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1.
Samples taken from a shooting range near Blacksburg, VA, USA provide information about the reservoirs and pathways of lead at shooting ranges in an upland setting and humid environment. The metallic lead shot corrodes rapidly and develops a coating of hydrocerussite (Pb3(CO3)2(OH)2). Hydrocerussite dissolution releases soluble lead at concentrations ranging from 2 ppb to 2 ppm depending the soil pH values at this site. This soluble lead is captured by the Fe and Mn oxides and carbonates soil fractions. The highest concentration of extractable lead contained in the soil was directly correlated with the highest concentration of lead shot and bullets measured on the shotgun range surface. Eh-pH and hydrolysis diagrams provide a useful geochemical framework for understanding the corrosion process, recognizing the corrosion product(s), understanding their solubility, and identifying the geochemical barriers to lead migration that provides a basis for selecting best management practices for this and other shooting range.  相似文献   

2.
Immobilization of trace elements in contaminated soils by zero-valent iron (ZVI) is a promising remediation method, but questions about its long-term performance remain unanswered. To quantify immobilization and predict possible contaminant remobilization on long timescales detailed knowledge about immobilization mechanisms is needed. This study aimed at assessing the long-term effect of ZVI amendments on dissolved copper and arsenic in contaminated soils, at exploring the immobilization mechanism(s), and at setting up a geochemical model able to estimate dissolved copper and arsenic under different scenarios. Samples from untreated and ZVI-treated plots in two field experiments where ZVI had been added 6 and 15 years ago were investigated by a combination of batch experiments, geochemical modeling and extended X-ray absorption fine structure (EXAFS) spectroscopy. Dissolved copper and arsenic concentrations were described by a multisurface geochemical model with surface complexation reactions, verified by EXAFS. The ZVI remained “reactive” after 6–15 years, i.e. the dissolved concentrations of copper and arsenic were lower in the ZVI-treated than in the untreated soils. There was a shift in copper speciation from organic matter complexes in the untreated soil to surface complexes with iron (hydr)oxides in the ZVI-treated soil. The pH value was important for copper immobilization and ZVI did not have a stabilizing effect if pH was lower than about 6. Immobilization of arsenic was slightly pH-dependent and sensitive to the competition with phosphate. If phosphate was ignored in the modeling, the dissolution of arsenate was greatly underestimated.  相似文献   

3.
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   

4.
The extent of historical U mining impacts is well documented for the North Cave Hills region of Harding County, South Dakota, USA. While previous studies reported watershed sediment and surface water As and U concentrations up to 90× established background concentrations, it was unclear whether or how localized changes in sediment redox behavior may influence contaminant remobilization. Five pore-water equilibration samplers (peepers) were spatially and temporally deployed within the study area to evaluate seasonal solid–liquid As and U distributions as a function of sediment depth. Pore-water and solid phase As and U concentrations, Fe speciation, Eh and pH were measured to ascertain specific geochemical conditions responsible for As and U remobilization and transport behavior. At a mine overburden sedimentation pond adjacent to the mine sites, high total aqueous As and U concentrations (4920 and 674 μg/L, respectively) were found within surface water during summer sampling; however pond dredging prior to autumn sampling resulted in significantly lower aqueous As and U concentrations (579 and 108 μg/L, respectively); however, both As and U still exceeded regional background concentrations (20 and 18 μg/L, respectively). At a wetlands-dominated deposition zone approximately 2 km downstream of the sedimentation pond, pore-water geochemical conditions varied seasonally. Summer conditions promoted reducing conditions in pore water, resulting in active release of As(III) to the water column. Autumn conditions promoted oxidizing conditions, decreasing pore-water As (Aspw) 5× and increasing Upw 10×. Peak U pore-water concentrations (781 μg/L) were 3.5× greater than determined for the surface water (226 μg/L), and approximately 40× background concentrations. At the Bowman–Haley reservoir backwaters 45 km downstream from the mine sites, As and U pore-water concentrations increased significantly between the summer and autumn deployments, attributed to increased Fe reduction processes. Geochemical modeling suggests solid-phase Fe reduction promotes the liberation of pore-water As and U via suppressing the formation of thioarsenite. Intermittent hydrological processes facilitate As and U transport and deposition throughout the watershed, while biogeochemical-influenced redox changes cycle As and U between pore and surface water within localized environments.  相似文献   

5.
Uranium(VI), which is often elevated in granitoidic groundwaters, is known to adsorb strongly to Fe (hydr)oxides under certain conditions. This process can be used in water treatment to remove U(VI). To develop a consistent geochemical model for U(VI) adsorption to ferrihydrite, batch experiments were performed and previous data sets reviewed to optimize a set of surface complexation constants using the 3-plane CD-MUSIC model. To consider the effect of dissolved organic matter (DOM) on U(VI) speciation, new parameters for the Stockholm Humic Model (SHM) were optimized using previously published data. The model, which was constrained from available X-ray absorption fine structure (EXAFS) spectroscopy evidence, fitted the data well when the surface sites were divided into low- and high-affinity binding sites. Application of the model concept to other published data sets revealed differences in the reactivity of different ferrihydrites towards U(VI). Use of the optimized SHM parameters for U(VI)-DOM complexation showed that this process is important for U(VI) speciation at low pH. However in neutral to alkaline waters with substantial carbonate present, Ca–U–CO3 complexes predominate. The calibrated geochemical model was used to simulate U(VI) adsorption to ferrihydrite for a hypothetical groundwater in the presence of several competitive ions. The results showed that U(VI) adsorption was strong between pH 5 and 8. Also near the calcite saturation limit, where U(VI) adsorption was weakest according to the model, the adsorption percentage was predicted to be >80%. Hence U(VI) adsorption to ferrihydrite-containing sorbents may be used as a method to bring down U(VI) concentrations to acceptable levels in groundwater.  相似文献   

6.
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7.
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.
Localized zones or lenses of naturally reduced sediments have the potential to play a significant role in the fate and transport of redox-sensitive metals and metalloids in aquifers. To assess the mineralogy, microbiology and redox processes that occur in these zones, several cores from a region of naturally occurring reducing conditions in a U-contaminated aquifer (Rifle, CO) were examined. Sediment samples from a transect of cores ranging from oxic/suboxic Rifle aquifer sediment to naturally reduced sediment were analyzed for U and Fe content, oxidation state, and mineralogy; reduced S phases; and solid-phase organic C content using a suite of analytical and spectroscopic techniques on bulk sediment and size fractions. Solid-phase U concentrations were higher in the naturally reduced zone, with a high proportion of the U present as U(IV). The sediments were also elevated in reduced S phases and Fe(II), indicating it is very likely that U(VI), Fe(III), and SO4 reduction has occurred or is occurring in the sediment. The microbial community was assessed using lipid- and DNA-based techniques, and statistical redundancy analysis was performed to determine correlations between the microbial community and the geochemistry. Increased concentrations of solid-phase organic C and biomass in the naturally reduced sediment suggests that natural bioreduction is stimulated by a zone of increased organic C concentration associated with fine-grained material and lower permeability to groundwater flow. Characterization of the naturally bioreduced sediment provides an understanding of the natural processes that occur in the sediment under reducing conditions and how they may impact natural attenuation of radionuclides and other redox sensitive materials. Results also suggest the importance of recalcitrant organic C for maintaining reducing conditions and U immobilization.  相似文献   

9.
The chemical reduction of U(VI) by Fe(II) is a potentially important pathway for immobilization of uranium in subsurface environments. Although the presence of surfaces has been shown to catalyze the reaction between Fe(II) and U(VI) aqueous species, the mechanism(s) responsible for the enhanced reactivity remain ambiguous. To gain further insight into the U-Fe redox process at a complexing, non-conducting surface that is relevant to common organic phases in the environment, we studied suspensions containing combinations of 0.1 mM U(VI), 1.0 mM Fe(II), and 4.2 g/L carboxyl-functionalized polystyrene microspheres. Acid-base titrations were used to monitor protolytic reactions, and Fe K-edge and U L-edge X-ray absorption fine structure spectroscopy was used to determine the valence and atomic environment of the adsorbed Fe and U species. In the Fe + surface carboxyl system, a transition from monomeric to oligomeric Fe(II) surface species was observed between pH 7.5 and pH 8.4. In the U + surface carboxyl system, the U(VI) cation was adsorbed as a mononuclear uranyl-carboxyl complex at both pH 7.5 and 8.4. In the ternary U + Fe + surface carboxyl system, U(VI) was not reduced by the solvated or adsorbed Fe(II) at pH 7.5 over a 4-month period, whereas complete and rapid reduction to U(IV) nanoparticles occurred at pH 8.4. The U(IV) product reoxidized rapidly upon exposure to air, but it was stable over a 4-month period under anoxic conditions. Fe atoms were found in the local environment of the reduced U(IV) atoms at a distance of 3.56 Å. The U(IV)-Fe coordination is consistent with an inner-sphere electron transfer mechanism between the redox centers and involvement of Fe(II) atoms in both steps of the reduction from U(VI) to U(IV). The inability of Fe(II) to reduce U(VI) in solution and at pH 7.5 in the U + Fe + carboxyl system is explained by the formation of a transient, “dead-end” U(V)-Fe(III) complex that blocks the U(V) disproportionation pathway after the first electron transfer. The increased reactivity at pH 8.4 relative to pH 7.5 is explained by the reaction of U(VI) with an Fe(II) oligomer, whereby the bonds between Fe atoms facilitate the transfer of a second electron to the hypothetical U(V)-Fe(III) intermediate. We discuss how this mechanism may explain the commonly observed higher efficiency of uranyl reduction by adsorbed or structural Fe(II) relative to aqueous Fe(II).  相似文献   

10.
《Chemical Geology》2006,225(1-2):156-171
Groundwater samples were collected along a groundwater flow path in the Carrizo Sand aquifer in south Texas, USA. Field measurements that included pH, specific conductivity, temperature, dissolved oxygen (DO), oxidation–reduction potentials (Eh in mV), alkalinity, iron speciation, and H2S concentrations were also conducted on site. The geochemistry (i.e., concentrations, shale-normalized patterns, and speciation) of dissolved rare element elements (REEs) in the Carrizo groundwaters are described as a function of distance along a flow path. Eh and other redox indicators (i.e., DO, Fe speciation, H2S, U, and Re) indicate that redox conditions change along the flow path in the Carrizo Sand aquifer. Within the region of the aquifer proximal to the recharge zone, groundwaters exhibit both highly oxidizing and localized mildly reducing conditions. However, from roughly 10 km to the discharge zone, groundwaters are reducing and exhibit a progressive decrease in redox conditions. Dissolved REE geochemical behavior exhibits regular variations along the groundwater flow path in the Carrizo Sand aquifer. The changes in REE concentrations, shale-normalized patterns, and speciation indicate that REEs are not conservative tracers. With flow down-gradient, redox conditions, pH and solution composite, and adsorption modify groundwater REE concentrations, fractionation patterns, and speciation.  相似文献   

11.
Sorption and desorption processes are an important part of biological and geochemical metallic isotope cycles. Here, we address the dynamic aspects of metallic isotopic fractionation in a theoretical and experimental study of Fe sorption and desorption during the transport of aqueous Fe(III) through a quartz-sand matrix. Transport equations describing the behavior of sorbing isotopic species in a water saturated homogeneous porous medium are presented; isotopic fractionation of the system (Δsorbedmetal-soln) being defined in terms of two parameters: (i) an equilibrium fractionation factor, αe; and (ii) a kinetic sorption factor, α1. These equations are applied in a numerical model that simulates the sorption-desorption of Fe isotopes during injection of a Fe(III) solution pulse into a quartz matrix at pH 0-2 and explores the effects of the kinetic and equilibrium parameters on the Fe-isotope evolution of porewater. The kinetic transport theory is applied to a series of experiments in which pulses of Na and Fe(III) chloride solutions were injected into a porous sand grain column. Fractionation factors of αe = 1.0003 ± 0.0001 and α1 = 0.9997 ± 0.0004 yielded the best fit between the transport model and the Fe concentration and δ56Fe data. The equilibrium fractionation (Δ56FesorbedFe-soln) of 0.3‰ is comparable with values deduced for adsorption of metallic cations on iron and manganese oxide surfaces and suggests that sandstone aquifers will fractionate metallic isotopes during sorption-desorption reactions. The ability of the equilibrium fractionation factor to describe a natural system, however, depends on the proximity to equilibrium, which is determined by the relative time scales of mass transfer and chemical reaction; low fluid transport rates should produce a system that is less dependent on kinetic effects. The results of this study are applicable to Fe-isotope fractionation in clastic sediments formed in highly acidic conditions; such conditions may have existed on Mars where acidic oxidizing ground and surface waters may have been responsible for clastic sedimentation and metallic element transport.  相似文献   

12.
Experimental data on Fe-CaCO3 interaction at 6 GPa and 1273–1873 K are presented. The system models the hypothetical redox interaction in subducting slabs at the contact with the reduced mantle and a putative process at the core-mantle boundary. The reaction is accompanied by carbonatite melt formation. It also produces Fe3C and calcium wustite, which form solid or liquid phases depending on experimental conditions. In iron-containing systems at 6 GPa, calcium carbonate melts in the range 1473–1573 K, which is consistent with aragonite disappearance from complex carbonate systems. The composition of calcium carbonate liquid is not influenced by metallic Fe. It corresponds to nearly pure CaCO3. Along the mantle adiabat or at slightly higher temperatures, nearly pure CaCO3 coexists with metallic iron or calcium wustite. This hypothesis explains the coexistence of metallic iron and carbonate inclusions in lithospheric and superdeep diamonds.  相似文献   

13.
《Applied Geochemistry》2004,19(6):917-936
Carbon dioxide disposal into deep aquifers is a potential means whereby atmospheric emissions of greenhouse gases may be reduced. However, our knowledge of the geohydrology, geochemistry, geophysics, and geomechanics of CO2 disposal must be refined if this technology is to be implemented safely, efficiently, and predictably. As a prelude to a fully coupled treatment of physical and chemical effects of CO2 injection, the authors have analyzed the impact of CO2 immobilization through carbonate mineral precipitation. Batch reaction modeling of the geochemical evolution of 3 different aquifer mineral compositions in the presence of CO2 at high pressure were performed. The modeling considered the following important factors affecting CO2 sequestration: (1) the kinetics of chemical interactions between the host rock minerals and the aqueous phase, (2) CO2 solubility dependence on pressure, temperature and salinity of the system, and (3) redox processes that could be important in deep subsurface environments. The geochemical evolution under CO2 injection conditions was evaluated. In addition, changes in porosity were monitored during the simulations. Results indicate that CO2 sequestration by matrix minerals varies considerably with rock type. Under favorable conditions the amount of CO2 that may be sequestered by precipitation of secondary carbonates is comparable with and can be larger than the effect of CO2 dissolution in pore waters. The precipitation of ankerite and siderite is sensitive to the rate of reduction of Fe(III) mineral precursors such as goethite or glauconite. The accumulation of carbonates in the rock matrix leads to a considerable decrease in porosity. This in turn adversely affects permeability and fluid flow in the aquifer. The numerical experiments described here provide useful insight into sequestration mechanisms, and their controlling geochemical conditions and parameters.  相似文献   

14.
Subsurface regions of alluvial sediments characterized by an abundance of refractory or lignitic organic carbon compounds and reduced Fe and S bearing minerals, which are referred to as naturally reduced zones (NRZ), are present at the Integrated Field Research Challenge site in Rifle, CO (a former U mill site), and other contaminated subsurface sites. A study was conducted to demonstrate that the NRZ contains a variety of contaminants and unique minerals and potential contaminant hosts, investigate micron-scale spatial association of U with other co-contaminants, and determine solid phase-bounded U valence state and phase identity. The NRZ sediment had significant solid phase concentrations of U and other co-contaminants suggesting competing sorption reactions and complex temporal variations in dissolved contaminant concentrations in response to transient redox conditions, compared to single contaminant systems. The NRZ sediment had a remarkable assortment of potential contaminant hosts, such as Fe oxides, siderite, Fe(II) bearing clays, rare solids such as ZnS framboids and CuSe, and, potentially, chemically complex sulfides. Micron-scale inspections of the solid phase showed that U was spatially associated with other co-contaminants. High concentration, multi-contaminant, micron size (ca. 5–30 μm) areas of mainly U(IV) (53–100%) which occurred as biogenic UO2 (82%), or biomass – bound monomeric U(IV) (18%), were discovered within the sediment matrix confirming that biotically induced reduction and subsequent sequestration of contaminant U(VI) via natural attenuation occurred in this NRZ. A combination of assorted solid phase species and an abundance of redox-sensitive constituents may slow U(IV) oxidation rates, effectively enhancing the stability of U(IV) sequestered via natural attenuation, impeding rapid U flushing, and turning NRZs into sinks and long-term, slow-release sources of U contamination to groundwater.  相似文献   

15.
Structural Fe(II) has been shown to reduce several oxidized environmental contaminants, including NO3, chlorinated solvents, Cr(VI), and U(VI). Studies investigating reduction of U(VI) by soils and sediments, however, suggest that abiotic reduction of U(VI) by Fe(II) is not significant, and that direct enzymatic reduction of U(VI) by metal-reducing bacteria is required for U(VI) immobilization as U(IV). Here evidence is presented for abiotic reduction and immobilization of U(VI) by structural Fe(II) in a redoximorphic soil collected from a hillside spring in Iowa. Oxidation of Fe(II) in the soil after reaction with U(VI) was demonstrated by Mössbauer spectroscopy and reduction of U(VI) by the pasteurized soil using U LIII-edge X-ray absorption spectroscopy (XAS). XAS indicates that both reduced U(IV) and oxidized U(VI) or U(V) are present after U(VI) interaction with the Fe(II) containing soil. The EXAFS data show the presence of a non-uraninite U(IV) phase and evidence of the oxidized U(V) or U(VI) fraction being present as a non-uranyl species. Little U(VI) reduction is observed by soil that has been exposed to air and oxidation of Fe(II) to goethite has occurred. Soil characterization based on chemical extractions, Mössbauer spectroscopy, and Fe K-edge XAS indicate that the majority of Fe(II) in the soil is structural in nature, existing in clay minerals and possibly a green rust-like phase. These data provide compelling evidence for abiotic reduction of U(VI) by structural Fe(II) from soil near Fe-rich oxic–anoxic boundaries in natural environments. The work highlights the potential for abiotic reduction of U(VI) by Fe(II) in reduced, Fe-rich environments.  相似文献   

16.
Models of geochemical controls on elements of concern (EOCs; e.g., As, Se, Mo, Ni) in U tailings are dominated by ferrihydrite. However, the evolution of aqueous concentrations of Al and Mg through the Key Lake (KL) U mill bulk neutralization process indicates that secondary Al and Mg minerals comprise a large portion of the tailings solids. X-ray diffraction, Al K-edge XAS, and TEM elemental mapping of solid samples collected from a pilot-scale continuous-flow synthetic raffinate neutralization system of the KL mill indicate the secondary Al–Mg minerals present include Mg–Al hydrotalcite, amorphous Al(OH)3, and an amorphous hydrobasaluminite-type phase. The ferrihydrite present contains Al and may be more accurately described as Al–Fe(OH)3. In the final combined tailings sample (pH 10.5) collected from the model experiments using raffinate with Al, Mg, and Fe, solid phase EOCs were associated with Al–Fe(OH)3 and Mg–Al hydrotalcite. In model experiments using raffinate devoid of Fe, aqueous EOC concentrations decreased greatly at pH 4.0 (i.e., where ferrihydrite would precipitate) and largely remained in the solid phase when increased to the terminal pH of 10.5; this suggests Al–Mg minerals can control aqueous concentrations of EOCs in the raffinate in the absence of Fe. Maximum adsorption capacities for individual and mixtures of adsorbates by Mg–Al hydrotalcite were determined. A revised model of the geochemical controls in U mill tailings is presented in which Al and Mg minerals co-exist with Fe minerals to control EOC concentrations.  相似文献   

17.
The development and application of geochemical techniques to identify redox conditions in modern and ancient aquatic environments has intensified over recent years. Iron (Fe) speciation has emerged as one of the most widely used procedures to distinguish different redox regimes in both the water column and sediments, and is the main technique used to identify oxic, ferruginous (anoxic, Fe(II) containing) and euxinic (anoxic, sulfidic) water column conditions. However, an international sediment reference material has never been developed. This has led to concern over the consistency of results published by the many laboratories that now utilise the technique. Here, we report an interlaboratory comparison of four Fe speciation reference materials for palaeoredox analysis, which span a range of compositions and reflect deposition under different redox conditions. We provide an update of extraction techniques used in Fe speciation and assess the effects of both test portion mass, and the use of different analytical procedures, on the quantification of different Fe fractions in sedimentary rocks. While atomic absorption spectroscopy and inductively coupled plasma‐optical emission spectrometry produced comparable Fe measurements for all extraction stages, the use of ferrozine consistently underestimated Fe in the extraction step targeting mixed ferrous–ferric minerals such as magnetite. We therefore suggest that the use of ferrozine is discontinued for this Fe pool. Finally, we report the combined data of four independent Fe speciation laboratories to characterise the Fe speciation composition of the reference materials. These reference materials are available to the community to provide an essential validation of in‐house Fe speciation measurements.  相似文献   

18.
The mechanism of pyrite oxidation in carbonate-containing alkaline solutions at 80 °C was investigated with the help of rate experiments, thermodynamic modeling and diffuse reflectance infrared spectroscopy (DRIFTS). Pyrite oxidation rate increased with pH and was enhanced by addition of bicarbonate/carbonate ions. The carbonate effect was found to be limited to moderately alkaline conditions (pH 8-11). Metastable Eh-pH diagrams, at 25 °C, indicate that soluble iron-carbonate complexes (FeHCO3−, FeCO30, Fe(CO3)(OH)− and FeCO32−) may coexist with pyrite in the pH range of 6-12.5. Above pH 11 and 13, the Fe(II) and Fe(III) hydroxocomplexes, respectively, become stable, even in the presence of carbonate/bicarbonate ions. Surface-bound carbonate complexes on iron were also identified with DRIFTS as products of pyrite oxidation in addition to iron oxyhydroxides and soluble sulfate species. The conditions under which thermodynamic and DRIFTS analyses indicate the presence of carbonate compounds also correspond to those in which the fastest rate of pyrite oxidation in carbonate solutions was observed. Following the Singer-Stumm model for pyrite oxidation in acidic solutions, it is assumed that Fe(III) is the preferred pyrite oxidant under alkaline conditions. We propose that carbonate ions facilitate the electron transfer from soluble iron(II)-carbonate to O2, increase the iron solubility, and provide buffered, favorable alkaline conditions at the reaction front, which in turn favors the overall kinetics of pyrite oxidation. Therefore, the electron transfer from sulfur atoms to O2 is facilitated by the formation of the cycle of Fe(II)-pyrite/Fe(III)-carbonate redox couple at the pyrite surface.  相似文献   

19.
氧化还原障在热液铀矿成矿中的作用   总被引：5，自引：0，他引：5  
铀是变价元素,氧化还原条件控制铀的迁移和沉淀。铀在氧化环境中呈U~(6+)形式存在,在还原条件下则以U~(4+)形式存在。氧化态六价铀主要以可溶的碳酸铀酰/氟化铀酰络合物形式在水溶液中迁移,还原态四价铀主要以沥青铀矿和铀石等形式富集沉淀成矿。热液铀矿的形成需要一对空间上密切共生的氧化障/氧化剂和还原障/还原剂,二者缺一不可。首先,氧化障中氧化剂将富铀岩石中的铀大量氧化形成U~(6+),溶解进入水溶液迁移;第二,高氧化性富铀溶液遇到还原障,U~(6+)还原成U~(4+)沉淀下来,富集形成铀矿。前人虽然对铀的地球化学性质及氧化还原反应在铀成矿中作用已比较了解,但如何在实际铀矿成矿系统中准确识别氧化还原障,有效利用氧化还原障的控矿机理指导找矿,还存在一些模糊认识,制约了铀成矿理论的发展和找矿方法的提升。本文以我国最重要的砂岩型铀矿、火山岩型铀矿、花岗岩型铀矿和变质型铀矿为例,总结了与铀矿化有关的氧化还原障的主要类型,探讨了红层等蒸发盐地层(氧化障),有机质、煌斑岩等中基性岩脉(还原障)与铀矿之间的关系及控矿机制,揭示了成矿盆地中铀-煤、铀-气(油)共生的机制,阐明了翁泉沟硼、铁、铀矿共生原因,建立了不同类型铀矿成矿模型。  相似文献   

20.
Tetrahedrites of composition (Cu, Ag)10(Cu2, Fe, Zn)2(Sb, As)4S13 or Cu12Sb14/3S13 have 208 valence electrons per unit cell and are expected to be semiconductors. The bands are full in these cases, whereas compositions towards the classical formula Cu12Sb4S13 (204 valence electrons per unit cell) have only partially filled bands and are therefore expected to be metallic. These predictions are supported by new optical absorption spectra of tetrahedrites with 205 and 208 valence electrons per unit cell. The gap between valence and conduction bands of the semiconductor is about 1.7 (±0.2) eV. A further prediction based on a nearly-free electron model is that 208 valence electrons per unit cell represent a compositional limit for tetrahedrites, and that the stability increases as compositions approach this limit. Existing data indicate an exponential increase in the number of occurrences as the limit is approached.  相似文献   

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