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1.
Structural constraints of ferric (hydr)oxides on dissimilatory iron reduction and the fate of Fe(II)
Colleen M. Hansel Shawn G. Benner Peter Nico Scott Fendorf 《Geochimica et cosmochimica acta》2004,68(15):3217-3229
Due to the strong reducing capacity of ferrous Fe, the fate of Fe(II) following dissimilatory iron reduction will have a profound bearing on biogeochemical cycles. We have previously observed the rapid and near complete conversion of 2-line ferrihydrite to goethite (minor phase) and magnetite (major phase) under advective flow in an organic carbon-rich artificial groundwater medium. Yet, in many mineralogically mature environments, well-ordered iron (hydr)oxide phases dominate and may therefore control the extent and rate of Fe(III) reduction. Accordingly, here we compare the reducing capacity and Fe(II) sequestration mechanisms of goethite and hematite to 2-line ferrihydrite under advective flow within a medium mimicking that of natural groundwater supplemented with organic carbon. Introduction of dissolved organic carbon upon flow initiation results in the onset of dissimilatory iron reduction of all three Fe phases (2-line ferrihydrite, goethite, and hematite). While the initial surface area normalized rates are similar (∼10−11 mol Fe(II) m−2 g−1), the total amount of Fe(III) reduced over time along with the mechanisms and extent of Fe(II) sequestration differ among the three iron (hydr)oxide substrates. Following 16 d of reaction, the amount of Fe(III) reduced within the ferrihydrite, goethite, and hematite columns is 25, 5, and 1%, respectively. While 83% of the Fe(II) produced in the ferrihydrite system is retained within the solid-phase, merely 17% is retained within both the goethite and hematite columns. Magnetite precipitation is responsible for the majority of Fe(II) sequestration within ferrihydrite, yet magnetite was not detected in either the goethite or hematite systems. Instead, Fe(II) may be sequestered as localized spinel-like (magnetite) domains within surface hydrated layers (ca. 1 nm thick) on goethite and hematite or by electron delocalization within the bulk phase. The decreased solubility of goethite and hematite relative to ferrihydrite, resulting in lower Fe(III)aq and bacterially-generated Fe(II)aq concentrations, may hinder magnetite precipitation beyond mere surface reorganization into nanometer-sized, spinel-like domains. Nevertheless, following an initial, more rapid reduction period, the three Fe (hydr)oxides support similar aqueous ferrous iron concentrations, bacterial populations, and microbial Fe(III) reduction rates. A decline in microbial reduction rates and further Fe(II) retention in the solid-phase correlates with the initial degree of phase disorder (high energy sites). As such, sustained microbial reduction of 2-line ferrihydrite, goethite, and hematite appears to be controlled, in large part, by changes in surface reactivity (energy), which is influenced by microbial reduction and secondary Fe(II) sequestration processes regardless of structural order (crystallinity) and surface area. 相似文献
2.
Stable Fe isotope fractionations produced by aqueous Fe(II)-hematite surface interactions 总被引：1，自引：0，他引：1
Lingling Wu Brian L. Beard Eric E. Roden Christopher B. Kennedy 《Geochimica et cosmochimica acta》2010,74(15):4249-8833
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
3.
William D. Burgos Yilin Fang Gour-Tsyh Yeh Byong-Hun Jeon 《Geochimica et cosmochimica acta》2003,67(15):2735-2748
This paper presents and validates a new paradigm for modeling complex biogeochemical systems using a diagonalized reaction-based approach. The bioreduction kinetics of hematite (α-Fe2O3) by the dissimilatory metal-reducing bacterium (DMRB) Shewanella putrefaciens strain CN32 in the presence of the soluble electron shuttling compound anthraquinone-2,6-disulfonate (AQDS) is used for presentation/validation purposes. Experiments were conducted under nongrowth conditions with H2 as the electron donor. In the presence of AQDS, both direct biological reduction and indirect chemical reduction of hematite by bioreduced anthrahydroquinone-2,6-disulfonate (AH2DS) can produce Fe(II). Separate experiments were performed to describe the bioreduction of hematite, bioreduction of AQDS, chemical reduction of hematite by AH2DS, Fe(II) sorption to hematite, and Fe(II) biosorption to DMRB. The independently determined rate parameters and equilibrium constants were then used to simulate the parallel kinetic reactions of Fe(II) production in the hematite-with-AQDS experiments. Previously determined rate formulations/parameters for the bioreduction of hematite and Fe(II) sorption to hematite were systematically tested by conducting experiments with different initial conditions. As a result, the rate formulation/parameter for hematite bioreduction was not modified, but the rate parameters for Fe(II) sorption to hematite were modified slightly. The hematite bioreduction rate formulation was first-order with respect to hematite ”free“ surface sites and zero-order with respect to DMRB based on experiments conducted with variable concentrations of hematite and DMRB. The AQDS bioreduction rate formulation was first-order with respect to AQDS and first-order with respect to DMRB based on experiments conducted with variable concentrations of AQDS and DMRB. The chemical reduction of hematite by AH2DS was fast and considered to be an equilibrium reaction. The simulations of hematite-with-AQDS experiments were very sensitive to the equilibrium constant for the hematite-AH2DS reaction. The model simulated the hematite-with-AQDS experiments well if it was assumed that the ferric oxide “surface” phase was more disordered than pure hematite. This is the first reported study where a diagonalized reaction-based model was used to simulate parallel kinetic reactions based on rate formulations/parameters independently obtained from segregated experiments. 相似文献
4.
Structural changes and surface oxidation state were examined following the reaction of hematite (0 0 1), (0 1 2), and (1 1 0) with aqueous Fe(II). X-ray reflectivity measurements indicated that Fe(II) induces changes in the structure of all three surfaces under both acidic (pH 3) and neutral (pH 7) conditions. The structural changes were generally independent of pH although the extent of surface transformation varied slightly between acidic and neutral conditions; no systematic trends with pH were observed. Induced changes on the (1 1 0) and (0 1 2) surfaces include the addition or removal of partial surface layers consistent with either growth or dissolution. In contrast, a <1 nm thick, discontinuous film formed on the (0 0 1) surface that appears to be epitaxial yet is not a perfect extension of the underlying hematite lattice, being either structurally defective, compositionally distinct, or nanoscale in size and highly relaxed. Resonant anomalous X-ray reflectivity measurements determined that the surface concentration of Fe(II) present after reaction at pH 7 was below the detection limit of approximately 0.5-1 μmol/m2 on all surfaces. These observations are consistent with Fe(II) oxidative adsorption, whereby adsorbed Fe(II) is oxidized by structural Fe(III) in the hematite lattice, with the extent of this reaction controlled by surface structure at the atomic scale. The observed surface transformations at pH 3 show that Fe(II) oxidatively adsorbs on hematite surfaces at pH values where little net adsorption occurs, based on historical macroscopic Fe(II) adsorption behavior on fine-grained hematite powders. This suggests that Fe(II) plays a catalytic role, in which an electron from an adsorbed Fe(II) migrates to and reduces a lattice Fe(III) cation elsewhere, which subsequently desorbs in a scenario with zero net reduction and zero net adsorption. Given the general pH-independence and substantial mass transfer involved, this electron and atom exchange process appears to be a significant subsystem within macroscopic pH-dependent Fe(II) adsorption. 相似文献
5.
T. Peretyazhko J.M. Zachara B.-H. Jeon C. Liu C.T. Resch 《Geochimica et cosmochimica acta》2008,72(6):1521-1539
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
6.
磁赤铁矿可以在厌氧微生物作用下固相转化为磁铁矿,这种转化过程具有重要的矿物学及环境磁学意义。文章通过开展硫酸盐还原菌（SRB） —磁赤铁矿交互作用实验,重点探讨了SRB 活性对磁赤铁矿—磁铁矿固相转化速率的影响。在31 d 培养期内,SO42-+SRB+磁赤铁矿体系中SRB 的生长导致16.7%的SO42-转化为酸可挥发性硫（AVS）,部分还原释放的Fe（II） 与AVS 反应生成单硫化物、双硫化物和多硫化物,同时铁氧化物因溶解作用粒径减小;在无SO42-的SRB+磁赤铁矿体系中, SRB 还原产生的Fe （II） 主要存在于铁氧化物中,没有次生沉淀产生。X 射线衍射和穆斯堡尔谱分析结果表明在SRB 作用下纳米磁赤铁矿逐渐向磁铁矿转化,加入SO42-时转化速率加快,与矿物接触的SRB 菌体的数量及其向磁赤铁矿传递电子的能力均得到了增强。在天然或人工厌氧条件下,SO42-是制约磁赤铁矿向磁铁矿转化的重要因素。 相似文献
7.
Competition between enzymatic and abiotic reduction of uranium(VI) under iron reducing conditions 总被引：1，自引：0，他引：1
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
8.
Summary Garnet occurs as a significant mineral constituent of felsic garnet-biotite granite in the southern edge of the Třebíč pluton.
Two textural groups of garnet were recognized on the basis of their shape and relationship to biotite. Group I garnets are
1.5–2.5 mm, euhedral grains which have no reaction relationship with biotite. They are zoned having high XMn at the rims and are considered as magmatic. Group II garnets form grain aggregates up to 2.5 cm in size, with anhedral shape
of individual grains. The individual garnet II grains are usually rimmed by biotite and have no compositional zoning. The
core of group I garnets and group II garnets contains 67–80 mol% of almandine, 5–19 mol% of pyrope, 7–17 mol% of spessartine
and 2–4 mol% of grossular. Biotite occurs in two generations; both are magnesian siderophyllites with Fe/(Fe + Mg) = 0.50–0.69.
The matrix biotite in granites (biotite I) has high Ti content (0.09–0.31 apfu) and Fe/(Fe + Mg) ratio between 0.50 and 0.59.
Biotite II forms reaction rims around garnet, is poor in Ti (0.00–0.06 apfu) and has a Fe/(Fe + Mg) ratio between 0.61 and
0.69. The textural relationship between biotite and garnet indicates that garnet reacted with granitic melt to form Ti-poor
biotite and a new granitic melt, depleted in Ti and Mg and enriched in Fe and Al. In contrast to the host durbachites (hornblende-biotite
melagranites), which originated by mixing of crustal melts and upper mantle melts, the origin of garnet-bearing granites is
related to partial melting of the aluminium-rich metamorphic series of the Moldanubian Zone. 相似文献
9.
Dissimilatory reduction of Fe(III) by Shewanella oneidensis MR-1 was evaluated using natural specular hematite as sole electron acceptor in an open system under dynamic flow conditions to obtain a better understanding of biologic Fe(III) reduction in the natural environment. During initial exposure to hematite under advective flow conditions, cells exhibited a transient association with the mineral characterized by a rapid rate of attachment followed by a comparable rate of detachment before entering a phase of surface colonization that was slower but steadier than that observed initially. Accumulation of cells on the hematite surface was accompanied by the release of soluble Fe(II) into the aqueous phase when no precautions were taken to remove amorphous Fe(III) from the mineral surface before colonization. During the period of surface colonization following the detachment phase, cell yield was estimated at 1.5-4 × 107 cells/μmol Fe(II) produced, which is similar to that reported in studies conducted in closed systems. This yield does not take into account those cells that detached during this phase or the Fe(II) that remained associated with the hematite surface. Hematite reduction by the bacterium led to localized surface pitting and localized discrete areas where Fe (II) precipitation occurred. The cleavage plane of hematite left behind after bacterial reduction, as revealed by our results, strongly suggests, that heterogeneous energetics of the mineral surface play a strong role in this bioprocess. AQDS, an electron shuttle shown to stimulate bioreduction of Fe(III) in other studies, inhibited reduction of hematite by this bacterium under the dynamic flow conditions employed in the current study. 相似文献
10.
我国砂岩型铀矿分带特征研究现状及存在问题 总被引：1，自引：0，他引：1
作为一种重要的国家战略资源,砂岩型铀矿床是当今世界上最重要的铀矿床类型之一。本文详细地介绍了砂岩型铀矿在国内外的分布特征及占比情况,并对外生地质作用矿床类型中表生流体作用形成的层间渗透砂岩型和潜水渗透砂岩型铀矿床进行了讨论,发现层间渗透砂岩型铀矿床在外表颜色、矿物组合以及地球化学等方面均具有明显的氧化-还原分带现象,此外,矿床内部还具有细菌分带现象。颜色分带在氧化带、氧化-还原过渡带以及还原带之间具有明显不同的特征;矿物组合在不同分带之间各不相同;地球化学分带表现为U、TOC含量以及Fe~(2+)/Fe~(3+)、Th/U比值在各分带之间差异较大。此外,硫酸盐还原菌、硫杆菌、铁细菌及硝化菌等细菌在不同分带之间的数量相差悬殊,而且硫酸盐还原菌数量与TOC呈明显正相关性。通过矿化带内的碳、硫同位素分析,发现硫酸盐还原菌参与了成矿过程,推测其可能是导致碳、硫同位素分馏的主要因素。总体来看,颜色分带、矿物分带、地球化学分带以及细菌分带均与氧化-还原分带呈耦合关系。本文通过总结层间渗透砂岩型和潜水渗透砂岩型铀矿床的成矿模式和当前分带研究中存在的问题,提出了由细菌、地球化学反应参与的砂岩型铀矿床成矿机理,以及未来亟需解决的若干关键科学问题。典型砂岩型铀矿床的分带现象在物、化、探、遥等领域的异常响应对寻找砂岩型铀矿床具有重要的指导意义。 相似文献
11.
《International Geology Review》2012,54(11):1387-1392
Bertrandite-phenacite, genthelvite (danalite), and euclase in association with magnetite (hematite)-feldspar metasomatites, quartz-magnetite-sulfide metasomatites, and quartz-chlorite veins, respectively, in tectonically controlled zones, are shown to be products of medium and low-temperature pneumatolytic-hydrothermal alterations of biotite granites. -- IGR Staff. 相似文献
12.
Uranium and polymetallic U mineralization hosted within brecciated albitites occurs one kilometer south of the magnetite-rich Au–Co–Bi–Cu NICO deposit in the southern Great Bear magmatic zone (GBMZ), Canada. Concentrations up to 1 wt% U are distributed throughout a 3 by 0.5 km albitization corridor defined as the Southern Breccia zone. Two distinct U mineralization events are observed. Primary uraninite precipitated with or without pyrite–chalcopyrite?±?molybdenite within magnetite–ilmenite–biotite–K-feldspar-altered breccias during high-temperature potassic–iron alteration. Subsequently, pitchblende precipitated in earthy hematite–specular hematite–chlorite veins associated with a low-temperature iron–magnesium alteration. The uraninite-bearing mineralization postdates sodic (albite) and more localized high-temperature potassic–iron (biotite–magnetite ± K-feldspar) alteration yet predates potassic (K-feldspar), boron (tourmaline) and potassic–iron–magnesium (hematite ± K-feldspar ± chlorite) alteration. The Southern Breccia zone shares attributes of the Valhalla (Australia) and Lagoa Real (Brazil) albitite-hosted U deposits but contains greater iron oxide contents and lower contents of riebeckite and carbonates. Potassium, Ni, and Th are also enriched whereas Zr and Sr are depleted with respect to the aforementioned albitite-hosted U deposits. Field relationships, geochemical signatures and available U–Pb dates on pre-, syn- and post-mineralization intrusions place the development of the Southern Breccia and the NICO deposit as part of a single iron oxide alkali-altered (IOAA) system. In addition, this case example illustrates that albitite-hosted U deposits can form in albitization zones that predate base and precious metal ore zones in a single IOAA system and become traps for U and multiple metals once the tectonic regime favors fluid mixing and oxidation-reduction reactions. 相似文献
13.
The textural characteristics and trace element geochemistry of hematite with U-W-Sn-Mo signatures from the Cu-U-Au-Ag orebody at Olympic Dam, South Australia, are documented. Olympic Dam is the archetype for iron-oxide copper–gold (IOCG) deposits where hematite is by far the most abundant mineral in the orebody. The deposit is located within hematite-bearing breccias (>5% Fe) hosted by the ∼1.6 Ga Roxby Downs Granite (RDG). Although such breccias are mostly derived from RDG, they also include volcanic clasts and sedimentary rocks. Samples cover the ∼6 km strike length and ∼2 km vertical extent of mineralisation, including hematite from the aforementioned lithologies. Hematite with U-W-Sn-Mo (‘granitophile’ elements) signatures is recognised throughout all lithologies and parts of the deposit. Hematite enriched in granitophile elements is represented by a variety of textures, of which zoned hematite, defined by oscillatory zonation patterns, is the most prominent and can be tied to the age of the RDG, and thus initiation of the IOCG system as confirmed by published U-Pb geochronology. Other categories of hematite with granitophile signatures include hematite resulting from replacement of pre-existing minerals (e.g., carbonates and feldspars), as well as replacement of previous oscillatory-zoned hematites. Matrix and vacuole filling hematite from volcanoclastic-dominated intervals also carry ‘granitophile’ signatures. In addition, some colloform types which likely post-date primary IOCG mineralisation are also rich in ‘granitophile’ elements. Trace element mapping and spot analysis by laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS) defines complex trace element signatures of hematite, which, in addition to the ‘granitophile’ elements, also comprise rare earth elements, high field strength elements, chalcogens and transition metals.The distinct geochemical signature, characterised by enrichment in the ‘granitophile’ elements (up to wt% levels of U and W within individual zones, and up to thousands of ppm Mo and Sn) prevails throughout the hematite in the deposit irrespective of textures. Iron-oxides have been repeatedly formed, reworked and overprinted by subsequent cycles of brecciation, fluid-mineral reaction, remobilization, element redistribution and recrystallisation. Coupled dissolution-replacement reactions are discussed as having played a major role in the modification of textural and geochemical patterns in hematite, but also allow for widespread preservation of primary geochemical signatures. Despite its simple chemistry, the crystal-structural modularity of hematite can adapt and retain evolving fluid signatures. The reported trace element signatures are fully concordant with conceptual frameworks for the genesis of IOCG systems, and may be an inherent, albeit hitherto under-reported characteristic of other IOCG systems. Hematite is probably by far the most important W-, Sn- and Mo-bearing phase in the deposit by mass. 相似文献
14.
Nicolas F. Spycher Montarat Issarangkun S. Sevinç ?engör Tim R. Ginn Rajesh K. Sani 《Geochimica et cosmochimica acta》2011,75(16):4426-4440
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
15.
George W. Fisher 《Contributions to Mineralogy and Petrology》1970,29(2):91-103
Mineral segregations formed by metamorphic differentiation are an important source of information on diffusion processes in metamorphism. Segregations consisting of andalusite-biotite-quartz cores surrounded by a quartz-feldspar mantle in sillimanite-biotitefeldspar-quartz gneiss near Västervik, Sweden (Loberg, 1963) formed by core-to-mantle migration of K, and mantle-to-core migration of Fe, Mg and Ca. These migrations can be represented by a set of interconnected ionic equilibria involving reaction of microcline and Fe(OH)+ in the core to form andalusite plus biotite, and reaction of K+, sillimanite and biotite in the mantle to form microcline. Equilibrium constants for these reactions, calculated for conditions inferred from the mineral assemblage and biotite composition, indicate gradients of K+ activity (higher in core) and Fe(OH)+ activity (higher in mantle). These gradients result simply from the free energy difference between andalusite and sillimanite, without invoking pre-existing megascopic inhomogeneities in the rock or surface energy effects. Although small, these gradients appear to be capable of driving the segregation process. 相似文献
16.
Several studies have shown that SO4-reducing bacteria (SRB) are active in acidic sulfide-rich mine tailings and sediments impacted by mining activities. SRB activity in acidic tailings has been shown to vary with seasons as a result of fluctuating in situ physico-chemical conditions. Iron-reducing bacteria (FeRB) also play an important role in Fe cycling in sediments impacted by mining activities, but their activity in mine tailings is poorly understood, despite the fact that geochemical evidence indicates that they might be active. The present study was undertaken to assess the seasonal changes in SRB and FeRB abundance and activity in alkaline Pb–Zn mine tailings (Calumet tailings) located near Ottawa, ON, Canada. Results showed that FeRB and SRB populations were present throughout the year at two different sampling sites at the Calumet tailings, but SO4 reduction rates (SRR) were lower in the spring than in the summer, indicating that SRB activity was affected by organic C availability and/or temperature. Surface agricultural runoff at one site provided ample nutrients and organic C to the tailings, but SRB activity remained lower than the site not impacted by nutrient runoff, suggesting that the type of organic C was different between the two sites and that less labile organic substrates were available to SRB in the organic-rich site. High SRB activity in the site containing low organic C inhibited the abundance of FeRB, and possibly their activity, as a result of abiotic reduction of Fe(III)-rich minerals by biogenic sulfides, which lowered the pool of final electron acceptors. The abiotic reduction pathway was consistent with the porewater data which showed that sulfide was consumed and SO4 produced, along with Fe(II). These results show a strong interdependence between SRB and FeRB activity, as observed in other environments, such as saltmarsh sediments. Low temperature did not appear to hinder FeRB abundance in alkaline tailings. Finally, despite evidence that SRB populations were active at both sites, the |S isotopic composition of the AVS and CRS fractions were not representative of biogenic sulfides, indicating that the overall S-isotope signature of mine tailings is more representative of abiotic sulfides originating from the ore body. 相似文献
17.
Numerous pegmatite dikes occur in the Sparrow pluton (muscovite-biotite granite) and in the adjacent cordierite-zone schist-hornfels of the Yellowknife Supergroup. Where pegmatite dikes cut granite, the adjacent granite is enriched in muscovite and apatite, and depleted in K-feldspar. Mass transfer calculations, based on rock, mineral, and modal analyses, indicate that H, P, and locally B, Ti, Fe, and Ca were added, and K, Sr, Ba, and locally Na were removed (hydrogen metasomatism). In one alteration zone (8 cm wide) the calculated change (in terms of mols/gram of unaltered granite) is, 600 K-feldspar+24 biotite+190 plagioclase +[770 H+36 P+3 Ti+13 Fe+13 Ca] 400 muscovite+1100 quartz +11 apatite+[240 Na+260 K]. Where pegmatite dikes cut schist-hornfels (biotite-plagioclase-quartz), the adjacent rock is, in places, enriched in tourmaline, apatite, and quartz, and depleted in biotite and plagioclase. These alteration zones are variable in width; most are less than 20 cm wide. Mass transfer calculations, based on rock, mineral, and modal analyses, indicate that B, P, Zn, and locally Ca, Fe, and Al were added, and that Na, K, Fe, Rb, Sr, Ba, and locally Mg and Si were removed (boron metasomatism). In one zone, 2 cm wide, the calculated reaction (in units of mols/gram of unaltered schist) is, 730 biotite+1530 plagioclase +[1080 B+600 H+430 P+360 Ca] 480 tourmaline+480 quartz+115 apatite +[3630 Si+870 Na+590 K+110 Fe]. Changes in the volume fraction of muscovite, K-feldspar, tourmaline, and biotite, relative to distance from pegmatite, are progressive, and in most alteration zones may be expressed by use of an error-function equation. Some tourmaline zones are more complex. Zone formation is considered in terms of a steady-state reaction model in which grainboundary diffusion is the transport mechanism. 相似文献
18.
In the mountainous Rio Icacos watershed in northeastern Puerto Rico, quartz diorite bedrock weathers spheroidally, producing a 0.2-2 m thick zone of partially weathered rock layers (∼2.5 cm thickness each) called rindlets, which form concentric layers around corestones. Spheroidal fracturing has been modeled to occur when a weathering reaction with a positive ΔV of reaction builds up elastic strain energy. The rates of spheroidal fracturing and saprolite formation are therefore controlled by the rate of the weathering reaction.Chemical, petrographic, and spectroscopic evidence demonstrates that biotite oxidation is the most likely fracture-inducing reaction. This reaction occurs with an expansion in d (0 0 1) from 10.0 to 10.5 Å, forming “altered biotite”. Progressive biotite oxidation across the rindlet zone was inferred from thin sections and gradients in K and Fe(II). Using the gradient in Fe(II) and constraints based on cosmogenic age dates, we calculated a biotite oxidation reaction rate of 8.2 × 10−14 mol biotite m−2 s−1. Biotite oxidation was documented within the bedrock corestone by synchrotron X-ray microprobe fluorescence imaging and XANES. X-ray microprobe images of Fe(II) and Fe(III) at 2 μm resolution revealed that oxidized zones within individual biotite crystals are the first evidence of alteration of the otherwise unaltered corestone.Fluids entering along fractures lead to the dissolution of plagioclase within the rindlet zone. Within 7 cm surrounding the rindlet-saprolite interface, hornblende dissolves to completion at a rate of 6.3 × 10−13 mol hornblende m−2 s−1: the fastest reported rate of hornblende weathering in the field. This rate is consistent with laboratory-derived hornblende dissolution rates. By revealing the coupling of these mineral weathering reactions to fracturing and porosity formation we are able to describe the process by which the quartz diorite bedrock disaggregates and forms saprolite. In the corestone, biotite oxidation induces spheroidal fracturing, facilitating the influx of fluids that react with other minerals, dissolving plagioclase and chlorite, creating additional porosity, and eventually dissolving hornblende and precipitating secondary minerals. The thickness of the resultant saprolite is maintained at steady state by a positive feedback between the denudation rate and the weathering advance rate driven by the concentration of pore water O2 at the bedrock-saprolite interface. 相似文献
19.
The Cu-Co-Au deposits of the Idaho Cobalt Belt are in lithostratigraphic zones of the Middle Proterozoic Yellowjacket Formation characterized by distinctive chemical and mineralogical compositions including high concentrations of Fe (15- > 30 wt. percent Fe2O3), Cl (0.1–1.10 wt. percent), and magnetite or biotite (> 50 vol. percent). The Cu-Co-Au deposits of the Blackbird mine are stratabound in Fe-silicate facies rocks that are rich in biotite, Fe, and Cl, but stratigraphically equivalent rocks farther than 10 km from ore deposits have similar compositions. A lower lithostratigraphic zone containing magnetite and small Cu-Co-Au deposits extends for more than 40 km. The Fe-rich strata are probably exhalative units related to mafic volcanism and submarine hot springs, but the origin of the high Cl concentrations is less clear. Former chlorine-rich pore fluids are suggested by the presence of supersaline fluid inclusions, by Cl-rich biotite and scapolite (as much as 1.87 percent Cl in Fe-rich biotite), and by high Cl concentrations in rock samples. Chlorine is enriched in specific strata and in zones characterized by soft-sediment deformation, thus probably was introduced during sedimentation or diagenesis. Unlike some metasedimentary rocks containing scapolite and high Cl, the Yellowjacket Formation lacks evidence for evaporitic strata that could have been a source of Cl. More likely, the Cl reflects a submarine brine that carried Fe, K, and base metals. Strata containing anomalous Fe-K-Cl are considered to be a guide to sub-basins favorable for the occurrence of stratiform base-metal deposits. 相似文献
20.
构造动力成岩成矿作用的实验研究 总被引：1，自引：1，他引：1
岳石 《大地构造与成矿学》1990,14(4):325-332
采用高温高压岩石蠕变实验装置,对实际的岩石进行高温高压变形实验,通过观察和测试样品组构和成份的变化,考察一定温压条件下,岩石的构造变形所带来的物质组分的迁移和聚集,探讨构造动力控制成岩成矿作用的机理。实验结果表明:伴随构造变形,物质组分迁移 主要可归纳为三种类型:1)塑性或韧性流动;2)扩散与化学反应;3)热液携带。在实验后的样品中观察到:黄铣矿通过韧性流动沿韧性剪切带,韧性挤压带和韧性扭曲构造带的迁移和富集;斜长石和黑云母发生矿物成份和矿物相的转化。在实验变形过程中,Cu,Pb,Zn等成矿元素易于活化迁移,从高压区迁向低压区,K,Na,Ca,Mg等成岩元素也易活化迁移,但规律不明显,Fe,Co,Ni等元素对花岗岩样品不易活化迁移而对矿石样品则易迁移。上述实验结果对探讨成矿规律具有非常重要意义。 相似文献