Low-oxygen and chemical kinetic constraints on the geochemical niche of neutrophilic iron(II) oxidizing microorganisms

Neutrophilic iron oxidizing bacteria (FeOB) must actively compete with rapid abiotic processes governing Fe(II) oxidation and as a result have adapted to primarily inhabit low-O₂ environments where they can more successfully compete with abiotic Fe(II) oxidation. The spatial distribution of these microorganisms can be observed through the chemical gradients they affect, as measured using in situ voltammetric analysis for dissolved Fe(II), Fe(III), O₂, and FeS_(aq). Field and laboratory determination of the chemical environments inhabited by the FeOB were coupled with detailed kinetic competition studies for abiotic and biotic oxidation processes using a pure culture of FeOB to quantify the geochemical niche these organisms inhabit. In gradient culture tubes, the maximum oxygen levels, which were associated with growth bands of Sideroxydans lithotrophicus (ES-1, a novel FeOB), were 15-50 μM. Kinetic measurements made on S. lithotrophicus compared biotic/abiotic (killed control) Fe oxidation rates. The biotic rate can be a significant and measurable fraction of the total Fe oxidation rate below O₂ concentrations of approximately 50 μM, but biotic Fe(II) oxidation (via the biotic/abiotic rate comparison) becomes difficult to detect at higher O₂ levels. These results are further supported by observations of conditions supporting FeOB communities in field settings. Variablity in cell densities and cellular activity as well as variations in hydrous ferrous oxide mineral quantities significantly affect the laboratory kinetic rates. The microbial habitat (or geochemical niche) where FeOB are active is thus largely controlled by the competition between abiotic and biotic kinetics, which are dependent on Fe(II) concentration, P_O2, temperature and pH in addition to the surface area of hydrous ferric oxide minerals and the cell density/activity of FeOB. Additional field and lab culture observations suggest a potentially important role for the iron-sulfide aqueous molecular cluster, FeS_(aq), in the overall cycling of iron associated with the environments these microorganisms inhabit.     

Biomineralization of lepidocrocite and goethite by nitrate-reducing Fe(II)-oxidizing bacteria: Effect of pH, bicarbonate, phosphate, and humic acids

Fe(III) solid phases are the products of Fe(II) oxidation by Fe(II)-oxidizing bacteria, but the Fe(III) phases reported to form within growth experiments are, at times, poorly crystalline and therefore difficult to identify, possibly due to the presence of ligands (e.g., phosphate, carbonate) that complex iron and disrupt iron (hydr)oxide precipitation. The scope of this study was to investigate the influences of geochemical solution conditions (pH, carbonate, phosphate, humic acids) on the Fe(II) oxidation rate and Fe(III) mineralogy. Fe(III) mineral characterization was performed using ⁵⁷Fe-Mössbauer spectroscopy and μ-X-ray diffraction after oxidation of dissolved Fe(II) within Mops-buffered cell suspensions of Acidovorax sp. BoFeN1, a nitrate-reducing, Fe(II)-oxidizing bacterium. Lepidocrocite (γ-FeOOH) (90%), which also forms after chemical oxidation of Fe(II) by dissolved O₂, and goethite (α-FeOOH) (10%) were produced at pH 7.0 in the absence of any strongly complexing ligands. Higher solution pH, increasing concentrations of carbonate species, and increasing concentrations of humic acids promoted goethite formation and caused little or no changes in Fe(II) oxidation rates. Phosphate species resulted in Fe(III) solids unidentifiable to our methods and significantly slowed Fe(II) oxidation rates. Our results suggest that Fe(III) mineralogy formed by bacterial Fe(II) oxidation is strongly influenced by solution chemistry, and the geochemical conditions studied here suggest lepidocrocite and goethite may coexist in aquatic environments where nitrate-reducing, Fe(II)-oxidizing bacteria are active.     

Products of abiotic U(VI) reduction by biogenic magnetite and vivianite

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.     

东北哈尼泥炭沼泽中酚酸的组成、酚铁相互作用及其环境意义

大量研究表明,溶解性有机质与铁的螯合对生物可利用性铁的输出有重要影响.然而,对于天然有机质,尤其是泥炭沼泽源的酚类物质,与铁相互作用的地球化学机制仍然缺乏研究.以长白山西麓哈尼泥炭沼泽为研究对象,调查了泥炭沼泽源水体可溶性总铁、亚铁、水溶性总酚等理化指标.同时,测定了泥炭中酚酸的组成及含量,分析对比泥炭与土壤中铁的主要赋存形态.并开展了酚铁相互作用模拟实验,研究了泥炭沼泽源水体中酚铁相互作用机制.结果表明:哈尼泥炭沼泽水体中亚铁浓度与水溶性总酚浓度显著相关,说明水溶性总酚对亚铁的存在及运移有重要影响.哈尼泥炭中含有原儿茶酸、咖啡酸、没食子酸、龙胆酸、丁香酸、阿魏酸、对羟基苯甲酸、对香豆酸、水杨酸、香草酸等多种酚酸.其中,具有儿茶酚或没食子酰基结构的原儿茶酸、咖啡酸和没食子酸能与亚铁形成稳定螯合物,是泥炭沼泽源水体中Fe(Ⅱ)保持稳定并可以远距离迁移的关键.研究还表明,原儿茶酸、咖啡酸、没食子酸和龙胆酸对Fe(Ⅲ)有显着的还原作用,有利于沼泽区水体中的保持较高Fe(Ⅲ)和Fe(Ⅱ)浓度.哈尼泥炭中铁主要以活动态(可交换态、络合态和无定形态)为主,为铁的迁移、转化和循环奠定了基础.鉴于泥炭沼泽在全球的分布面积巨大以及亚铁对海洋生物有促进作用,酚酸对铁的作用机制对陆地系统向海洋输送生物可利用铁具有重要意义,并对碳循环、硫循环以及气候变化有重要影响.      

金属硫化物微生物氧化的机制和效应

岩石露头和矿山废弃物中的金属硫化物在地表、近地表条件下的氧化作用往往导致多种环境问题,因此,金属硫化物的地表风化一直是备受关注的表生过程之一。越来越多的证据表明微生物对矿物的氧化在金属硫化物风化过程中发挥着重要作用。实验研究发现:微生物在金属硫化物表面附着并形成微生物膜,在矿物-微生物膜界面微环境中存在着强烈的微生物氧化和化学氧化作用,两种氧化作用相互协同、共同促进。在此过程中,金属硫化物的S、As、Fe等元素经历了复杂的电子传递、逐级氧化的动力学过程,最终形成稳定的高铁硫酸盐或氧化物,并形成大量的酸性排水。该过程受多种因素的影响,包括细菌种类、光照和溶液Fe~(2+)浓度等。金属硫化物的微生物氧化直接导致重金属大量释放和严重的环境危害,释放的酸性排水还引发碳酸盐矿物分解和CO_2排放,会对全球碳循环产生不可忽视的影响。在地球演化的早期阶段,金属硫化物氧化消耗大气氧气可能导致大氧化进程滞后。尽管关于金属硫化物-微生物相互作用研究取得了长足的进展,但金属硫化物微生物氧化的分子机制和全球尺度的元素地球化学循环还有待深入研究,原位纳米观测技术的引入和全球物质循环模型研究具有必要性和紧迫性,同时也对生物冶金技术的发展有着重要的意义。     

Immobilization of uranium in the presence of Fe0(s): Model development and simulation of contrasting experimental conditions

A geochemical model is developed for the immobilization of U in the presence of metallic Fe. Zero-valent iron (ZVI) serves as a reducing agent inducing the reductive-precipitation of U, and ZVI corrosion products can serve as absorbing agents for U. The numerical model developed allows the complex interactions of U in solution in differing concentrations to be examined, under variable pH and redox conditions, with or without carbonate, in the presence of ZVI of different size and surface area. It incorporates Fe corrosion, Fe(II) and Fe(III) corrosion product formation, reductive-precipitation of U from the soluble U(VI) valence to the poorly soluble U(IV) valence, adsorption/de-sorption of U onto the Fe oxide corrosion products, and aqueous speciation. The processes of Fe corrosion and reductive precipitation of U are simulated as non-equilibrium, an improvement over other geochemical models. The reductive-precipitation process may use either ZVI or Fe(II) as the reducing agent. The model is calibrated using 3 separate sets of experimental data from published literature that cover a wide range of redox conditions. Sensitivity of the model predictions to variations in input parameters is examined. The simulation results show that the different published experimental results can be explained by different solution chemistries in the studies, specifically O₂ and CO₂ availability and pH, and the amount and surface area of the metallic Fe. With this numerical model the behavior of U in ZVI containing systems over a range of conditions realistic for groundwater can be investigated. By synthesizing observations across several experimental studies, it will lead to a broader understanding of the processes controlling U immobilization under varied geochemical conditions.     

氧化锰矿物的生物成因及其性质的研究进展

土壤中的氧化锰矿物是原生矿物风化和成土过程的产物,是最具反应活性的一类矿物,决定着环境中许多物质的形态、迁移和转化,在元素生物地球化学循环中起着重要的作用,其形成机制和环境效应备受关注。已有的研究表明,环境中氧化锰的形成与微生物作用紧密相关,微生物作用可使自然环境中的Mn(Ⅱ)氧化速率提高105倍。参与Mn(Ⅱ)氧化的微生物在环境中广泛存在,已知的典型锰氧化细菌分布在变形菌门、放线菌门或厚壁菌门,它们均通过胞外聚合物中的多铜氧化酶来催化氧化Mn(Ⅱ)。细菌氧化Mn(II)成Mn(Ⅳ)是酶催化的两个连续的快速单电子传递过程,Mn(Ⅲ)在溶液中以与酶结合的瞬时中间态出现。生物形成氧化锰的最初形态为层状锰矿物,与δ-MnO2或酸性水钠锰矿很类似,且结晶弱,粒径小,锰氧化度高,结构中的八面体空穴多,因而比化学形成的氧化锰具有更强的吸附、氧化等表面活性。环境中Mn(Ⅱ)微生物氧化及形成的Mn(Ⅲ)中间体与碳、氮、硫等生命元素的地球化学循环的关系令人关注。     

Anaerobic Metabolism in Tidal Freshwater Wetlands: III. Temperature Regulation of Iron Cycling

Understanding the ecological processes that regulate the production and fate of methane (CH₄) in wetland soils is essential for forecasting wetland CH₄ emissions. Iron reduction is an important carbon mineralization pathway that is capable of suppressing CH₄ production in freshwater wetlands, but our understanding of temperature regulation of iron oxide respiration and the subsequent impacts on CH₄ production is limited. We tested the hypothesis that temperature regulates iron reduction rates indirectly through differential effects on Fe(II) oxidation versus Fe(III) reduction, which ultimately determines the size of the microbially labile, poorly crystalline Fe(III) pool. Our study indicates that rates of iron reduction are more sensitive to changes in temperature than rates of iron oxidation, which creates imbalance in the relative proportion of Fe(II) and Fe(III) in the poorly crystalline soil iron pool as temperatures change. Our results suggest that warmer temperatures can cause the Fe(III) oxide pool to decline, limiting the Fe(III) supply to iron reducers and relieving competition for organic carbon with methanogens.     

从矿物粉晶表面反应性到矿物晶面反应性——以黄铁矿氧化行为的晶面差异性为例

地球系统中各种矿物相的物理化学反应大多是从矿物表面或界面开始的。要揭示矿物表面反应性的本质,就需要从控制其反应性的表面结构入手。由于实验条件的限制,绝大多数关于矿物表面物理化学性质的研究主要采用粉晶作为研究对象。尽管粉晶方法在研究诸如硅酸盐、碳酸盐溶解和沉淀结晶等过程中被普遍采用,但这种基于矿物粉晶的研究方法还是有一定的不足。因为形成粉晶的破碎研磨过程会导致晶体高能面的出现,高能面所具有的高活性可能会加速其反应过程,应用于地球化学反应的计算结果就可能高估了实际的地球化学反应速率。本研究以黄铁矿表面氧化反应的晶面差异性为例,从晶面结构制约反应性的角度出发,重新审视了黄铁矿氧化的相关问题,弥补了传统"粉晶研究"中对黄铁矿氧化速率和氧化机理认识的缺陷。黄铁矿宽范围的氧化速率实测值很可能是由不同晶面间较大的反应性差异导致;水在黄铁矿的氧化过程中同时扮演着传递电子的催化剂和反应物的角色,也是黄铁矿氧化反应速控步(rate-limiting step)的核心物质。这些认识首次明确了黄铁矿不同晶面反应性差异的重要性,并提示我们应将传统表面矿物学的研究推向更为精确的晶面矿物学水平。这一从晶面角度考察发生在矿物表面的地球化学反应的研究方法可为构建更为精确的地球化学模型提供理论基础。     

Evidence for equilibrium iron isotope fractionation by nitrate-reducing iron(II)-oxidizing bacteria

Iron isotope fractionations produced during chemical and biological Fe(II) oxidation are sensitive to the proportions and nature of dissolved and solid-phase Fe species present, as well as the extent of isotopic exchange between precipitates and aqueous Fe. Iron isotopes therefore potentially constrain the mechanisms and pathways of Fe redox transformations in modern and ancient environments. In the present study, we followed in batch experiments Fe isotope fractionations between Fe(II)_aq and Fe(III) oxide/hydroxide precipitates produced by the Fe(III) mineral encrusting, nitrate-reducing, Fe(II)-oxidizing Acidovorax sp. strain BoFeN1. Isotopic fractionation in ⁵⁶Fe/⁵⁴Fe approached that expected for equilibrium conditions, assuming an equilibrium Δ⁵⁶Fe_{Fe(OH)3-Fe(II)aq} fractionation factor of +3.0‰. Previous studies have shown that Fe(II) oxidation by this Acidovorax strain occurs in the periplasm, and we propose that Fe isotope equilibrium is maintained through redox cycling via coupled electron and atom exchange between Fe(II)_aq and Fe(III) precipitates in the contained environment of the periplasm. In addition to the apparent equilibrium isotopic fractionation, these experiments also record the kinetic effects of initial rapid oxidation, and possible phase transformations of the Fe(III) precipitates. Attainment of Fe isotope equilibrium between Fe(III) oxide/hydroxide precipitates and Fe(II)_aq by neutrophilic, Fe(II)-oxidizing bacteria or through abiologic Fe(II)_aq oxidation is generally not expected or observed, because the poor solubility of their metabolic product, i.e. Fe(III), usually leads to rapid precipitation of Fe(III) minerals, and hence expression of a kinetic fractionation upon precipitation; in the absence of redox cycling between Fe(II)_aq and precipitate, kinetic isotope fractionations are likely to be retained. These results highlight the distinct Fe isotope fractionations that are produced by different pathways of biological and abiological Fe(II) oxidation.     

The Bizielle vein (valle de Gistain): A case of iron oxide transformations at the Pyrenees of Spain

The Bizielle vein has some unique features among the Pyrenean alpine veins that allow us to address the question of the nature of iron oxides transformations under low temperature hydrothermal conditions, which is well known to prevailed over wide areas of western Europe between early Triassic to early Cretaceous times. Isotopic studies indicate a deep-seated origin of the ore-forming fluids and suggest that the metals were leached from the Variscan basement (mainly from granites). Isotopic geothermometry and regional evidences point to a 250 °C and reducing fluid, being SH₂ the predominant S specie. Under such conditions, the proposed in situ deposition of hematite is a consequence of Fe carbonates dissolution and oxidation involving dissolution/precipitation processes in the sense of Putnis. Non-redox model is a quite plausible origin for subsequent hematite to magnetite conversion.     

Oxidation of As(III) by MnO2 in the absence and presence of Fe(II) under acidic conditions

Oxidation of As(III) by natural manganese (hydr)oxides is an important geochemical reaction mediating the transformation of highly concentrated As(III) in the acidic environment such as acid mine drainage (AMD) and industrial As-contaminated wastewater, however, little is known regarding the presence of dissolved Fe(II) on the oxidation process. In this study, oxidation of As(III) in the absence and presence of Fe(II) by MnO₂ under acidic conditions was investigated. Kinetic results showed that the presence of Fe(II) significantly inhibited the removal of As(III) (including oxidation and sorption) by MnO₂ in As(III)-Fe(II) simultaneous oxidation system even at the molar ratio of Fe(II):As(III) = 1/64:1, and the inhibitory effects increased with the increasing ratios of Fe(II):As(III). Such an inhibition could be attributed to the formation of Fe(III) compounds covering the surface of MnO₂ and thus preventing the oxidizing sites available to As(III). On the other hand, the produced Fe(III) compounds adsorbed more As(III) and the oxidized As(V) on the MnO₂ surface with an increasing ratio of Fe(II):As(III) as demonstrated in kinetic and XPS results. TEM and EDX results confirmed the formation of Fe compounds around MnO₂ particles or separated in solution in Fe(II) individual oxidation system, Fe(II) pre-treated and simultaneous oxidation processes, and schwertmannite was detected in Fe(II) individual and Fe pre-treated oxidation processes, while a new kind of mineral, probably amorphous FeOHAs or FeAsO₄ particles were detected in Fe(II)-As(III) simultaneous oxidation process. This suggests that the mechanisms are different in Fe pre-treated and simultaneous oxidation processes. In the Fe pre-treated and MnO₂-mediated oxidation pathway, As(III) diffused through a schwertmannite coating formed around MnO₂ particles to be oxidized. The newly formed As(V) was adsorbed onto the schwertmannite coating until its sorption capacity was exceeded. Arsenic(V) then diffused out of the coating and was released into the bulk solution. The diffusion into the schwertmannite coating and the oxidation of As(III) and sorption of both As(V) and As(III) onto the coating contributed to the removal of total As from the solution phase. In the simultaneous oxidation pathway, the competitive oxidation of Fe(II) and As(III) on MnO₂ occurred first, followed by the formation of FeOHAs or FeAsO₄ around MnO₂ particles, and these poorly crystalline particles of FeOHAs and FeAsO₄ remained suspended in the bulk solution to adsorb As(III) and As(V). The present study reveals that the formation of Fe(III) compounds on mineral surfaces play an important role in the sorption and oxidation of As(III) by MnO₂ under acidic conditions in natural environments, and the mechanisms involved in the oxidation of As(III) depend upon how Fe(II) is introduced into the As(III)-MnO₂ system.     

Sorption and precipitation of Co(II) in Hanford sediments and alkaline aluminate solutions

Sorption and precipitation of Co(II) in simplified model systems related to the Hanford site high-level nuclear waste tank leakage were investigated through solution studies, geochemical modeling, and X-ray absorption fine structure (XAFS) spectroscopy. Studies of Co(II) sorption to pristine Hanford sediments (ERDF and Sub), which consist predominantly of quartz, plagioclase, and alkali feldspar, show an adsorption edge centered at pH ≈ 8.0 for both sediments studied, with sorption >99% above pH ≈ 9.0. Aqueous SiO₂ resulting from dissolution of the sediments increased in concentration with increasing pH, though the systems remained undersaturated with respect to quartz. XAFS studies of Co(II) sorption to both sediment samples reveal the oxidation of Co(II) to Co(III), likely by dissolved O₂, although this oxidation was incomplete in the Sub sediment samples. The authors propose that Fe(II) species, either in aqueous solution or at mineral surfaces, partially inhibited Co(II) oxidation in the Sub sediment samples, as these sediments contain significantly higher quantities of Fe(II)-bearing minerals which likely partially dissolved under the high-pH solution conditions. In alkaline solutions, Al precipitated as bayerite, gibbsite, or a mixture of the two at pH > 7; an amorphous gel formed at pH values less than 7. Aqueous Co concentrations were well below the solubility of known Co-bearing phases at low pH, suggesting that Co was removed from solution through an adsorption mechanism. At higher pH values, Co concentrations closely matched the solubility of a Co-bearing hydrotalcite-like solid. XAFS spectra of Co(II) sorbed to Al-hydroxide precipitates are similar to previously reported spectra for such hydrotalcite-like phases. The precipitation processes observed in this study can significantly reduce the environmental hazard posed by ⁶⁰Co in the environment.     

Size, density and composition of cell-mineral aggregates formed during anoxygenic phototrophic Fe(II) oxidation: Impact on modern and ancient environments

Cell-Fe(III) mineral aggregates produced by anoxygenic Fe(II)-oxidizing photoautotrophic microorganisms (photoferrotrophs) may be influential in the modern Fe cycle and were likely an integral part of ancient biogeochemical cycles on early Earth. While studies have focused on the environmental conditions under which modern photoferrotrophs grow and the kinetics, physiology and mechanism of Fe(II) oxidation, no systematic analyses of the physico-chemical characteristics of those aggregates, such as shape, size, density and chemical composition, have as yet been conducted. Herein, experimental results show most aggregates are bulbous or ragged in shape, with an average particle size of 10-40 μm, and densities that typically range between 2.0 and 2.4 g/cm³; the cell fraction of the aggregates increased and their density decreased with initial Fe(II) concentration. The mineralogy of the ferric iron phase depended on the composition of the medium: goethite formed in cultures grown by oxidation of dissolved Fe(II) medium in the presence of low phosphate concentrations, while poorly ordered ferrihydrite (or Fe(III) phosphates) formed when amorphous Fe(II) minerals (Fe(II)-phosphates) and high concentrations of phosphate were initially present. Importantly, in all experiments, a fraction of the photoautotrophic cells remained planktonic, demonstrating a constant stoichiometric excess of Fe(III) compared to the autotrophically fixed carbon in the biogenic precipitate. These results not only have an important bearing on nutrient and trace element cycling in the modern water column, but the size, shape and composition of the aggregates can be used to estimate aggregate reactivity during sediment diagenesis over short and geologic time scales.     

Dependence of microbial magnetite formation on humic substance and ferrihydrite concentrations

Iron mineral (trans)formation during microbial Fe(III) reduction is of environmental relevance as it can influence the fate of pollutants such as toxic metal ions or hydrocarbons. Magnetite is an important biomineralization product of microbial iron reduction and influences soil magnetic properties that are used for paleoclimate reconstruction and were suggested to assist in the localization of organic and inorganic pollutants. However, it is not well understood how different concentrations of Fe(III) minerals and humic substances (HS) affect magnetite formation during microbial Fe(III) reduction. We therefore used wet-chemical extractions, magnetic susceptibility measurements and X-ray diffraction analyses to determine systematically how (i) different initial ferrihydrite (FH) concentrations and (ii) different concentrations of HS (i.e. the presence of either only adsorbed HS or adsorbed and dissolved HS) affect magnetite formation during FH reduction by Shewanella oneidensis MR-1. In our experiments magnetite formation did not occur at FH concentrations lower than 5 mM, even though rapid iron reduction took place. At higher FH concentrations a minimum fraction of Fe(II) of 25-30% of the total iron present was necessary to initiate magnetite formation. The Fe(II) fraction at which magnetite formation started decreased with increasing FH concentration, which might be due to aggregation of the FH particles reducing the FH surface area at higher FH concentrations. HS concentrations of 215-393 mg HS/g FH slowed down (at partial FH surface coverage with sorbed HS) or even completely inhibited (at complete FH surface coverage with sorbed HS) magnetite formation due to blocking of surface sites by adsorbed HS. These results indicate the requirement of Fe(II) adsorption to, and subsequent interaction with, the FH surface for the transformation of FH into magnetite. Additionally, we found that the microbially formed magnetite was further reduced by strain MR-1 leading to the formation of either dissolved Fe(II), i.e. Fe²⁺, in HEPES buffered medium or Fe(II) carbonate (siderite) in bicarbonate buffered medium. Besides the different identity of the Fe(II) compound formed at the end of Fe(III) reduction, there was no difference in the maximum rate and extent of microbial iron reduction and magnetite formation during FH reduction in the two buffer systems used. Our findings indicate that microbial magnetite formation during iron reduction depends on the geochemical conditions and can be of minor importance at low FH concentrations or be inhibited by adsorption of HS to the FH surface. Such scenarios could occur in soils with low iron mineral or high organic matter content.     

Iron Speciation of Mud Breccia from the Dushanzi Mud Volcano in the Xinjiang Uygur Autonomous Region, NW China

Organic-inorganic interactions occurring in petroleum-related mud volcanoes can help predict the chemical processes that are responsible for methane emissions to the atmosphere. Seven samples of mud breccia directly ejected from one crater were collected in the Dushanzi mud volcano, along with one argillite sample of the original reddish host rocks distal from the crater, for comparison purposes. The mineral and chemical compositions as well as iron species of all samples were determined using XRD, XRF and M?ssbauer spectroscopy, respectively. The results indicate that a series of marked reactions occurred in the mud volcano systems, more specifically in the mud breccia when compared to the original rocks. Changes mainly included: (1) some conversion of clay minerals from smectite into chlorite and illite, and the precipitation of secondary carbonate minerals such as calcite and siderite; (2) silicon depletion and significant elemental enrichment of iron, manganese, magnesium, calcium and phosphorus; and (3) transformation of iron from ferric species in hematite and smectite into ferrous species in siderite, chlorite and illite. These geochemical reactions likely induced the color changes of the original reddish Neogene argillite to the gray or black mud breccia, as a result of reduction of elements and/or alteration of minerals associated with the oxidation of hydrocarbons. Our results also suggest that greenhouse gases emitted from the mud volcanoes are lowered through a series of methane oxidation reactions and carbon fixation (i.e., through carbonate precipitation).     

Pyrite oxidation: a state-of-the-art assessment of the reaction mechanism

The oxidation of pyrite to release ferrous iron and sulfate ions to solution involves the transfer of seven electrons from each sulfur atom in the mineral to an aqueous oxidant. Because only one or, at most, two electrons can be transferred at a time, the overall oxidation process is quite complex. Furthermore, pyrite is a semiconductor, so the electrons are transferred from sulfur atoms at an anodic site, where oxygen atoms from water molecules attach to the sulfur atoms to form sulfoxy species, through the crystal to cathodic Fe(II) sites, where they are acquired by the oxidant species. The reaction at the cathodic sites is the rate-determining step for the overall process. This paper maps out the most important steps in this overall process.     

萨瓦甫齐铀矿床层间氧化带地球化学特征

萨瓦甫齐铀矿床不同地段层间氧化带的氧化还原程度是不同的。利用诸如w（Fe3＋）/w（Fe2＋）、w（Ra）/w（U）和有机炭等地球化学参数探讨了萨瓦甫齐铀矿床层间氧化带的地球化学特征,即矿床西南部层间氧化带氧化程度较弱,表现为全硫（∑S）、总铁（TFe）和矿石的铀质量分数低;而矿床中部及东北部层间氧化带氧化程度较强,尤其以东北部突出,它们的全硫、总铁和矿石的铀质量分数均高。铀矿化强弱明显与层间氧化带的氧化还原程度有关,层间氧化带的氧化程度越强,铀矿化则愈强;反之,则弱。     

Relative contributions of abiotic and biological factors in Fe(II) oxidation in mine drainage

The oxidation of Fe(II) is apparently the rate-limiting step in passive treatment of coal mine drainage. Little work has been done to determine the kinetics of oxidation in such field systems, and no models of passive treatment systems explicitly consider iron oxidation kinetics. A Stella II^™ model using Fe(II)_init concentration, pH, temperature, Thiobacillus ferrooxidans and O₂ concentration, flow rate, and pond volume is used to predict Fe(II) oxidation rates and concentrations in seventeen ponds under a wide range of conditions (pH 2.8 to 6.8 with Fe(II) concentrations of less than 240 mg L⁻¹) from 6 passive treatment facilities. The oxidation rate is modeled based on the combination of published abiotic and biological laboratory rate laws. Although many other variables have been observed to influence Fe(II) oxidation rates, the 7 variables above allow field systems to be modeled reasonably accurately for conditions in this study.Measured T. ferrooxidans concentrations were approximately 10⁷ times lower than concentrations required in the model to accurately predict field Fe(II) concentrations. This result suggests that either 1) the most probable number enumeration method underestimated the bacterial concentrations, or 2) the biological rate law employed underestimated the influence of bacteria, or both. Due to this discrepancy, bacterial concentrations used in the model for pH values of less than 5 are treated as fit parameters rather than empirically measured values.Predicted Fe(II) concentrations in ponds agree well with measured Fe(II) concentrations, and predicted oxidation rates also agree well with field-measured rates. From pH 2.8 to approximately pH 5, Fe(II) oxidation rates are negatively correlated with pH and catalyzed by T. ferrooxidans. From pH 5 to 6.4, Fe(II) oxidation appears to be primarily abiotic and is positively correlated with pH. Above pH 6.4, oxidation appears to be independent of pH. Above pH 5, treatment efficiency is affected most by changing design parameters in the following order: pH>temperature≈influent Fe(II)>pond volume≈O₂. Little to no increase in Fe(II) oxidation rate occurs due to pH increases above pH 6.4. Failure to consider Fe(II) oxidation rates in treatment system design may result in insufficient Fe removal.     

Geochemical and mineralogical aspects of sulfide mine tailings

Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO₄, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS₂], pyrrhotite [Fe_(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H₂S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.