH 2. Six samples from each dopant population were used to provide a statistically robust comparison; two natural samples from Leadville, CO (major impurities Pb, As, Bi, Ag, Zn) and Elba, Italy (Co, As) were also included. In each experiment, three reaction progress variables were monitored: ferric iron, ferrous iron, and sulfate. The pyrite samples with impurities have average oxidation rates that are faster than the undoped samples, with As- and Co-doped pyrite having the highest rates. As, Co, and Ni were released to solution in accordance with their concentrations in the solid samples. As concentrations in the batch reactor experiments tended to remain constant, in contrast to Co and Ni, which increased over time. Initial rates, calculated from the batch reactor experiments, were faster than the steady-state rates calculated from the mixed flow-through reactor experiments. Apparent rates calculated using sulfate were faster than apparent rates calculated using ferric and ferrous iron, reflecting oxidation of ferrous iron in solution by dissolved oxygen. The results imply that impurities in pyrite do contribute to its reactivity, in agreement with studies using electrochemical methods. Oxidation rate differences among pyrite samples with different impurities are probably too small to warrant explicit consideration in environmental modeling applications, but are important to understanding pyrite oxidation mechanisms and semiconducting properties.  相似文献    15. Equilibrium iron isotope fractionation factors of minerals: Reevaluation from the data of nuclear inelastic resonant X-ray scattering and Mössbauer spectroscopy      V.B. Polyakov  R.N. Clayton  S.D. Mineev 《Geochimica et cosmochimica acta》2007,71(15):3833-3846 We have critically reevaluated equilibrium iron isotope fractionation factors for oxide and sulfide minerals using recently acquired data obtained by Mössbauer spectroscopy and inelastic nuclear resonant X-ray scattering (INRXS) synchrotron radiation. Good agreement was observed in the iron β-factors of metallic iron (α-Fe) and hematite calculated using both Mössbauer- and INRXS-derived data, which supports the validity and reliability of the calculations. Based on this excellent agreement, we suggest the use of the present data on the iron β-factors of hematite as a reference.The previous Mössbauer-derived iron β-factor for magnetite has been modified significantly based on the Fe-sublattice density of states obtained from the INRXS experiments. This resolves the disagreement between naturally observed iron isotope fractionation factors for mineral pairs involving magnetite and those obtained from the calculated β-factors. The correctness of iron β-factor for pyrite has been corroborated by the good agreement with experimental data of sulfur isotope geothermometers of pyrite-galena and pyrite-sphalerite. A good correlation between the potential energy of the cation site, the oxidation state of iron and the iron β-factor value has been established. Specifically, ferric compounds, which have a higher potential energy of iron than ferrous compounds, have higher β-factors. A similar dependence of β-factors on the oxidation state and potential energy could be extended to other transition metals. Extremely low values of INRXS-derived iron β-factors for troilite and Fe3S significantly widen the range of iron β-factors for covalently bonded compounds.  相似文献    16. 含金黄铁矿氧化过程中金溶解机理的探讨——与王恩德、关广岳先生商榷   总被引：2，自引：0，他引：2   郑大中  郑若锋 《地质论评》1997,43(1):45-51 含金黄铁矿在细菌氧化、化学氧化过程中,除生成高铁的硫酸盐和硫酸外,还生成了亚铁的硫酸盐及硫的低价氧化物,体系中的电位较低,距溶解自然金呈Au(SO_4)_2~-所需电位甚远,实验表明,金不溶于硫酸铁溶液中。当氧化程度加深,介质pH>4,黄铁矿氧化产生的硫代硫酸根可稳定存在时,自然金呈稳定的硫代硫酸盐配合物溶解。  相似文献    17. Sedimentary iron monosulfides: Kinetics and mechanism of formation      Albert J Pyzik  Sheldon E Sommer 《Geochimica et cosmochimica acta》1981,45(5):687-698 The reaction between hydrous iron oxides and aqueous sulfide species was studied at estuarine conditions of pH, total sulfide, and ionic strength to determine the kinetics and formation mechanism of the initial iron sulfide. Total, dissolved and acid extractable sulfide, thiosulfate, sulfate, and elemental sulfur were determined by spectrophotometric methods. Polysulfides, S42? and S52?, were determined from ultraviolet absorbance measurements and equilibrium calculations, while product hydroxyl ion was determined from pH measurements and solution buffer capacity.Elemental sulfur, as free and polysulfide sulfur, was 86% of the sulfide oxidation products; the remainder was thiosulfate. Rate expressions for the reduction and precipitation reactions were determined from analysis of electron balance and acid extractable iron monosulfide vs time, respectively, by the initial rate method. The rate of iron reduction in moles/liter/minute was given by $\text{d(}\text{reduction}\text{Fe)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^{0.5}\text{(J}{}^{\mathrm{+}}\text{)}{}^{0.5}\text{A}{}_{\mathrm{FeOOH}}{}^1$ where St was the total dissolved sulfide concentration, (H+) the hydrogen ion activity, both in moles/ liter; and AFeOOH the goethite specific surface area in square meters/liter. The rate constant, k, was 0.017 ± 0.002m?2 min?1. The rate of reduction was apparently determined by the rate of dissolution of the surface layer of ferrous hydroxide. The rate expression for the precipitation reaction was $\text{d(FeS)}\text{dt}\text{= kS}{}_{\mathrm{t}}{}^1\text{(H}{}^{\mathrm{+}}\text{)}{}^1\text{A}{}_{\mathrm{FeOOH}}{}^1$ where $\text{d(FeS)}\text{dt}$ was the rate of precipitation of acid extractable iron monosulfide in moles/liter/minute, and k = 82 ± 18 mol?1l2m?2 min?1.A model is proposed with the following steps: protonation of goethite surface layer; exchange of bisulfide for hydroxide in the mobile layer; reduction of surface ferric ions of goethite by dissolved bisulfide species which produces ferrous hydroxide surface layer elemental sulfur and thiosulfate; dissolution of surface layer of ferrous hydroxide; and precipitation of dissolved ferrous specie and aqueous bisulfide ion.  相似文献    18. On the Occurrence of Silician Magnetites   总被引：2，自引：0，他引：2   Hidehiko Shimazaki 《Resource Geology》1998,48(1):23-29 Abstract: About 120 specimens of magnetite from various localities are examined by an electron microprobe analyzer. Magnetites containing more than one weight percent of silica but lack of any other components than ferrous and ferric iron, called silician magnetites in the present paper, are recognized in 23 skarn, one vein and one thermally metamorphosed massive sulfide deposits. Thus it is confirmed that this mineral occurs in nature much more frequently than so far expected. Besides silician magnetites, magnetites with appreciable amounts of Al2O3, CaO, MgO and other components along with silica, are also recognized in some skarn deposits. Magnetites with such unusual compositions are found only in hydrothermal environments, and it is suggested that precipitation mechanisms seem to be responsible for their formation. In silician magnetites, excess electric charge brought by the replacement of ferric iron in tetrahedral site by silicon, could be compensated by the replacement of ferric iron in octahedral site by ferrous iron, known as γ–Fe2SiO4 component. The natural occurrence of silician magnetites, however, gives no positive support to the existence of this component at crustal pressures. Instead a preliminary Mössbauer experiment demonstrates that one silician magnetite has a maghemite –like structure by the omission of ferrous iron from octahedral site.  相似文献    19. Impact of isostatic land uplift and artificial drainage on oxidation of brackish-water sediments rich in metastable iron sulfide   总被引：1，自引：0，他引：1   Anton Boman  Sören Fröjdö  Mats E. Åström 《Geochimica et cosmochimica acta》2010,74(4):1268-177 This study examines the dynamics of sulfur and trace elements (As, Co, Mo, Ni, Ti and Zn) when brackish-water sediments, unusually rich in metastable iron sulfide (probably a mixture of mackinawite and greigite), are brought into the oxidation zone by postglacial isostatic land uplift and farmland drainage. When subaqueous sediments approach the sea level, metastable iron sulfide is oxidized in the upmost layers and pyrite preserved and even accumulated concomitantly trapping Co, Ni and Zn but not As and Mo. When the land uplift has brought the sediments above sea level and natural drainage thus is initiated, the pyrite is oxidized and Co, Ni and Zn are released and transported down the profile. If this setting remained undisturbed, the slightly oxidized sediment (unripe soil) would become covered by peat and thus protected from further oxidation and metal translocation. Often these sediments are, however, artificially drained resulting in extensive oxidation and fast soil-profile development. The soil is an acid sulfate (AS) soil, characterized by low pH (<4), extensive leaching of metals and an abundance of disseminated brownish Fe(III) precipitates. We suggest that the fast soil development is due to initial oxidation of metastable iron sulfide, followed by pyrite oxidation. Drain bottom sediment, which in terms of chemistry and S-isotopes resembled that of the surfacing sea bottom strata, acted during the sampling period as a sink for metals. The abundant preservation of metastable iron sulfide below the groundwater table, even long periods after uplift above the sea level, is a puzzling feature. We suggest that it is the net result of sulfur starvation, an abundance of Fe(II) and strongly reducing conditions.  相似文献    20. Surface oxidation of pyrite under ambient atmospheric and aqueous (pH = 2 to 10) conditions: electronic structure and mineralogy from X-ray absorption spectroscopy      E.C Todd 《Geochimica et cosmochimica acta》2003,67(5):881-893 The nature of the surface oxidation phase on pyrite, FeS2, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur LIII edge, and iron LII,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS2 can be detected in the X-ray absorption spectra. In a 1.667 × 10−3 mol/L Fe3+ solution with ferric iron present as FeCl3 in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.  相似文献