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1.
Pyrite is an environmentally significant mineral being the major contributor to acid rock drainage. Synchrotron based SPEM (scanning photoelectron microscopy) and micro-XPS (X-ray photoelectron spectroscopy) have been used to characterise fresh and oxidised pyrite (FeS2) with a view to understanding the initial oxidation steps that take place during natural weathering processes. Localised regions of the pyrite surface containing Fe species of reduced coordination have been found to play a critical role. Such sites not only initiate the oxidation process but also facilitate the formation of highly reactive hydroxyl radical species, which then lead the S oxidation process.Four different S species are found to be present on fresh fractured pyrite surfaces: S22−(bulk) (4-fold coordination), S22−(surface) (3-fold coordination), S2− and S0/Sn2− (metal deficient sulfide and polysulfide respectively). These species were found to be heterogeneously distributed on the fractured pyrite surface. Both O2 and H2O gases are needed for effective oxidation of the pyrite surface. The process is initiated when O2 dissociatively and H2O molecularly adsorb onto the surface Fe sites where high dangling bond densities exist. H2O may then dissociate to produce OH radicals. The adsorption of these species leads to the formation of Fe-oxy species prior to the formation of sulfoxy species. Evidence suggests that Fe-O bonds form prior to Fe-OH bonds. S oxidation occurs through interactions of OH radicals formed at the Fe sites, with formation of SO42− occurring via S2O32−/SO32− intermediates. The pyrite oxidation process is electrochemical in nature and was found to occur in patches, where site specific adsorption of O2 and H2O has occurred. Fe and S oxidation was found to occur within the same area of oxidation probably in atomic scale proximity. Furthermore, the O in SO42− arises largely from H2O; however, depending on the surface history, SO42− formed early in the oxidation process may also contain O from O2.  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.
Capture of Mo by FeS2 is an important sink for marine Mo. X-ray spectroscopy has shown that Mo forms Mo-Fe-S cuboidal clusters on pyrite. Reduction of MoVI must occur to stabilize these structures. Sulfide alone is a poor reductant for Mo, producing instead a series of MoVI thioanions (MoOxS4−x2−, x = 0-3). In solutions that contain both H2S and S0-donors (i.e. polysulfides; dissolved S8), Mo is transformed to MoIV or MoV2 polysulfide/sulfide anions. This intramolecular reduction requires no external reducing agent. Remarkably, an oxidizing agent (S0 donor), rather than a reducing agent, stabilizes the reducible MoVI complex. Thiomolybdates and their reduction products do not precipitate spontaneously; solutions supersaturated by 109 with respect to molybdenite, MoS2, produce no precipitate in 40 days. In 10-minute exposures, pyrite can scavenge MoOS32− and MoS42− weakly at mildly alkaline pH but can scavenge an unidentified product of the S0-induced reduction of MoOS32− very strongly. On the basis of these observations, a reaction pathway for Mo capture by pyrite is proposed. Conditions that favor Mo capture by this pathway also favor pyrite growth. Ascribing Mo capture simply to low redox potential is too simplistic and neglects the likely role of oxidizing S0-donors. The aqueous speciation of Mo in anoxic environments will be a function of the activity of zero-valent sulfur as well as the activity of H2S(aq).  相似文献   

4.
The nature of the surface oxidation phase on pyrite, FeS2, reacted in aqueous electrolytes at pH = 2 to 10 and with air under ambient atmospheric conditions was studied using synchrotron-based oxygen K edge, sulfur LIII edge, and iron LII,III edge X-ray absorption spectroscopy. We demonstrate that O K edge X-ray absorption spectra provide a sensitive probe of sulfide surface oxidation that is complementary to X-ray photoelectron spectroscopy. Using total electron yield detection, the top 20 to 50 Å of the pyrite surface is characterized. In air, pyrite oxidizes to form predominantly ferric sulfate. In aqueous air-saturated solutions, the surface oxidation products of pyrite vary with pH, with a marked transition occurring around pH 4. Below pH = 4, a ferric (hydroxy)sulfate is the main oxidation product on the pyrite surface. At higher pH, we find iron(III) oxyhydroxide in addition to ferric (hydroxy)sulfate on the surface. Under the most alkaline conditions, the O K edge spectrum closely resembles that of goethite, FeOOH, and the surface is oxidized to the extent that no FeS2 can be detected in the X-ray absorption spectra. In a 1.667 × 10−3 mol/L Fe3+ solution with ferric iron present as FeCl3 in NaCl, the oxidation of pyrite is autocatalyzed, and formation of the surface iron(III) oxyhydroxide phase is promoted at low pH.  相似文献   

5.
Pyrite (FeS2) and iron monosulfide (FeS) play a central role in the sulfur and iron cycles of marine sediments. They may be buried in the sediment or oxidized by O2 after transport by bioturbation to the sediment surface. FeS2 and FeS may also be oxidized within the anoxic sediment in which NO3−, Fe(III) oxides, or MnO2 are available as potential electron acceptors. In chemical experiments, FeS2 and FeS were oxidized by MnO2 but not with NO3− or amorphous Fe(III) oxide (Schippers and Jørgensen, 2001). Here we also show that in experiments with anoxic sediment slurries, a dissolution of tracer-marked 55FeS2 occurred with MnO2 but not with NO3− or amorphous Fe(III) oxide as electron acceptor. To study a thermodynamically possible anaerobic microbial FeS2 and FeS oxidation with NO3− or amorphous Fe(III) oxide as electron acceptor, more than 300 assays were inoculated with material from several marine sediments and incubated at different temperatures for > 1 yr. Bacteria could not be enriched with FeS2 as substrate or with FeS and amorphous Fe(III) oxide. With FeS and NO3−, 14 enrichments were obtained. One of these enrichments was further cultivated anaerobically with Fe2+ and S0 as substrates and NO3− as electron acceptor, in the presence of 55FeS2, to test for co-oxidation of FeS2, but an anaerobic microbial dissolution of 55FeS2 could not been detected. FeS2 and FeS were not oxidized by amorphous Fe(III) oxide in the presence of Fe-complexing organic compounds in a carbonate-buffered solution at pH 8. Despite many different experiments, an anaerobic microbial dissolution of FeS2 could not be detected; thus, we conclude that this process does not have a significant role in marine sediments. FeS can be oxidized microbially with NO3− as electron acceptor. O2 and MnO2, but not NO3− or amorphous Fe(III) oxide, are chemical oxidants for both FeS2 and FeS.  相似文献   

6.
Fracture surfaces of a natural carrollite specimen have been characterised by synchrotron and conventional X-ray photoelectron spectroscopy and near-edge X-ray absorption spectroscopy. For the synchrotron X-ray measurements, the mineral surfaces were prepared under clean ultra high vacuum and were unoxidised. The characterisation was undertaken primarily to establish unequivocally the oxidation state of the Cu in the mineral, but also to obtain information on the electronic environments of the Co and S, and on the surface species. Experimental and simulated Cu L2,3-edge absorption spectra confirmed an oxidation state of CuI, while Co 2p photoelectron and Co L2,3 absorption spectra were largely consistent with the CoIII established previously by nuclear magnetic resonance spectroscopy. S 2p photoelectron spectra provided no evidence for S to be present in the bulk in more than one state, and were consistent with an oxidation state slightly less negative than S-II. Therefore it was concluded that carrollite can be best represented by CuICoIII2(S4)-VII. The CuI oxidation state is in agreement with that expected for Cu tetrahedrally coordinated by S, but is in disagreement with the CuII deduced previously from some magnetic, magnetic resonance and Cu L-edge X-ray absorption spectroscopic measurements. A significant concentration of S species with core electron binding energies both lower and higher than the bulk value were formed at fracture surfaces, and these entities were assigned to monomeric and oligomeric surface S species. The density of Cu d states calculated for carrollite differed from that previously reported but was consistent with the observed Cu L3 X-ray absorption spectrum. The initial oxidation of carrollite in air under ambient conditions was confirmed to be congruent, unlike the incongruent reaction undergone by a number of non-thiospinel sulfide minerals.  相似文献   

7.
To understand the retention of As on a natural manganese sand, the structural, textural and chemical properties of the solid were first investigated by combining scanning electron microscopy (SEM), transmission electron microscopy (TEM), electron-energy-loss spectroscopy (EELS), X-ray diffraction (XRD), BET N2 gas adsorption, diffuse reflectance Fourier transform infrared (FT-IR) spectroscopy and X-ray photoelectron spectroscopy (XPS) analysis. Manganese sand could be mainly described as a mixture of a phyllomanganate, lithiophorite [(Al,Li)MnO2(OH)2], and pyrolusite (MnO2). Iron particle, kaolinite and gibbsite type-phases were also observed. Particles organization led to the presence of a mesoporosity with pore diameters ranging from 100 to 200 Å and a specific surface area of 23 m2 g−1. Contact with an As(V) solution (0.67 mmol L−1) led to an average fractional surface coverage of 0.4. Both As (V) and (III) were present on the surface of the sand in a 1:1 ratio. As(V) was sorbed on lithiophorite-type particles through surface complexation type reaction. As(III) was thought to result from As(V) reduction mechanism on iron particles.  相似文献   

8.
Techniques of X-ray photoelectron and Auger electron spectroscopy, scanning probe microscopy were used to demonstrate that the natural surface of hydrothermally synthesized pyrite, as well as vacuum fractures, contain a number of sulfide-sulfur species: disulfide, monosulfide, and, more rarely, polysulfide. The natural surface of hydrothermal pyrite is chemically modified compared to the inner volume into a nonautonomous phase film up to ～500 nm thick, which has a variable composition resembling that of pyrrhotite but with broader variations toward FeS2. Its principal distinctive feature is the presence of a peak at ～710 eV in the XPS Fe 2p3/2 spectrum, which is often higher than the main peak of bivalent low-spin Fe(II) in the pyrite structure (707 eV). The “basic” structure of the nonautonomous phase is a layer of variable composition Fe2+[S, S2, S n ]2?, whose S/S2 ratio varies from ～0.5 to ～2.0, averaging at ～1.1. This layer may include admixtures of minor elements, as follows from the appearance of a nonautonomous phase in the presence of As, which does not, however, form an individual phase. The polymerization of S at the surface is thereby more significant. The major oxisulfide components of this phase may be the sulfite and thiosulfate ions at a subordinate concentration of sulfate because of the instability of coexisting sulfate and disulfide ions, which results, in the presence of oxygen, in sulfite (thiosulfate) and sulfide ions in the nonautonomous phase. In line with XPS, scanning probe microscopic (SPM) data show that, at a high S activity in the “pure” system, the surface of the crystals contains practically no nanometer-sized phases and is characterized by low roughness (14–17 nm). At a low S fugacity in equilibrium with pyrrhotite and sphalerite, the average roughness of the surface increases to 25–65 nm, with the maximum height of the surface features of ～100–500 nm. This is consistent with Auger spectroscopic data, obtained after the etching (ion milling) of the surface with Ar+, on the thickness of the nonstoichiometric surface layer. Comparison with analogous data on other sulfides shows that crystals growing in hydrothermal environments have surface layers up to ～500 nm thick, which are different from the main volume of the crystal in chemistry, stoichiometry, and, possibly, also structure. This is scale of the surface heterogeneity at which the typochemistry of mineral surfaces may be manifested. The typochemistry of pyrite stems from the ability of the nonautonomous phase to “record” the growth conditions of crystals in terms of two major factors: the purity of the system (the occurrence of other phases, including virtual ones, i.e., potentially possible phases of admixture elements) and S fugacity (which influences the S/S2 ratio at the surface). The geochemical role of the surface nonautonomous phase in pyrite may be very significant, particularly when minor elements are captured that are incompatible with the pyrite structure but can be easily accommodated in the less rigid structure of the nonautonomous phase.  相似文献   

9.
The sulfide minerals exhibit a rich diversity in sturctural chemistry and in electrical, magnetic and other physical properties. Models based on molecular orbital theory and incorporating some elements of band theory can be developed to describe the diverse valence electron behavior in these minerals. Qualitative models can be proposed on the basis of observed properties, and the models can be tested and refined using experimental data from X-ray emission and X-ray photoelectron spectroscopy and quantum mechanical calculations performed on cluster units which form the basic building blocks of the crystals. This approach to chemical bonding in sulfide minerals is illustrated for binary non-transition metal sulfides (ZnS, CdS, HgS, PbS), binary transition metal sulfides (FeS2, CoS2, NiS2, CuS2 ZnS2) and more complex sulfides (CuFeS2, Cu2S, Ag2S, CuS, Co3S4, CuCo2S4, Fe3S4). The relationship between qualitative and quantitative theories is reviewed with reference to the pyrite-marcasite-arsenopyrite-loellingite series of minerals. Application of the models to understanding structure-determining principles, relative stabilities, solid solution limits and properties such as color, reflectance and hardness are discussed.  相似文献   

10.
Interatomic potential parameters have been derived at simulated temperatures of 0 K and 300 K to model pyrite FeS2. The predicted pyrite structures are within 1% of those determined experimentally, while the calculated bulk modulus is within 7%. The model is also able to simulate the properties of marcasite, even though no data for this phase were included in the fitting procedure. There is almost no difference in results obtained for pyrite using the two potential sets; however, when used to model FeS2 marcasite, the potential fitted at 0 K performs better. The potentials have also been used to study the high-pressure behaviour of pyrite up to 44 GPa. The calculated equation of state gives good agreement with experiment and shows that the Fe–S bonds shorten more rapidly that the S–S dimer bonds. The behaviour of marcasite at high pressure is found to be similar to that of pyrite.  相似文献   

11.
Arsenite sorption on troilite (FeS) and pyrite (FeS2)   总被引：4，自引：0，他引：4  
Arsenic is a toxic metalloid whose mobility and availability are largely controlled by sorption on sulfide minerals in anoxic environments. Accordingly, we investigated reactions of As(III) with iron sulfide (FeS) and pyrite (FeS2) as a function of total arsenic concentration, suspension density, sulfide concentration, pH, and ionic strength. Arsenite partitioned strongly on both FeS and FeS2 under a range of conditions and conformed to a Langmuir isotherm at low surface coverages; a calculated site density of near 2.6 and 3.7 sites/nm2 for FeS and FeS2, respectively, was obtained. Arsenite sorbed most strongly at elevated pH (>5 to 6). Although solution data suggested the formation of surface precipitates only at elevated solution concentrations, surface precipitates were identified using X-ray absorption spectroscopy (XAS) at all coverages. Sorbed As was coordinated to both sulfur [d(As-S) = 2.35 Å] and iron [d(As-Fe) = 2.40 Å], characteristic of As coordination in arsenopyrite (FeAsS). The absorption edge of sorbed As was also shifted relative to arsenite and orpiment (As2S3), revealing As(III) reduction and a complete change in As local structure. Arsenic reduction was accompanied by oxidation of both surface S and Fe(II); the FeAsS-like surface precipitate was also susceptible to oxidation, possibly influencing the stability of As sorbed to sulfide minerals in the environment. Sulfide additions inhibit sorption despite the formation of a sulfide phase, suggesting that precipitation of arsenic sulfide is not occurring. Surface precipitation of As on FeS and FeS2 supports the observed correlation of arsenic and pyrite and other iron sulfides in anoxic sediments.  相似文献   

12.
Sulfur K-edge X-ray absorption near edge structure (XANES) spectra were recorded for experimental glasses of various compositions prepared at different oxygen fugacities (fO2) in one-atmosphere gas-mixing experiments at 1400 °C. This sample preparation method only results in measurable S concentrations under either relatively reduced (log fO2 < −9) or oxidised (log fO2 > −2) conditions. The XANES spectra of the reduced samples are characterised by an absorption edge crest at 2476.4 eV, typical of S2−. In addition, spectra of Fe-bearing compositions exhibit a pronounced absorption edge shoulder. Spectra for all the Fe-free samples are essentially identical, as are the spectra for the Fe-bearing compositions, despite significant compositional variability within each group. The presence of a sulfide phase, such as might exsolve on cooling, can be inferred from a pre-edge feature at 2470.5 eV.The XANES spectra of the oxidised samples are characterised by an intense transition at 2482.1 eV, typical of the sulfate anion SO42−. Sulfite (SO32−) has negligible solubility in silicate melts at low pressures. The previous identification of sulfite species in natural glass samples is attributed to an artefact of the analysis (photoreduction of S6+). S4+ does, however, occur unambiguously with S6+ in Fe-free and Fe-poor compositions prepared in equilibrium with CaSO4 at 4-16 kbar, and when buffered with Re/ReO2 at 10 kbar. Solubility of S4+ thus requires partial pressures of SO2 considerably in excess of 1 bar. A number of experiments were undertaken in an attempt to access intermediate fO2s more applicable to terrestrial volcanism. Although these were largely unsuccessful, S2− and S6+ were found to coexist in some samples that were not in equilibrium with the imposed fO2.The XANES spectra of natural olivine-hosted melt inclusions and submarine glasses representative of basalts at, or close to, sulfide saturation show mainly dissolved S2−, but with minor sulfate, and additionally a peak at 2469.5 eV, which, although presumably due to immiscible sulfide, is 1 eV lower than that typical of FeS. These sulfate and sulfide-related peaks disappear with homogenisation of the inclusions by heating to 1200 °C followed by rapid quenching, suggesting that both these features are a result of cooling under natural conditions. The presence of small amounts of sulfate in otherwise reduced basaltic magmas may be explained by the electron exchange reaction: S2− + 8Fe3+ = S6+ + 8Fe2+, which is expected to proceed strongly to the right with decreasing temperature. This reaction would explain why S2− and S6+ are frequently found together despite the very limited fO2 range over which they are thermodynamically predicted to coexist. The S XANES spectra of water-rich, highly oxidised, basaltic inclusions hosted in olivine from Etna and Stromboli confirm that nearly all S is dissolved as sulfate, explaining their relatively high S contents.  相似文献   

13.
Chalcopyrite (CuFeS2) leaching in perchloric acid (HClO4) at an initial pH of one and a temperature of 85 °C has been examined. The rate of leaching of Cu and Fe increased progressively over the duration of the experiment. The Cu leach rate was initially greater (up to 24 h) but thereafter the leach rates for Cu and Fe were approximately equal. After 313 h 81% Cu release was achieved at which time the leach experiment was terminated. Only 25% of the available S was released into solution during the leaching process. Surface speciation over the duration of the leach was examined using X-ray photoelectron spectroscopy (XPS), time of flight secondary ion mass spectrometry (ToF-SIMS) and scanning electron microscopy (SEM). As a result, a three-step reaction pathway is proposed. The first oxidation step involves the release of Cu and Fe into solution and the polymerisation of monosulfide (S2−) to polysulfide . The subsequent reduction step does not result in the release of cations to solution but does result in the reformation of surface S2− and other short chain polysulfides, which then on further oxidation restructure to form crystalline elemental sulfur (S0). This final oxidation step is accompanied by further cation release.  相似文献   

14.
XANES analyses at the sulfur K-edge were used to determine the oxidation state of S species in natural and synthetic basaltic glasses and to constrain the fO2 conditions for the transition from sulfide (S2−) to sulfate (S6+) in silicate melts. XANES spectra of basaltic samples from the Galapagos spreading center, the Juan de Fuca ridge and the Lau Basin showed a dominant broad peak at 2476.8 eV, similar to the spectra obtained from synthetic sulfide-saturated basalts and pyrrhotite. An additional sharp peak at 2469.8 eV, similar to that of crystalline sulfides, was present in synthetic glasses quenched from hydrous melts but absent in anhydrous glasses and may indicate differences in sulfide species with hydration or presence of minute sulfide inclusions exsolved during quenching. The XANES spectra of a basalt from the 1991 eruption of Mount Pinatubo, Philippines, and absarokitic basalts from the Cascades Range, Oregon, USA, showed a sharp peak at 2482.8 eV, characteristic of synthetic sulfate-saturated basaltic glasses and crystalline sulfate-bearing minerals such as hauyne. Basaltic samples from the Lamont Seamount, the early submarine phase of Kilauea volcano and the Loihi Seamount showed unequivocal evidence of the coexistence of S2− and S6+ species, emphasizing the relevance of S6+ to these systems. XANES spectra of basaltic glasses synthesized in internally-heated pressure vessels and equilibrated at fO2 ranging from FMQ − 1.4 to FMQ + 2.7 showed systematic changes in the features related to S2− and S6+ with changes in fO2. No significant features related to sulfite (S4+) species were observed. These results were used to construct a function that allows estimates of S6+/ΣS from XANES data. Comparison of S6+/ΣS data obtained by S Kα shifts measured with electron probe microanalysis (EPMA), S6+/ΣS obtained from XANES spectra, and theoretical considerations show that data obtained from EPMA measurements underestimate S6+/ΣS in samples that are sulfate-dominated (most likely because of photo-reduction effects during analysis) whereas S6+/ΣS from XANES provide a close match to the expected theoretical values. The XANES-derived relationship for S6+/ΣS as a function of fO2 indicates that the transition from S2− to S6− with increasing fO2 occurs over a narrower interval than what is predicted by the EPMA-derived relationship. The implications for natural systems is that small variation of fO2 above FMQ + 1 will have a large effect on S behavior in basaltic systems, in particular regarding the amount of S that can be transported by basaltic melts before sulfide saturation can occur.  相似文献   

15.
The gradual oxidation of dry mackinawite (tetragonal FeS1? x ) has been studied using X-ray diffraction (XRD), transmission electron microscopy (TEM), transmission Mössbauer spectroscopy (TMS) and X-ray photoelectron spectroscopy (XPS). The initial material and samples exposed to the air (5?min to 6?months) have been analysed. Diffraction patterns showed the slow disappearance of mackinawite with time with concomitant appearance of greigite (Fe3S4) and elemental sulphur (S(0)) as well as iron (oxyhydr)oxides, i.e. magnetite (Fe3O4) and probably goethite (α-FeOOH). After 6 months' air exposure, mackinawite and also greigite were entirely converted into elemental sulphur and iron (oxyhydr)oxide(s), indicating that greigite was an intermediate reaction product. Mössbauer spectra of samples oxidized in air appeared rather complex for interpreting what was easily conceivable in view of the association of several phases, as revealed by the diffraction patterns. The low-temperature Mössbauer spectrum obtained after 6?months air exposure was attributed to magnetite, although a mixture of magnetite and goethite was not completely excluded. XPS iron and oxygen data confirmed the formation of Fe(III) (oxyhydr)oxides at the surface after an induction period. Sulphur spectra demonstrated various oxidation states from S(-II) (monosulphide) to S(VI) (sulphate) for the longest experiments. Mackinawite in these experiments reacted mainly with adsorbed O2 to form elemental sulphur and magnetite. Additionally, sufficient sulphur was generated to react stoichiometrically with mackinawite to produce greigite. Finally, greigite, in the longest experiments, was transformed into elemental sulphur and magnetite.  相似文献   

16.
Self-diffusion of sulfur in pyrite (FeS2) was characterized over the temperature range ∼500-725 °C (∼1 bar pressure) by immersing natural specimens in a bath of molten elemental 34S and characterizing the resulting diffusive-exchange profiles by Rutherford backscattering spectroscopy (RBS). The temperature dependence of the sulfur diffusivity (DS) conforms to DS = Do exp(−Ea/RT), where the pre-exponential constant (Do) and the activation energy (Ea) are constrained as follows:
  相似文献   

17.
X-ray photoelectron and absorption spectra have been obtained for natural specimens of cubanite and compared with the corresponding spectra for chalcopyrite. Synchrotron X-ray photoelectron spectra of surfaces prepared by fracture under ultra-high vacuum revealed some clear differences for the two minerals, most notably those reflecting their different structures. In particular, the concentration of the low binding energy S species formed at cubanite fracture surfaces was approximately double that produced at chalcopyrite surfaces. However, the core electron binding energies for the two S environments in cubanite were not significantly different, and were similar to the corresponding values for the single environment in chalcopyrite. High binding energy features in the S 2p and Cu 2p spectra were not related to surface species produced either by the fracture or by oxidation, and most probably arose from energy loss due to inter-band excitation. Differences relating to the Fe electronic environments were detectable, but were smaller than expected from some of the observed physical properties and Mössbauer spectroscopic parameters for the two minerals. X-ray absorption and photoelectron spectra together with the calculated densities of states for cubanite confirmed an oxidation state of CuI in the mineral. It was concluded that the best formal oxidation state representation for cubanite is CuI(Fe2)VS 3 ?II .  相似文献   

18.
Compounds with mixed and intermediate sulfur valences form cloudy small inclusions in banded pyrite and 2–4 mm large rounded aggregates in pyrite stalactites. Such areas under high magnification of SEM appear to be a mixture of FeS2 with FeS2O3. Some of the microareas of 40–50 m are homogeneous and can be identified by reflected light microscopy, microprobe and soft X-ray spectroscopy as Fe-thiosulphate, FeS2O3 or (Fe, Pb)2S3O7 with this compound having one sulfur –2 and two sulfurs +6. The intermediate sulfur compounds are enriched in Pb, Ni, Co and As.  相似文献   

19.
Recent experimental studies have reported the existence of two new Sb sulfide species, Sb2S52− and Sb2S62−, in alkaline sulfidic solutions in equilibrium with stibnite, Sb2S3, and orthorhombic S. These species contain Sb(V), which has also recently been identified in similar solutions using EXAFS by other researchers. This represents a significant change from the consensus a decade ago that sulfidic solutions of Sb contained only Sb(III) species. I have calculated from first principles of quantum mechanics the energetics for the oxidation of the Sb(III) sulfide dimer Sb2S42− to the mixed Sb(III,V) dimer Sb2S52− and then to the all Sb(V) dimer, Sb2S62−. Gas-phase reaction energies have been evaluated using polarized valence double zeta effective core potential basis sets and Moller-Plesset second order treatments of electron correlation. All translational, rotational and vibrational contributions to the gas-phase reaction free energy have been calculated. Hydration energies have been obtained using the COSMO version of the self-consistent reaction field polarizable continuum method. Negative free energy changes are calculated for the oxidation of the dianion of the III,III dimer to the III,V dimer by both small polysulfides, like S4H−, and elemental S, modeled as S8. For the further oxidation of the III,V dimer to the V,V dimer the reaction free energies are calculated to be close to zero. The partially protonated Sb III,III dimer monoanion HSb2S4− can also be oxidized, but the reaction is not so favorable as for the dianion. Comparison of the calculated aqueous deprotonation energies of H2Sb2S4, H2Sb2S5 and H2Sb2S6 and their dianions with values calculated for various oxyacids indicates that the III,V and V,V dimers will have pKa2 values <5, so that their dianions will be the dominant species in alkaline solutions. These results are thus consistent with the recent identification of Sb2S52− and Sb2S62− species. I have also calculated the Raman spectra of Sb2S52− and Sb2S62− to assist in their identification. The calculated vibrational frequencies of the III,V and V,V dimers are characteristically higher than those of the III,III dimer I previously studied. The III,V dimer may contribute shoulders to the Raman spectrum.  相似文献   

20.
《Chemical Geology》2007,236(3-4):228-246
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