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1.
A magnetic and spectroscopic characterisation has been performed on a natural bornite sample from the Natural History Museum of the University of Florence. The combination of magnetic measurements and continuous-wave electron paramagnetic resonance (cw-EPR) spectroscopy at different temperatures and frequencies provided information about the distribution and valence states of Cu and Fe in bornite. The studied sample was found to obey the Curie–Weiss law with a transition from a paramagnetic to an antiferromagnetic phase at 64 K; its possible attribution to a disordered spin glass phase was ruled out by ac susceptibility measurements. Q- and X-band cw-EPR measurements confirmed the presence of Fe(III) as fundamental valence state in bornite: the single EPR line registered in the temperature range from 300 to 65 K can be assigned, in fact, to the Fe(III) single ions. Some Cu(II) signals were revealed in the low temperature EPR spectra and attributed to an early stage of the surface alteration. The width of the Fe(III) EPR spectrum, which hinders any characteristic spectral structure, can be ascribed to the exchange interaction. The pure antiferromagnetic character of the magnetic transition confirms the ordering between Fe and Cu in the bornite structure, at least at low temperature (≤70 K). Moreover, the relatively high Nèel temperature suggests the accepted model of Collins et al.’s (Can J Phys 59:535–539, 1981) to conveniently explain the overall magnetic properties in the range 298–4 K. Despite the increasing of the susceptibility in the paramagnetic range, in fact, the integrated EPR line area decreases by lowering the temperature, thus suggesting a progressive rising of the antiferromagnetic interactions among next-nearest-neighbouring paramagnetic centres.  相似文献   

2.
Tetragonal FeS1−x mackinawite, has been synthesized by reacting metallic iron with a sodium sulfide solution and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). Based on XRD and TEM analyses, synthetic mackinawite exhibits crystallization and is identical to the natural mineral. Unit cell parameters derived from XRD data are a = b = 0.3670 nm and c = 0.5049 nm. The bulk Fe:S ratio derived from the quantitative dispersive energy analysis is practically 1. XPS analyses, however, showed that mackinawite surface is composed of both Fe(II) and Fe(III) species bound to monosulfide. Accordingly, monosulfide is the dominant S species observed at the surface with lesser amount of polysulfides and elemental sulfur. TMS analysis revealed the presence of both Fe(II) and Fe(III) in the mackinawite structure, thus supporting the XPS analysis. We propose that the iron monosulfide phase synthesized by reacting metallic iron and dissolved sulfide is composed of Fe(II) and S(-II) atoms with the presence of a weathered thin layer covering the bulk material that consists of both Fe(II) and Fe(III) bound to S(-II) atoms and in a less extent of polysulfide and elemental sulfur.  相似文献   

3.
An EPR and SQUID magnetometry study of Cu2FeSnS4 (stannite) and Cu2ZnSnS4 (kesterite) has been performed in order to gain a deeper insight into the crystal chemistry of these minerals, in which the mixed character of bonds lends uncertainty to the determination of the metal valence states. EPR investigations were performed down to almost liquid nitrogen temperature on both natural and synthetic samples of stannite and kesterite. The interpretation of their parameters (g- and T-tensors) was refined by computer simulation. The main feature of all the spectra is the unstructured signal centered at about 0.310 T due to the presence of Cu(II). The absence of structure in the signal is due to spin-spin exchange interaction between Cu(II) and Fe(II), pointing to a diluted distribution of Cu(II). The temperature dependence of the Cu(II) signal can be related to a topological variation of the first-neighbors coordination. The SQUID measurements, while allowing a more precise interpretation of the EPR data, led to a full characterization of magnetic behavior of stannite and kesterite down to liquid helium temperature, evidencing antiferromagnetic interactions between the Fe(II) ions in all samples but in synthetic kesterite. From the EPR and SQUID experimental data no evidence was provided for the existence of two different structures for stannite and kesterite. Received: 2 August 1999 / Accepted: 7 January 2000  相似文献   

4.
Electron paramagnetic resonance (EPR) spectroscopy analysis of marine samples from different environments appears to differentiate between adsorbed and structural Mn (II) and Fe (III) sites in the sediment. This suggests that EPR may provide a means of distinguishing different environmental influences on sediment. Acid extract solutions from sediment samples exhibit clearly defined EPR spectra due to Mn(II), Ti(III), Fe(III), and VO(IV), which are amenable to qualitative and quantitative analysis at concentrations below one part per million. Spectra of several shellfish vary considerably, both between species, and within a species, depending on sampling localities. Resonances from Mn(II), Mo(V), and Fe(III) can be obtained. Mn(II) is substituted for Ca(II) in the calcite structure of some shells. The low detection limits, small sample size, required and identification of oxidation states by EPR complement other analytical techniques and may prove useful in marine systems.  相似文献   

5.
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   

6.
A wide investigation of the synthetic analogue of tetrahedrite, Cu12Sb4S13, has been performed by a combination of several techniques, magnetisation and differential scanning calorimetric measurements, cw, and pulsed EPR spectroscopy, to obtain complementary information about the presence and the distribution of Cu(II). The high temperature susceptibility of the sample accounts for two Cu(II) per formula unit, in agreement with the charge balance. However, strong antiferromagnetic interactions, observed even at room temperature, are associated with a transition at 83(3) K. At lower temperatures a residual susceptibility is observed. At 4.2 K ESEEM experiments enabled observation of the chemical environment of the residual paramagnetic species. Cu(II) was found randomly distributed in the M(1) site. The statistical presence of nearest neighbouring Cu(II) ions justify the observed antiferromagnetic interactions and transition. Nevertheless, isolated paramagnetic ions have been determined below the Néel temperature: they are mainly located near the surface of the grains. A colour centre, previously observed in natural samples, has been also identified.  相似文献   

7.
We report on a paramagnetic anisotropy study of three layered phyllosilicates. The mineral samples were characterized through X-ray powder diffraction (XRPD), X-ray photoelectron spectroscopy (XPS) and electron paramagnetic resonance (EPR). Based on EPR measurements of samples oriented parallel or perpendicular to the magnetic field lines, we show how the substitutional iron is transformed from Fe(II) (biotite) into Fe(III) (muscovite and kaolinite) species and from axial Fe(III) coordination sites (muscovite) to rhombic (kaolinite) sites in response to weathering.  相似文献   

8.
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   

9.
Recently, the wide application of CuO nanoparticles (NPs) in engineering field inevitably leads to its release into various geologic settings, which has aroused great concern about the geochemical behaviors of CuO NPs due to its high surface reactivity and impact on the fate of co-existing contaminants. However, the redox transformation of pollutants mediated by CuO NPs and the underlying mechanism still remain poorly understood. Here, we studied the interaction of CuO NPs with As(III), and explored the reaction pathways using batch experiments and multiple spectroscopic techniques. The results of in situ quick scanning X-ray absorption spectroscopy (Q-XAS) analysis verified that CuO NPs is capable of catalytically oxidize As(III) under dark conditions efficiently at a wide range of pHs. As(III) was firstly adsorbed on CuO NPs surface and then gradually oxidized to As(V) with dissolved O2 as the terminal electron acceptor. As(III) adsorption increased to the maximum at a pH close to PZC of CuO NPs (~?pH 9.2), and then sharply decreased with increasing pH, while the oxidation capacity monotonically increased with pH. X-ray photoelectron spectroscopy and electron paramagnetic resonance characterization of samples from batch experiments indicated that two pathways may be involved in As(III) catalytic oxidation: (1) direct electron transfer from As(III) to Cu(II), followed by concomitant re-oxidation of the produced Cu(I) by dissolved O2 back to Cu(II) on CuO NPs surface, and (2) As(III) oxidation by reactive oxygen species (ROS) produced from the above Cu(I) oxygenation process. These observations facilitate a better understanding of the surface catalytic property of CuO NPs and its interaction with As(III) and other elements with variable valence in geochemical environments.  相似文献   

10.
An extensive characterisation of the magnetic properties of synthetic powders of kuramite, with formal composition Cu3SnS4, was performed. Powders were investigated through superconducting quantum interference device (SQUID) magnetometry, electron paramagnetic resonance (EPR) spectroscopy, X-ray powder diffraction (XRPD), scanning and transmission electron microscopies (SEM and TEM) and microanalysis. SEM and TEM reveal the presence of nanodimensioned particles. XRPD clearly shows that Cu3SnS4 crystallised in a cubic sphalerite-type structural model, in spite of the stannite-type tetragonal structure described for the natural phase. This difference arises from a full random distribution of cations. Synthetic kuramite nanopowders exhibit a marked paramagnetism, originated by the presence of Cu(II), definitely assessed by EPR measurements. Moreover, the overall magnetic behaviour of the sample cannot be simply ascribed to diluted paramagnetism, and this suggests the presence of strong superexchange interactions among Cu(II) ions even at room temperature. The main consequences of these results are the definitive assessment of the chemical formula Cu(I)2Cu(II)SnS4 and of a random distribution of Cu(II), Cu(I) and Sn(IV) ions within the available tetrahedral sites.  相似文献   

11.
The biologically-mediated reduction of synthetic samples of the Fe(III)-bearing minerals hematite, goethite, lepidocrocite, feroxhyte, ford ferrihydrite, akaganeite and schwertmannite by Geobacter sulfurreducens has been investigated using microbiological techniques in conjunction with X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and X-ray Photoelectron Spectroscopy (XPS). This combination of approaches offers unique insights into the influence of subtle variations in the crystallinity of a given mineral on biogeochemical processes, and has highlighted the importance of (oxyhydr)oxide crystallite morphology in determining the changes occurring in a given mineral phase. Problems arising from normalising the biological Fe(III) reduction rates relative to the specific surface areas of the starting materials are also highlighted. These problems are caused primarily by particle aggregation, and compounded when using spectrophotometric assays to monitor reduction. For example, the initial rates of Fe(III) reduction observed for two synthetic feroxyhytes with different crystallinities (as shown by XRD and TEM studies) but almost identical surface areas, differ substantially. Both microbiological and high-resolution TEM studies show that hematite and goethite are susceptible to limited amounts of Fe(III) reduction, as evidenced by the accumulation of Fe(II) during incubation with G. sulfurreducens and the growth of nodular structures on crystalline goethite laths during incubation. Lepidocrocite and akaganeite readily transform into mixtures of magnetite and goethite, and XRD data indicate that the proportion of magnetite increases within the transformation products as the crystallinity of the starting material decreases. The presence of anthraquinone-2,6-disulfonate (AQDS) as an electron shuttle increases both the initial rate and longer term extent of biological Fe(III) reduction for all of the synthetic minerals examined. High-resolution XPS indicates subtle but measurable differences in the Fe(III):Fe(II) ratios at the mineral surfaces following extended incubation. For example, for a poorly crystalline schwertmannite, deconvolution of the Fe2p3/2 peak suggests that the Fe(III):Fe(II) ratio of the near-surface regions varies from 1.0 in the starting material to 0.9 following 144 h of incubation with G.sulfurreducens, and to 0.75 following the same incubation period in the presence of 10 μM AQDS. These results have important implications for the biogeochemical cycling of iron.  相似文献   

12.
We measured the Fe isotope fractionation during the reactions of Fe(II) with goethite in the presence and absence of a strong Fe(III) chelator (desferrioxamine mesylate, DFAM). All experiments were completed in an O2-free glove box. The concentrations of aqueous Fe(II) ([Fe(II)aq]) decreased below the initial total dissolved Fe concentrations ([Fe(II)total], 2.15 mM) due to fast adsorption within 0.2 day. The concentration of adsorbed Fe(II) ([Fe(II)ads]) was determined as the difference between [Fe(II)aq] and the concentration of extracted Fe(II) in 0.5 M HCl ([Fe(II)extr]) (i.e., [Fe(II)ads] = [Fe(II)extr] − [Fe(II)aq]). [Fe(II)ads] also decreased with time in experiments with and without DFAM, documenting that fast adsorption was accompanied by a second, slower reaction. Interestingly, [Fe(II)extr] was always smaller than [Fe(II)total], indicating that some Fe(II) was sequestered into a pool that is not HCl-extractable. The difference was attributed to Fe(II) incorporated into goethite structure (i.e., [Fe(II)inc] = [Fe(II)total] −[Fe(II)extr]). More Fe(II) was incorporated in the presence of DFAM than in its absence at all time steps. Regardless of the presence of DFAM, both aqueous and extracted Fe(II) (δ56/54Fe(II)aq and δ56/54Fe(II)extr) became isotopically lighter than or similar to goethite (− 0.27‰) at day 7, implying that the isotope exchange occurred between bulk goethite and aqueous Fe. Consistently, the mass balance indicated that the incorporated Fe is isotopically heavier than extracted Fe. These observations suggested that (i) co-adsorption of Fe(II) with DFAM resulted in more pervasive electron transfer, (ii) the electron transfer from heavy Fe(II) in the adsorbed Fe(II) to light Fe(III) in goethite results in the fixation of heavy adsorbed Fe(III) on the surface and accumulation of Fe(II) within the goethite, and (iii) desorption of the reduced, light Fe from goethite does not necessarily occur at the same surface sites where adsorption occurred.  相似文献   

13.
We studied the effects of humic substances (HS) on the sorption of Fe(II) onto Al-oxide and clay sorbents at pH 7.5 with a combination of batch kinetic experiments and synchrotron Fe K-edge EXAFS analyses. Fe(II) sorption was monitored over the course of 4 months in anoxic clay and Al-oxide suspensions amended with variable HS types (humic acid, HA; or fulvic acid, FA) and levels (0, 1, and 4 wt%), and with differing Fe(II) and HS addition sequences (co-sorption and pre-coated experiments, where Fe(II) sorbate was added alongside and after HS addition, respectively). In the Al-oxide suspensions, the presence of HS slowed down the kinetics of Fe(II) sorption, but had limited, if any, effect on the equilibrium aqueous Fe(II) concentrations. EXAFS analyses revealed precipitation of Fe(II)–Al(III)-layered double hydroxide (LDH) phases as the main mode of Fe(II) sorption in both the HA-containing and HA-free systems. These results demonstrate that HS slow down Fe(II) precipitation in the Al-oxide suspensions, but do not affect the composition or stability of the secondary Fe(II)–Al(III)-LDH phases formed. Interference of HS with the precipitation of Fe(II)–Al(III)-LDH was attributed to the formation organo-Al complexes HS limiting the availability of Al for incorporation into secondary layered Fe(II)-hydroxides. In the clay systems, the presence of HA caused a change in the main Fe(II) sorption product from Fe(II)–Al(III)-LDH to a Fe(II)-phyllosilicate containing little structural Al. This was attributed to complexation of Al by HA, in combination with the presence of dissolved Si in the clay suspension enabling phyllosilicate precipitation. The change in Fe(II) precipitation mechanism did not affect the rate of Fe(II) sorption at the lower HA level, suggesting that the inhibition of Fe(II)–Al(III)-LDH formation in this system was countered by enhanced Fe(II)-phyllosilicate precipitation. Reduced rates of Fe(II) sorption at the higher HA level were attributed to surface masking or poisoning by HA of secondary Fe(II) mineral growth at or near the clay surface. Our results suggest that HS play an important role in controlling the kinetics and products of Fe(II) precipitation in reducing soils, with effects modulated by soil mineralogy, HS content, and HS properties. Further work is needed to assess the importance of layered Fe(II) hydroxides in natural reducing environments.  相似文献   

14.
Metal L2,3, sulfur K and oxygen K near-edge X-ray absorption fine structure (NEXAFS) spectra for chalcopyrite, bornite, chalcocite, covellite, pyrrhotite and pyrite have been determined from single-piece natural mineral specimens in order to assess claims that chalcopyrite should be regarded as CuIIFeIIS2 rather than CuIFeIIIS2, and that copper oxide species are the principal initial oxidation products on chalcopyrite and bornite exposed to air. Spectra were obtained using both fluorescence and electron yields to obtain information representative of the bulk as well as the surface. Where appropriate, NEXAFS spectra have been interpreted by comparison with the densities of unfilled states and simulated spectra derived from ab initio calculations using primarily the FEFF8 code and to a lesser extent WIEN2k. Metal 2p and S 2p photoelectron spectra excited by monochromatised Al Kα X-rays were determined for each of the surfaces characterised by NEXAFS spectroscopy. The X-ray excited Cu LMM Auger spectrum was also determined for each copper-containing sulfide. FEFF8 calculations were able to simulate the experimental NEXAFS spectra quite well in most cases. For covellite and chalcocite, it was found that FEFF8 did not provide a good simulation of the Cu L3-edge spectra, but WIEN2k simulations were in close agreement with the experimental spectra. Largely on the basis of these simulations, it was concluded that there was no convincing evidence for chalcopyrite to be represented as CuIIFeIIS2, and no strong argument for some of the Cu in either bornite or covellite to be regarded as Cu(II). The ab initio calculations for chalcopyrite and bornite indicated that the density of Cu d-states immediately above the Fermi level was sufficient to account for the Cu L3-edge absorption spectrum, however these incompletely filled Cu d-states should not be interpreted as indicating some Cu(II) in the sulfide structure. It was also concluded that the X-ray absorption spectra were quite consistent with the initial oxidation products on chalcopyrite and bornite surfaces being iron oxide species, and inconsistent with the concomitant formation of copper-oxygen species.  相似文献   

15.
Reducing heavy metal concentrations to allowable levels in landfill leachate before discharge is an extremely important process to prevent environmental pollution. Iron oxide-coated gravel was used in order to remove Cd(II), Cu(II), Pb(II), Fe(III) and Al(III) simultaneously in high-strength synthetic leachate samples. Batch and column studies were performed to determine the kinetics and mechanism of adsorption process. The experimental data obtained from batch study satisfactorily fitted to the Freundlich model indicating surface heterogeneity and multilayer adsorption process. The data obtained from kinetic studies followed the pseudo-second-order kinetics indicating adsorption governed by chemisorption. The metal adsorption order observed in the batch study was Pb(II)(99.72%) ≈ Cu(II)(99.61%) ≈ Cd(II)(99.51%) ≈ Fe(III)(99.3%) > Al(III)(93.3%) at pH 7. Average metal removals in the fixed-bed column were found to be 96.5% for Cu(II), 94.8% for Pb(II), 90% for Cd(II), 84% for Fe(III) and 67% for Al(III). Iron oxide-coated gravel column adsorption capacity ranged from 0.56 to 66.82 mg/g. Recovery efficiency of adsorbed metals via desorption was between 5–97.75% in first cycle and 2–80.3% in second cycle.  相似文献   

16.
The Bemidji aquifer in Minnesota, USA is a well-studied site of subsurface petroleum contamination. The site contains an anoxic groundwater plume where soluble petroleum constituents serve as an energy source for a region of methanogenesis near the source and bacterial Fe(III) reduction further down gradient. Methanogenesis apparently begins when bioavailable Fe(III) is exhausted within the sediment. Past studies indicate that Geobacter species and Geothrix fermentens-like organisms are the primary dissimilatory Fe-reducing bacteria at this site. The Fe mineralogy of the pristine aquifer sediments and samples from the methanogenic (source) and Fe(III) reducing zones were characterized in this study to identify microbiologic changes to Fe valence and mineral distribution, and to identify whether new biogenic mineral phases had formed. Methods applied included X-ray diffraction; X-ray fluorescence (XRF); and chemical extraction; optical, transmission, and scanning electron microscopy; and Mössbauer spectroscopy.All of the sediments were low in total Fe content (≈ 1%) and exhibited complex Fe-mineralogy. The bulk pristine sediment and its sand, silt, and clay-sized fractions were studied in detail. The pristine sediments contained Fe(II) and Fe(III) mineral phases. Ferrous iron represented approximately 50% of FeTOT. The relative Fe(II) concentration increased in the sand fraction, and its primary mineralogic residence was clinochlore with minor concentrations found as a ferroan calcite grain cement in carbonate lithic fragments. Fe(III) existed in silicates (epidote, clinochlore, muscovite) and Fe(III) oxides of detrital and authigenic origin. The detrital Fe(III) oxides included hematite and goethite in the form of mm-sized nodular concretions and smaller-sized dispersed crystallites, and euhedral magnetite grains. Authigenic Fe(III) oxides increased in concentration with decreasing particle size through the silt and clay fraction. Chemical extraction and Mössbauer analysis indicated that this was a ferrihydrite like-phase. Quantitative mineralogic and Fe(II/III) ratio comparisons between the pristine and contaminated sediments were not possible because of textural differences. However, comparisons between the texturally-similar source (where bioavailable Fe(III) had been exhausted) and Fe(III) reducing zone sediments (where bioavailable Fe(III) remained) indicated that dispersed detrital, crystalline Fe(III) oxides and a portion of the authigenic, poorly crystalline Fe(III) oxide fraction had been depleted from the source zone sediment by microbiologic activity. Little or no effect of microbiologic activity was observed on silicate Fe(III). The presence of residual “ferrihydrite” in the most bioreduced, anoxic plume sediment (source) implied that a portion of the authigenic Fe(III) oxides were biologically inaccessible in weathered, lithic fragment interiors. Little evidence was found for the modern biogenesis of authigenic ferrous-containing mineral phases, perhaps with the exception of thin siderite or ferroan calcite surface precipitates on carbonate lithic fragments within source zone sediments.  相似文献   

17.
To increase the understanding of uranium transport in the environment and in the presence of steel corrosion products, the interaction of U(VI) with natural magnetite has been studied. Sorption studies have been carried out using X-ray photoelectron spectroscopy (XPS) and secondary ion mass spectrometry (SIMS). The XPS results clearly indicate the reduction of U(VI) to U(IV) on the surface of magnetite facilitated by electron transfer between the Fe and U, leading to a coupled oxidation of Fe(II) to Fe(III).  相似文献   

18.
《Applied Geochemistry》2005,20(7):1268-1283
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.  相似文献   

19.
Electron probe micro-analysis(EPMA) and scanning electron microscopy(SEM) equipped with energy dispersive spectrometry(EDS) have been used to investigate the principal ore minerals and coexisting metallic mineral inclusions in polished thin sections from the Tiegelongnan deposit, which consists of a high-sulfidation epithermal system(HSES) and a porphyry system(PS). Molybdenite,chalcopyrite, bornite, tennantite, enargite, digenite, anilite, covellite, and tetrahedrite have been identified by EPMA. Intergrowth, cross-cutting and replacement relationships between the metallic minerals suggest that molybdenite formed first(stage 1),followed by chalcopyrite ± bornite ± hematite(stage 2),then bornite ± Cu-sulfides ± Cu-Fe-sulfoarsenides(stage 3),and lastly Cu-Fe-sulfoarsenides ±Cu-sulfides(stage 4). Pyrite is developed throughout all the stages. Droplet-like inclusions of Au-Te minerals commonly occur in tennantite but not in the other major sulfides(molybdenite, chalcopyrite and bornite),implying that tennantite is the most important Au telluride carrier. The pervasive binary equilibrium phases of calaverite and altaite constrain f_(Te2) in the range from ～-6.5 to ～-8 and f_(S2)-11.The intergrowth of bornite and chalcopyrite and the conversion from bornite to digenite suggest fluctuated and relatively low precipitation temperature conditions in the HSES relative to the PS.Contrastingly, the dominance of chalcopyrite in the PS, with minor bornite, suggests relatively high temperature conditions. These new results are important for further understanding the mineral formation processes superimposed by HSES and PS systems.  相似文献   

20.
Analytical methods used for determining dissolved Fe(II) often yield inaccurate results in the presence of high Fe(III) concentrations. Accurate analysis of Fe(II) in solution when it is less than 1% of the total dissolved Fe concentration (FeT) is sometimes required in both geochemical and environmental studies. For example, such analysis is imperative for obtaining the ratio Fe(II)/Fe(III) in rocks, soils and sediments, for determining the kinetic constants of Fe(II) oxidation in chemical or biochemical systems operating at low pH, and is also important in environmental engineering projects, e.g. for proper control of the regeneration step (oxidation of Fe(II) into Fe(III)) applied in ferric-based gas desulphurization processes. In this work a method capable of yielding accurate Fe(II) concentrations at Fe(II) to FeT ratios as low as 0.05% is presented. The method is based on a pretreatment procedure designed to separate Fe(II) species from Fe(III) species in solution without changing the original Fe(II) concentration. Once separated, a modified phenanthroline method is used to determine the Fe(II) concentration, in the virtual absence of Fe(III) species. The pretreatment procedure consists of pH elevation to pH 4.2–4.65 using NaHCO3 under N2(g) environment, followed by filtration of the solid ferric oxides formed, and subsequent acidification of the Fe(II)-containing filtrate. Accuracy of Fe(II) analyses obtained for samples (Fe(II)/FeT ratios between 2% and 0.05%) to which the described pretreatment was applied was >95%. Elevating pH to above 4.65 during pretreatment was shown to result in a higher error in Fe(II) determination, likely resulting from adsorption of Fe(II) species and their removal from solution with the ferric oxide precipitate.  相似文献   

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