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1.
Sulfide compositions with known Re, Os, Ir, Ru, Rh, Pt, and Pd contents are synthesized to be used as standards for noble metal analysis in solid solution in sulfides. Major elements were added as metals and elemental S. The noble metals, i.e. 35 and 60 ppm each, were added as solutions by micro syringe. Following synthesis at 1 atm the sulfides were sintered at 1.5 to 2 GPa to obtain pellets with theoretical density. Aliquots of the pellets were analysed by isotope dilution ICP-MS for bulk Re and platinum-group elements (PGE). The spatial noble metal distribution was investigated with an ArF excimer laser coupled to a single collector ICP mass spectrometer. Sample homogeneity is shown to depend on the metal/S spectrum and the major element composition of the sulfide, as well as on more subtle factors like oxygen partial pressure during synthesis, run temperature, and degree of partial melting. The most homogeneous sulfide composition is a (Fe,Ni)1 − x S monosulfide with 5 wt % Ni and 1-sigma variations in 34S-normalized noble metal count rates of <3.6%. Nearly as homogeneous is a pure Fe1 − x S monosulfide with 1-sigma variations in 34S-normalized noble metal count rates of <5.8 %. A Cu-bearing Fe1 − x S monosulfide with 2 wt % Cu was found to be considerably more heterogeneous, suggesting that Cu in solid solution in monosulfides promotes noble metal heterogeneity. The sulfide composition least suitable for the synthesis of noble metal sulfide standards is NiS.  相似文献   

2.
Organic sulfur in marine sediment is 34S enriched relative to the co-existing pyrite. This phenomenon is still enigmatic. Timing of the sulfur incorporation, immobilization and different sulfur species involved are part of the explanations. The reduced sulfur species incorporation into organic matter (OM) is generally assumed to have negligible δ34S fractionation. This assumption has never been confirmed by laboratory experimental data. The present study measures the δ34S changes resulting from reduced sulfur species (sulfides and polysulfide anions) incorporation into organic model compounds in an aquatic and low temperature (25 °C) system that simulates diagenetic marine environment. In addition, we also investigate the δ34S fractionation and the isotope chemical mixing in the formation of polysulfide anions produced from elemental sulfur and sulfide anions. The results showed total isotope mixing between the two species in the formation of polysulfides. Acidification of the polysulfides solution caused δ34S fractionation between the released elemental sulfur and H2S. The incorporation of polysulfides and sulfides into carbonyl groups, caused 34S enrichment relative to the starting polysulfides and sulfide of 4–5‰. The 34S enrichment of the sulfurized carbonyl groups showed a minimal effect by temperature (0–70 °C) and is not affected by salinity, polysulfides composition, reaction time or solubility in water. The incorporation of polysulfides and sulfides into brominated organic compounds was negligibly 34S enriched. The chemical mechanisms controlling the polysulfides incorporation into OM depend mostly on the functional groups and determine the 34S enrichment of the sulfurized OM. The results presented in this study can explain part of the difference between pyrite δ34S and sulfurized OM δ34S in natural marine sediments.  相似文献   

3.
Faecal pellet deposition and bioturbation may lead to heterogeneously distributed particles of localized highly reactive organic matter (microniches) being present below the oxygen penetration depth. Where O2, NO3−, and Fe/Mn oxyhydroxides become depleted within these microniches or where they exist in zones of sulfate reduction, significant localized peaks in sulfide concentration can occur. These discrete zones of sulfide evolution can cause formation of iron sulfides that would not be predicted by analysis of the ‘bulk’ sediment. Using a reaction-transport model developed specifically for investigating spherical microniches, and incorporating 3D diffusion, we investigated how the rate constants of organic matter (OM) degradation, particle porosity and niche lifetime, affect dissolved sulfide and iron concentrations, and formation of iron sulfide at such niches. For all of the modelled scenarios the saturation index for iron sulfide is positive, indicating favourable conditions for FeS precipitation in all niches. Those simulations within the microniche lifetime range of 2.5-5 days gave comparable concentration ratios of sulfide to iron in solution within the niche to experimentally observed values. Our model results provide insight into the mechanisms of preservation of OM, including soft tissue, in the paleo record, by predicting conditions that result in preferential deposition of precipitates at the edge of microniches. Decreases in porosity, shorter niche lifetimes and increases in OM degradation rate constants, all tend to increase the likelihood that FeS precipitation will preferentially occur at the edges of a niche, rather than uniformly throughout the niche volume.  相似文献   

4.
与基性-超基性侵入体有关的Ni-Cu-PGE硫化物矿床是镍-铜-铂族元素矿床的最重要类型。传统观点认为,Ni-Cu-PGE硫化物矿床是由成矿岩浆分异演化、熔离形成的,与围岩性质关系不大。实际上,大部分基性-超基性岩浆是硫化物不饱和的,在岩浆自身演化过程中难以聚集大量硫化物而形成有经济价值的大型高品位NiCu-PGE硫化物矿床。因此,壳源硫的加入是基性-超基性岩浆中硫化物浓度达到过饱和,熔离形成Ni-Cu-PGE硫化物矿床的关键。膏盐层是富含石膏等硫酸盐(SO24-)的蒸发沉积建造,除SO24-外,还富含Cl-、CO23-、Na+、K+等盐类物质,在自然界分布广、面积大,是地壳中重要的硫源层和氧化障。但膏盐层在Ni-Cu-PGE硫化物矿床中的作用长期被忽视,制约了Ni-Cu-PGE硫化物矿床成矿找矿理论的发展。文章以世界最大的俄罗斯诺里尔斯克Ni-CuPGE硫化物矿床为例,介绍了膏盐层与矿床分布的空间关系、石膏等硫酸盐矿物在矿床和蚀变围岩中的分布、成矿元素和硫同位素组成特征及变化规律,阐明了膏盐层在成矿中的作用和控矿机理。膏盐(SO24-)的加入,可以大幅度提高成矿系统的氧逸度,将成矿岩浆中Fe2+氧化成Fe3+,形成铁氧化物,SO24-自身被还原,向成矿系统提供还原硫S2-,与Cu2+、Ni2+等结合,形成铜镍硫化物等,使基性-超基性成矿岩浆由硫化物不饱和变为过饱和,形成硫化物小液滴,在岩浆房经聚集-熔离-富集,形成岩浆型Ni-Cu-PGE硫化物矿床。除膏盐层外,富含硫化物的地层也是形成Ni-Cu-PGE硫化物矿床的重要硫源层。  相似文献   

5.
《Applied Geochemistry》1988,3(3):333-344
The sediments of Lake Anna, Virginia, act as a major sink for incoming acid mine drainage (AMD) pollutants (Fe, SO42−, H+) due to bacterial sulfate reduction (SR). Acid-volatile sulfide (AVS), elemental S, and pyrite concentrations in the sediments of the polluted arm of the lake are significantly greater than those in unpolluted sections of the lake. Measurements of SR using 35SSO42− showed that AVS and S0 are the major short-term (48 h) products of SR in these sediments. Inorganic forms of S(AVS, S0, and FeS2) made up from 60 to 100% of the total sediment S concentration. Pyrite concentrations in the sediment were high but decreased exponentially with distance from the AMD source, suggesting that the pyrite was deposited as stream detritus from the abandoned mines. Iron monosulfide and elemental S concentrations were highest at a station 1 km away from the AMD inflow, indicating formation in situ. There was no evidence for the formation of organic S species. The results suggest that in Fe- and S-rich locations such as those contaminated with acid mine drainage, the distribution of end products of SR may vary substantially from those reported for more moderate environments.  相似文献   

6.
A complete analysis of a sulfide rich water from a sedimentary area has been achieved. The formation of metastable sulfur species (polysulfide ions, colloidal sulfur and thiosulfate) is very important. The relative concentrations of the sulfur species is controlled by bacterial processes (Desulfovibrio and Thiobacteriaceae). Electrochemical measurements and results of the analyses are in agreement. A possible repartition of polysulfide ions is S2?6 ≈- S2?5 >S2?4. This repartition, although out of equilibrium, is characteristic of the processes leading to the formation of the metastable sulfur species.The water is in equilibrium with amorphous FeS formation. When sulfide, polysulfide and thiosulfate complexing of trace metals Cu, Cd and Pb is taken into account, an agreement is reached between their concentrations in water and their concentrations in the FeS precipitate.  相似文献   

7.
Garnet–spinel lherzolites from Antarctica and peridotites from Mongolia were fluid saturated, which is indicated by the presence of fluid inclusions in their minerals. Flows of reactive fluids caused extensive metasomatic alteration of mantle materials. The cryometric and Raman spectroscopic investigation of the Antarctic xenoliths showed that their fluid was a complex mixture of CO2, N2, H2S, and H2O with a density of up to 1.23 g/cm3. The entrapment of fluids was accompanied by the formation of clusters of numerous sulfide inclusions. The compositions of these inclusions correspond to a Ni-rich sulfide melt and a monosulfide solid solution. The partition coefficient of Ni between them (DNi mss/melt) ranges from 0.99 to 3.23, which suggests that the two-phase sulfide assemblages in the partly decrepitated inclusions equilibrated at 920–1060°C. In order to refine the initial P-T conditions of the development of the Antarctic peridotites, the results of our investigation were evaluated in the light of experimental data on (1) the stability field of the two-phase assemblage mss + sulfide melt, (2) the solidus of peridotite + 0.9CO2 + 0.1 H2O, and (3) isochores of 0.8CO2 + 0.2N2 fluid. The obtained parameters are close to 1270–1280°C and 2.2 GPa and lie near the Sp–Gar boundary. The temperature of the existence of sulfide melt at a pressure of 2.2 GPa must be near 1300°C and corresponds to the boundary between the occurrence of carbon as CO2 fluid and carbonate (carbonate melt).  相似文献   

8.
Reactions between reduced inorganic sulfur and organic compounds are thought to be important for the preservation of organic matter (OM) in sediments, but the sulfurization process is poorly understood. Sulfur isotopes are potentially useful tracers of sulfurization reactions, which often occur in the presence of a strong porewater isotopic gradient driven by microbial sulfate reduction. Prior studies of bulk sedimentary OM indicate that sulfurized products are 34S-enriched relative to coexisting sulfide, and experiments have produced 34S-enriched organosulfur compounds. However, analytical limitations have prevented the relationship from being tested at the molecular level in natural environments. Here we apply a new method, coupled gas chromatography – inductively coupled plasma mass spectrometry, to measure the compound-specific sulfur isotopic compositions of volatile organosulfur compounds over a 6 m core of anoxic Cariaco Basin sediments. In contrast to current conceptual models, nearly all extractable organosulfur compounds were substantially depleted in 34S relative to coexisting kerogen and porewater sulfide. We hypothesize that this 34S depletion is due to a normal kinetic isotope effect during the initial formation of a carbon–sulfur bond and that the source of sulfur in this relatively irreversible reaction is most likely the bisulfide anion in sedimentary porewater. The 34S-depleted products of irreversible bisulfide addition alone cannot explain the isotopic composition of total extractable or residual OM. Therefore, at least two different sulfurization pathways must operate in the Cariaco Basin, generating isotopically distinct products. Compound-specific sulfur isotope analysis thus provides new insights into the timescales and mechanisms of OM sulfurization.  相似文献   

9.
Black shale oxidative weathering plays a significant role in a variety of processes including acid mine drainage and atmospheric CO2 control. The modeling of weathering is highly dependent on reactive surface area. In this study it is shown that black shale oxidative weathering is regulated mainly by the external, geometrical surface area of rock polyhedrons and the organic matter’s (OM) internal surface area. The internal rock surface area decreases dramatically during OM dissolution from ∼15 m2/g to ∼5 m2/g. A linear relationship was found between the decrease of internal rock surface area and quantity of OM dissolved. Optical roughness analyses of black and bleached shale surface area reveal the formation of macropores due to the dissolution of mesoporous and probably microporous OM. However, due to deconsolidation, the geometrical external rock polyhedron surface area increases during weathering. Black shale polyhedrons show a doubling of their external surface area as OM decreases. This provokes an increase of the shale volume which is easily accessible by fluids. The increase of the external rock surface area seems to be self-accelerating during weathering. The upscaling of external and internal rock surface area evolution during weathering presented in this study demonstrates the possible application of these results to the improved understanding of a chemical transport in a variety of natural systems.  相似文献   

10.
Pyritization in late Pleistocene sediments of the Black Sea is driven by sulfide formed during anaerobic methane oxidation. A sulfidization front is formed by the opposing gradients of sulfide and dissolved iron. The sulfidization processes are controlled by the diffusion flux of sulfide from above and by the solid reactive iron content. Two processes of diffusion-limited pyrite formation were identified. The first process includes pyrite precipitation with the accumulation of iron sulfide precursors with the average chemical composition of FeSn (n = 1.10-1.29), including greigite. Elemental sulfur and polysulfides, formed from H2S by a reductive dissolution of Fe(III)-containing minerals, serve as intermediates to convert iron sulfides into pyrite. In the second process, a “direct” pyrite precipitation occurs through prolonged exposure of iron-containing minerals to dissolved sulfide. Methane-driven sulfate reduction at depth causes a progressive formation of pyrite with a δ34S of up to +15.0‰. The S-isotopic composition of FeS2 evolves due to contributions of different sulfur pools formed at different times. Steady-state model calculations for the advancement of the sulfidization front showed that the process started at the Pleistocene/Holocene transition between 6360 and 11 600 yr BP. Our study highlights the importance of anaerobic methane oxidation in generating and maintaining S-enriched layers in marine sediments and has paleoenvironmental implications.  相似文献   

11.
董宇  魏博  王焰 《岩石学报》2021,37(9):2875-2888
金川铜镍硫化物矿床是我国最主要的铂族元素(PGE)资源产地,其矿石受热液蚀变作用影响明显,并产出多种铂族矿物(PGM)。岩浆演化和热液蚀变过程中PGE的迁移富集机制和PGM的成因,一直是研究PGE地球化学行为非常关注的问题。本文对金川铜镍硫化物矿床中PGM的研究发现,其主要类型包括含PGE的硫砷化物(硫砷铱矿)和砷化物(砷铂矿),Pd的铋化物、碲化物和硒化物,以及少量其他铂族矿物。其中,硫砷铱矿可包裹于各种贱金属硫化物(镍黄铁矿、磁黄铁矿和黄铜矿)中,表明硫砷铱矿可能结晶于早期的含As硫化物熔体,随后被包裹于硫化物熔体冷凝分异产生的单硫化物固溶体(MSS)和中间硫化物固溶体(ISS)中。硫化物熔体中的As可能主要通过地壳混染作用加入幔源岩浆。大量铋钯矿(PdBi)呈微细乳滴状包裹于黄铜矿中,为晚期ISS冷凝形成黄铜矿过程中出溶的产物。少量铋钯矿(PdBi_2)呈不规则状充填于矿物裂隙,与次生磁铁矿脉紧密共生,并随矿石的蚀变程度增加,铋钯矿的化学成分由PdBi逐渐向PdBi_2转变,表明这部分铋钯矿为后期热液蚀变产物。铋碲钯矿和钯的硒化物则主要产出于镍黄铁矿裂隙且与次生磁铁矿紧密共生,指示明显的热液成因。钯的硒化物的出现表明,岩浆期后酸性、高盐度、高氧逸度的富Cl~-流体对金川铜镍硫化物矿床中Pd的迁移和富集起到了关键控制作用。  相似文献   

12.
Sorptive stabilization of organic matter by amorphous Al hydroxide   总被引：3，自引：0，他引：3  
Amorphous Al hydroxides (am-Al(OH)3) strongly sorb and by this means likely protect dissolved organic matter (OM) against microbial decay in soils. We carried out batch sorption experiments (pH 4.5; 40 mg organic C L−1) with OM extracted from organic horizons under a Norway spruce and a European beech forest. The stabilization of OM by sorption was analyzed by comparing the CO2 mineralized during the incubation of sorbed and non-sorbed OM. The mineralization of OM was evaluated based in terms of (i) the availability of the am-Al(OH)3, thus surface OM loadings, (ii) spectral properties of OM, and (iii) the presence of phosphate as a competitor for OM. This was done by varying the solid-to-solution ratio (SSR = 0.02-1.2 g L−1) during sorption. At low SSRs, hence limited am-Al(OH)3 availability, only small portions of dissolved OM were sorbed; for OM from Oa horizons, the mineralization of the sorbed fraction exceeded that of the original dissolved OM. The likely reason is competition with phosphate for sorption sites favouring the formation of weak mineral-organic bindings and the surface accumulation of N-rich, less aromatic and less complex OM. This small fraction controlled the mineralization of sorbed OM even at higher SSRs. At higher SSRs, i.e., with am-Al(OH)3 more available, competition of phosphate decreased and aromatic compounds were sorbed selectively, which resulted in pronounced resistance of sorbed OM against decay. The combined OC mineralization of sorbed and non-sorbed OM was 12-65% less than that of the original DOM. Sorbed OM contributed only little to the overall OC mineralization. Stabilization of OC increased in direct proportion to am-Al(OH)3 availability, despite constant aromatic C (∼30%). The strong stabilization at higher mineral availability is primarily governed by strong Al-OM bonds formed under less competitive conditions. Due to these strong bonds and the resulting strong stabilization, the surface loading, a proxy for the mineral’s occupation by OM, was not a factor in the mineralization of sorbed OM over a wide range of C sorption (0.2-1.1 mg C m−2). This study demonstrates that sorption to am-Al(OH)3 results in stabilization of OM. The mineral availability as well as the inorganic solution chemistry control sorptive interactions, thereby the properties of sorbed OM, and the stability of OM against microbial decay.  相似文献   

13.
The Garson Ni–Cu–platinum group element deposit is a deformed, overturned, low Ni tenor contact-type deposit along the contact between the Sudbury Igneous Complex (SIC) and stratigraphically underlying rocks of the Huronian Supergroup in the South Range of the 1.85-Ga Sudbury structure. The ore bodies are coincident with steeply south-dipping, north-over-south D1 shear zones, which imbricated the SIC, its ore zones, and underlying Huronian rocks during mid-amphibolite facies metamorphism. The shear zones were reactivated as south-over-north, reverse shear zones during D2 at mid-greenschist facies metamorphism. Syn-D2 metamorphic titanite yields an age of 1,849?±?6 Ma, suggesting that D1 and D2 occurred immediately after crystallization of the SIC during the Penokean Orogeny. The ore bodies plunge steeply to the south parallel to colinear L1 and L2 mineral lineations, indicating that the geometry of the ore bodies are strongly controlled by D1 and D2. Sulfide mineralization consists of breccia ores, with minor disseminated sulfides hosted in norite, and syn-D2 quartz–calcite–sulfide veins. Mobilization by ductile plastic flow was the dominant mechanism of sulfide/metal mobilization during D1 and D2, with additional minor hydrothermal mobilization of Cu, Fe, and Ni by hydrothermal fluids during D2. Metamorphic pentlandite overgrows a S1 ferrotschermakite foliation in D1 deformed ore zones. Pentlandite was exsolved from recrystallized polygonal pyrrhotite grains after cessation of D1, which resulted in randomly distributed large pentlandite grains and randomly oriented pentlandite loops along the grain boundaries of polygonal pyrrhotite within the breccia ore. It also overgrows a S2 chlorite foliation in D2 shear zones. Pyrrhotite recrystallized and was flattened during D2 deformation of breccia ore along narrow shear zones. Exsolution of pentlandite loops along the grain boundaries of these flattened grains produced a pyrrhotite–pentlandite layering that is not observed in D1 deformed ore zones. The overprinting of the two foliations by pentlandite and exsolution of pentlandite along the grain boundaries of flattened pyrrhotite grains suggest that the Garson ores reverted to a metamorphic monosulfide solid solution at temperatures ranging between 550 and 600 °C during D1 and continued to deform as a monosulfide solid solution during D2.  相似文献   

14.
The sulfur cycle of Mariager Fjord was studied by following the pool of sulfide in the anoxic water and its isotopic composition during a period of 3 yr. Though most of the sulfide accumulating in the fjord was formed in the sediment, the isotopic composition of sulfide in the water was different from the isotopic composition of sulfide diffusing into the water from the sediment. The mean isotopic composition of the water column sulfide (δ34S) varied during the year between −13‰ and −21‰ with the most negative values reached during winter/early spring, while the sulfide diffusing into the water from the sediment had a mean isotope composition of −11.3‰. This annual pattern suggested that processes in the oxidative part of the sulfur cycle were responsible for the excess fractionation, and mass-balance considerations indicated that the excess fractionation of the sulfur isotopes could be accounted for by disproportionation of S0 or S2O32− in the water column, but not by water column sulfate reduction or sulfide oxidation alone. MPN counts demonstrated that a population of more than 3 × 104 cells mL−1 capable of growing by disproportionation of these two substrates was present in all depths of the fjord. The results presented in this communication demonstrate that the isotopic depletion of sulfide in anoxic systems may vary between periods of net sulfate reduction versus periods of net sulfide oxidation and indicate that disproportionation of sulfur compounds may be an important step in the sulfur cycle of euxinic basins.  相似文献   

15.
Thermodynamic calculation of distribution of dissolved aqueous species in the Red Sea geothermal brine provides a model of ore transport and deposition in good agreement with observed accumulations of base metal sulfides, anhydrite, and barite.The Red Sea brine is recirculated seawater that acquires high salinity by low-temperature interaction with Miocene evaporites and is subsequently heated to temperatures in excess of 200°C by interaction with recent rift zone intrusive rocks. At temperatures up to 250°C, NaSO?4 and MgSO04 are the dominant sulfur-bearing species. H2S forms by inorganic sulfate reduction at the higher temperatures but is maintained at a uniform concentration of about 2 ppm by the strength of the sulfate complexes.Chloride complexes solubilize metals at the higher temperatures, and thus sulfide and metals are carried together into the Atlantis II Deep. Below 150°C, the brine becomes supersaturated with respect to chalcopyrite, sphalerite, galena, and iron monosulfide due to chloride-complex dissociation. Sulfide precipitation rates, based on the rate of brine influx, are in good agreement with measured sedimentation rates. Anhydrite precipitates as crystalline fissure infillings from high-temperature inflowing brine. Barite forms from partial oxidation of sulfides at the interface between the lower hot brine and the transitional brine layer.  相似文献   

16.
金川含矿超镁铁岩侵入体侵位序列   总被引：1，自引：0，他引：1       下载免费PDF全文
金川铜镍硫化物矿床是世界第三大镍矿床,但其成岩成矿过程及侵位机制一直存在较大争论。根据金川含矿超镁铁岩岩石学特征、穿插关系、矿物成分及地球化学特征,提出了金川含矿岩体5阶段的成岩、成矿侵位序列,它们分别是:(1)超镁铁质岩浆侵位;(2)浸染状硫化物矿浆侵位;(3)网状硫化物矿浆侵位;(4)块状硫化物矿浆侵位;(5)铂钯富集体侵位。金川铜镍(铂)矿床中Ni,Cu,Pt,Pd,Rh,Ir,Ru,及Co与S呈正相关关系;当ω(S)=5%～15%时,铂族元素发生明显的分离作用,铂族金属主要富集在铂钯富集体中。铂钯富集体是硫化物矿浆经单硫化物固溶体结晶后的残余熔浆;块状矿石是单硫化物固溶体堆积而成的产物。金川铜镍硫化物矿床的侵位机制为岩墙型岩浆通道。  相似文献   

17.
The opaque minerals in eclogite xenoliths from Stockdale Kimberlite are rutile, ilmenite, and a complex polysulfide assemblage. Rutile shows exsolutions of ilmenite and spinel. Discrete ilmenite contains up to 10 wt % MgO in solid solution and is a primary mineral, but not of kimberlitic origin. Pyrrhotite containing exsolved pentlandite is the major sulfide mineral, and is usually rimmed by chalcopyrite which may display exsolution of cubanite. A veneer of monosulfide solid solution (12 wt % Ni and 5 wt % Cu) forms a rim on the chalcopyrite-pyrrhotite masses. The simple model of sulfide liquid immiscibility within a silicate melt may account for the origin of the pyrrhotite-pentlandite-chalcopyrite assemblage, but it fails to explain the occurrence within one and the same sulfide globule of a monosulfidess rim, separated from an exsolved pyrrhotite core by chalcopyrite. The monosulfidess is probably a metastable phase produced by the partial melting of a preexisting sulfide assemblage of similar bulk chemical composition to that existing at present. The melting possibly took place instantaneously when the eclogite was incorporated into the rising hot kimberlitic magma. Fast cooling during the explosive ascent of the kimberlite could have led to the quenching of the monosulfide solid solution. Rutile in the eclogite xenolith was unaffected by the heating, but secondary amphibole and biotite may have possibly formed during this event.  相似文献   

18.
Further knowledge as to the nature of the structure of a terrestrial sample of troilite, FeS [stoichiometric iron(II) sulfide] is revealed by a combination of XPS studies and dissolution studies in acid. The XPS analysis of a pristine troilite surface (the sample being cleaved under high vacuum) is compared to that of a surface polished in an inert atmosphere and a surface after reaction in deoxygenated acid. Further comparison is made with polished and acid-reacted surfaces of pyrrhotite (Fe1-xS) and pyrite (FeS2). The pristine troilite S2p spectrum comprises mainly monosulfide 161.1 eV, within the reported range of monosulfide, together with evidence of an unsatisfied monosulfide surface state arising from S-Fe bond rupture. Small, higher oxidation state sulfur contributions, including a disulfide-like state are also present, which suggest the presence of defects due to some nonstoichiometry. The dissolution studies showed that the troilite, in addition to dissolving in acid as an ionic solid to produce H2S, also exhibits some oxidation of sulfur in the surface layers. In addition, a study of the dissolution behavior of troilite under the influence of cathodic applied potential supported the existence of a proportion of the sulfur within troilite needing reduction before dissolution forming HS− or H2S can occur. A significant increase in the dissolution rate was observed with application of −105 mV (SHE), but further stepped decreases in potential to −405 mV and −705 mV resulted in a decreased rate of dissolution, a response typical of an ionic solid. The results of the studies emphasise the viewing of iron(II) sulfides as a continuum. Pyrrhotite has been reported previously to dissolve in acid both oxidatively (like pyrite) and nonoxidatively (like troilite) on the same surface. Dissolution studies using troilite, in Ar-purged acid, indicate that dissolution of this material may not be uniformly nonoxidative. XPS evidence of restructuring of the surface of troilite to pyrrhotite and the surface of pyrrhotite towards a FeS2 type structure, after exposure to Ar-purged acid, is presented.  相似文献   

19.
The chalcogenes (S, Se, Te), semimetals (As, Sb) and the metal Bi are important ligands for noble metals and form a wide range of compositionally diverse minerals with the platinum-group elements (PGE). With the exception of S, few experimental data exist to quantify the behavior of these elements in magmatic sulfide systems. Here we report experimental partition coefficients for Se, Te, As, Sb, and Bi between monosulfide solid solution (mss) and sulfide melt, determined at 950 °C at a range of sulfur fugacities (fS2) bracketed by the Fe-FeS (metal-troilite) and the Fe1−×S-Sx (mss-sulfur) equilibria. Selenium is shown to partition in mss-saturated sulfide melt as an anion replacing S2−. Arsenic changes its oxidation state with fS2 from predominantly anionic speciation at low fS2, to cationic speciation at high fS2. The elements Sb, Te, and Bi are so highly incompatible with mss that they can only be present in sulfide melt as cations and/or as neutral metallic species. The partition coefficients derived fall with increasing atomic radius of the element. They also reflect the positions of the respective elements in the Periodic Table: within a group (e.g., As, Sb, Bi) the partition coefficients fall with increasing atomic radius, and within a period the elements of the 15th group are more incompatible with mss than the neighboring elements of the 16th group.  相似文献   

20.
A four month study of a man-made lake used for hydroelectric power generation in northeastern Pennsylvania USA was conducted to investigate seasonal anoxia and the effects of sulfide species being transported downstream of the power generation equipment. Water column analyses show that the system is iron-rich compared to sulfide. Total Fe(II) concentrations in the hypolimnion are typically at least twice the total sulfide levels. In situ voltammetric analyses show that free Fe(II) as [Fe(H2O)6]2+ or free H2S as H2S/HS- are either not present or at trace levels and that iron-rich sulfide complexes are present. From the in situ data and total Fe(II) and H2S measurements, we infer that these iron-rich sulfide complexes may have stoichiometries such as Fe2SH3+ (or polymeric forms of this and other stoichiometries). These iron-rich sulfide complexes appear related to dissolution of the iron-rich FeS mineral, mackinawite, because IAP calculations on data from discrete bottle samples obtained from bottom waters are similar to the pKsp of mackinawite. Soluble iron-sulfide species are stable in the absence of O2 (both in lake waters and the pipeline) and transported several miles during power generation. However, iron-sulfide complexes can react with O2 to oxidize sulfide and can also dissociate releasing volatile H2S when the waters containing them are exposed to the atmosphere downstream of the powerplant. Sediment analyses show that the lake is rich in oxidized iron solids (both crystalline and amorphous). Fe concentrations in FeS solids are low (<5 μmole/grdry wt) and the pyrite concentration ranges from about equal to the solid FeS to 30 times the solid FeS concentration. The degree of pyritization is below 0.12 indicating that pyrite formation is limited by free sulfide, which can react with the iron-rich sulfide complexes.  相似文献   

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