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1.
We present results of incubation studies conducted at low temperatures (∼4°C) in the vicinity of a seafloor hydrothermal vent system. We reacted Fe-, S-, Cu-, and Zn-bearing minerals including pyrite, marcasite, chalcopyrite, sphalerite, elemental sulfur, and a portion of a natural chimney sulfide structure for 2 months at the Main Endeavour Segment of the Juan de Fuca Ridge in the Pacific Ocean. Our study utilizes Fluorescent In Situ Hybridizations (FISH), Scanning and Transmission Electron Microscopy (SEM, TEM), and light microscopic analysis. The surfaces of these minerals are solely colonized by Bacteria and not by Archaea. Colonization densities vary over an order of magnitude with the following sequence: elemental sulfur > chimney sulfide > marcasite > pyrite > sphalerite > chalcopyrite, and correspond well with the abiotic oxidation kinetics of these materials, excepting elemental sulfur, which is both the least reactive to oxidizing species and the most heavily colonized. Colonization densities also correspond with apparent degree of reaction (dissolution pitting + accumulation of secondary alteration products). Heavy accumulations of secondary Fe oxides on Fe-bearing minerals, most notably on the chimney sulfide, form in situ as the result of mineral dissolution and the activity of neutrophilic Fe-oxidizing bacteria. Results suggest that mineral-oxidizing bacteria play a prominent role in weathering of seafloor sulfide deposits, and that microbial utilization of mineral substrates contributes to biomass production in seafloor hydrothermal environments.  相似文献   

2.
Data on the mineral and chemical composition of samples of sulfide deposits from the Broken Spur and TAG (Mid-Atlantic Ridge) are presented. The main minerals in the Broken Spur field are marcasite, pyrrhotite, pyrite, chalcopyrite, and sphalerite; in sample from TAG: chalcopyrite, pyrite, and marcasite. It has been established that these sulfide minerals of Fe, Cu, and Zn are natural ion exchangers and belong to the class of adsorbents. Exchange capacity of sulfide minerals in terms of heavy metal cations (Ni2+, Co2+, Cd2+, and Pb2+) is 0.022–0.32 mg-equiv/g. In the exchange reaction products, the mineral composition of sulfide deposits is retained, and new phases do not appear. It is suggested that the adsorbed heavy metal cations populate either vacant cationic or interstitial defect sites in the structures of sulfide minerals. Bond strength of the adsorbed heavy metal cations with the main structural elements of minerals is low, which is confirmed by their high extraction in an acid medium. The results of adsorption-desorption experiments indicate two forms of heavy metal cations in sulfide minerals: adsorbed (basic) and chemically bound.  相似文献   

3.
The net result of acid-generating and-neutralizing reactions within mining wastes is termed acid rock drainage (ARD). The oxidation of sulfide minerals is the major contributor to acid generation. Dissolution and alteration of various minerals can contribute to the neutralization of acid. Definitions of alkalinity, acidity, and buffer capacity are reviewed, and a detailed discussion of the dissolution and neutralizing capacity of carbonate and silicate minerals related to equilibium conditions, dissolution mechanism, and kinetics is provided. Factors that determine neutralization rate by carbonate and silicate minerals include: pH, PCO 2, equilibrium conditions, temperature, mineral composition and structure, redox conditions, and the presence of foreign ions. Similar factors affect sulfide oxidation. Comparison of rates shows sulfides react fastest, followed by carbonates and silicates. The differences in the reaction mechanisms and kinetics of neutralization have important implications in the prediction, control, and regulation of ARD. Current static and kinetic prediction methods upon which mine permitting, ARD control, and mine closure plans are based do not consider sample mineralogy or the kinetics of the acid-generating and-neutralizing reactions. Erroneous test interpretations and predictions can result. The importance of considering mineralogy for site-specific interpretation is highlighted. Uncertainty in prediction leads to difficulties for the mine operator in developing satisfactory and cost-effective control and remediation measures. Thus, the application of regulations and guidelines for waste management planning need to beflexible.  相似文献   

4.
The extraction of mineral resources requires access through underground workings, or open pit operations, or through drillholes for solution mining. Additionally, mineral processing can generate large quantities of waste, including mill tailings, waste rock and refinery wastes, heap leach pads, and slag. Thus, through mining and mineral processing activities, large surface areas of sulfide minerals can be exposed to oxygen, water, and microbes, resulting in accelerated oxidation of sulfide and other minerals and the potential for the generation of low-quality drainage. The oxidation of sulfide minerals in mine wastes is accelerated by microbial catalysis of the oxidation of aqueous ferrous iron and sulfide. These reactions, particularly when combined with evaporation, can lead to extremely acidic drainage and very high concentrations of dissolved constituents. Although acid mine drainage is the most prevalent and damaging environmental concern associated with mining activities, generation of saline, basic and neutral drainage containing elevated concentrations of dissolved metals, non-metals, and metalloids has recently been recognized as a potential environmental concern. Acid neutralization reactions through the dissolution of carbonate, hydroxide, and silicate minerals and formation of secondary aluminum and ferric hydroxide phases can moderate the effects of acid generation and enhance the formation of secondary hydrated iron and aluminum minerals which may lessen the concentration of dissolved metals. Numerical models provide powerful tools for assessing impacts of these reactions on water quality.  相似文献   

5.
Hydrochemical data were gathered throughout the last 12 years from 57 sampling stations in the drainage basin of the Sarcheshmeh copper mine, Kerman Province, Iran. The mean values of these data for each sampling station were used to evaluate water quality and to determine processes that control water chemistry. Principal component analyses specified the oxidation of sulfide minerals, dissolution of carbonate and sulfate minerals and weathering of silicate minerals as the principal processes responsible for the chemical composition of water in the study area. Q-mode cluster analysis revealed three main water groups. The first group had a Ca-HCO3–SO4 composition whereas the second and third groups had Ca–SO4 and Ca–Mg–SO4 composition, respectively. The results of this study clearly indicated the role of sulfide minerals oxidation and the buffering processes in the geochemical evolution of water in the Sarcheshmeh area. Due to these processes, extensive changes occurred in the chemical composition of water by passage through the mining area or waste and low-grade dumps, so that the fresh water of the peripheral area of the pit evolved to an acid water rich in sulfate and heavy metals at the outlet of the pit and in the seepages of waste and low-grade dumps.  相似文献   

6.
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7.
Sulfide sulfur in mid-oceanic ridge hydrothermal vents is derived from leaching of basaltic-sulfide and seawater-derived sulfate that is reduced during high temperature water rock interaction. Conventional sulfur isotope studies, however, are inconclusive about the mass-balance between the two sources because 34S/32S ratios of vent fluid H2S and chimney sulfide minerals may reflect not only the mixing ratio but also isotope exchange between sulfate and sulfide. Here, we show that high-precision analysis of S-33 can provide a unique constraint because isotope mixing and isotope exchange result in different Δ33S (≡δ33S-0.515 δ34S) values of up to 0.04‰ even if δ34S values are identical. Detection of such small Δ33S differences is technically feasible by using the SF6 dual-inlet mass-spectrometry protocol that has been improved to achieve a precision as good as 0.006‰ (2σ).Sulfide minerals (marcasite, pyrite, chalcopyrite, and sphalerite) and vent H2S collected from four active seafloor hydrothermal vent sites, East Pacific Rise (EPR) 9-10°N, 13°N, and 21°S and Mid-Atlantic Ridge (MAR) 37°N yield Δ33S values ranging from −0.002 to 0.033 and δ34S from −0.5‰ to 5.3‰. The combined δ34S and Δ33S systematics reveal that 73 to 89% of vent sulfides are derived from leaching from basaltic sulfide and only 11 to 27% from seawater-derived sulfate. Pyrite from EPR 13°N and marcasite from MAR 37°N are in isotope disequilibrium not only in δ34S but also in Δ33S with respect to associated sphalerite and chalcopyrite, suggesting non-equilibrium sulfur isotope exchange between seawater sulfate and sulfide during pyrite precipitation. Seafloor hydrothermal vent sulfides are characterized by low Δ33S values compared with biogenic sulfides, suggesting little or no contribution of sulfide from microbial sulfate reduction into hydrothermal sulfides at sediment-free mid-oceanic ridge systems. We conclude that 33S is an effective new tracer for interplay among seawater, oceanic crust and microbes in subseafloor hydrothermal sulfur cycles.  相似文献   

8.
Tailings generated during processing of sulfide ores represent a substantial risk to water resources. The oxidation of sulfide minerals within tailings deposits can generate low-quality water containing elevated concentrations of SO4, Fe, and associated metal(loid)s. Acid generated during the oxidation of pyrite [FeS2], pyrrhotite [Fe(1−x)S] and other sulfide minerals is neutralized to varying degrees by the dissolution of carbonate, (oxy)hydroxide, and silicate minerals. The extent of acid neutralization and, therefore, pore-water pH is a principal control on the mobility of sulfide-oxidation products within tailings deposits. Metals including Fe(III), Cu, Zn, and Ni often occur at high concentrations and exhibit greater mobility at low pH characteristic of acid mine drainage (AMD). In contrast, (hydr)oxyanion-forming elements including As, Sb, Se, and Mo commonly exhibit greater mobility at circumneutral pH associated with neutral mine drainage (NMD). These differences in mobility largely result from the pH-dependence of mineral precipitation–dissolution and sorption–desorption reactions. Cemented layers of secondary (oxy)hydroxide and (hydroxy)sulfate minerals, referred to as hardpans, may promote attenuation of sulfide-mineral oxidation products within and below the oxidation zone. Hardpans may also limit oxygen ingress and pore-water migration within sulfide tailings deposits. Reduction–oxidation (redox) processes are another important control on metal(loid) mobility within sulfide tailings deposits. Reductive dissolution or transformation of secondary (oxy)hydroxide phases can enhance Fe, Mn, and As mobility within sulfide tailings. Production of H2S via microbial sulfate reduction may promote attenuation of sulfide-oxidation products, including Fe, Zn, Ni, and Tl, via metal-sulfide precipitation. Understanding the dynamics of these interrelated geochemical and mineralogical processes is critical for anticipating and managing water quality associated with sulfide mine tailings.  相似文献   

9.
Subaerial exposure and oxidation of organic carbon (Corg)-rich rocks is believed to be a key mechanism for the recycling of buried C and S back to Earth's surface. Importantly, processes coupled to microbial Corg oxidation are expected to shift new biomass δ13Corg composition towards more negative values relative to source. However, there is scarcity of information directly relating rock chemistry to oxidative weathering and shifting δ13Corg at the rock-atmosphere interface. This is particularly pertinent to the sulfidic, Corg-rich alum shale units of the Baltoscandian Basin believed to constitute a strong source of metal contaminants to the natural environment, following subaerial exposure and weathering. Consistent with independent support, we show that atmospheric oxidation of the sulfidic, Corg-rich alum shale sequence of the Cambrian-Devonian Baltoscandian Basin induces intense acid rock drainage at the expense of progressive oxidation of Fe sulfides. Sulfide oxidation takes priority over microbial organic matter decomposition, enabling quantitative massive erosion of Corg without producing a δ13C shift between acid rock drainage precipitates and shale. Moreover, 13C enrichment in inorganic carbon of precipitates does not support microbial Corg oxidation as the predominant mechanism of rock weathering upon exposure. Instead, a Δ34S = δ34Sshale − δ34Sprecipitates ≈ 0, accompanied by elevated S levels and the ubiquitous deposition of acid rock drainage sulfate minerals in deposited efflorescent precipitates relative to shales, provide strong evidence for quantitative mass oxidation of shale sulfide minerals as the source of acidity for chemical weathering. Slight δ15N depletion in the new surface precipitates relative to shale, coincides with dramatic loss of N from shales. Collectively, the results point to pyrite oxidation as a major driver of alum black shale weathering at the rock-atmosphere interface, indicating that quantitative mass release of Corg, N, S, and key metals to the environment is a response to intense sulfide oxidation. Consequently, large-scale acidic weathering of the sulfide-rich alum shale units is suggested to influence the fate and redistribution of the isotopes of C, N, and S from shale to the immediate environment.  相似文献   

10.
Research on hydrogeochemistry for mineral exploration for inland Australia includes development of weathering models and extensive mine-scale and regional groundwater data. Mineral saturation indices for groundwater, activity–activity plots and reaction modelling simulate weathering of volcanic-hosted massive sulfide (VHMS) deposits in deeply weathered environments. At 10 m or more below surface, dissolved O2 is very low and other solutes such as sulfate, carbonate and nitrate are more likely oxidants. Modelling indicates that these processes differ from oxic weathering of highly eroded terrains, and provide the framework to develop robust hydrogeochemical exploration procedures in covered terrains. Sulfide weathering potentially occurs in two or more phases that effect surrounding groundwaters in differing manners. Deeper oxidative alteration of sulfides (e.g. bornite to chalcopyrite), occurring tens to hundreds of metres below surface, uses sulfate and carbonate as oxidants, causing neutral to alkaline conditions. In this zone, only pyritic massive sulfides potentially generate acidic conditions. Thus, deep sulfide-rich rocks are indicated by sulfate-depleted groundwater. Closer to the surface, sulfides are oxidised to soluble sulfates by dissolved nitrate, with much less acid production than if dissolved oxygen was the main oxidant. Thus, in shallow groundwater, sulfides are indicated by sulfate enrichment and nitrate depletion. Elements are released from sulfides and wall rocks by acid or alkaline conditions. The derived FeS (pH–Eh + Fe + Mn) and AcidS (Li + Mo + Ba + Al) indices distinguish sulfide systems through tens of metres of cover. VHMS systems are distinguished from other non-economic sulfide deposits where there is little transported cover, using various dissolved elements, including Zn, Pb and Cu. Elsewhere, ‘patchiness’ and limited aerial extent of metal signals are due to adsorption effects, that intensify with depth. Other elements such as Mn and Co have lesser diminution effects, but are less selective indicators for VHMS. There is exploration potential for elements such as Pt or Ag. These varying sulfide indicators have moderate utility, even for large-scale (～5 km spacing) sampling. Results indicate that hydrogeochemistry can add value to greenfields exploration for VHMS ore deposits in deeply weathered terrains. It is also moderately successful at indicating the presence of sulfide-rich systems (whether magmatic or hydrothermal) under >100 m cover, thus providing a rapid and cost-effective regional prospectivity tool for deeply buried terrains. Such mineral exploration tools will encourage exploration investment for more difficult regions of Australia and in other deeply weathered regions of the world.  相似文献   

11.
郭海棠 《地质与勘探》2014,50(3):486-493
穆斯堡尔谱对确定铁离子占位、核外环境及氧化态方面有着独特的优势。在红山铜金矿床氧化带硫酸盐矿物的XRD、TA、湿法化学分析和红外光谱测试的基础上,测定了板铁矾、针绿矾等8种硫酸盐矿物的室温57Fe穆斯堡尔谱,并根据常温下硫酸盐矿物穆斯堡尔谱参数和其晶体结构中Fe3+和Fe2+的占据位置对其谱峰进行了指派。结果表明本矿床氧化带硫酸盐矿物的穆斯堡尔谱的同质异能位移较小、四级矩分裂值分布范围较大、无磁超精细分裂等特征,且硫酸盐矿物结构中存在着共价键。通过与青海锡铁山铅锌矿氧化带硫酸盐矿物的穆斯堡尔谱相比较,两者在近地表风化及氧化过程中所处的物理化学条件基本相同,酸性和氧化性的环境为硫酸盐矿物的产生和保存提供了良好条件,但红山矿床更为干旱少雨,导致两者硫酸盐的穆斯堡尔谱参数略有不同。  相似文献   

12.
Elevated As concentrations have been measured in wells in the St. Peter Sandstone aquifer of eastern Wisconsin, USA. The primary source is As-bearing sulfide minerals (pyrite and marcasite) within the aquifer. There is concern that well disinfection by chlorination may facilitate As release to groundwater by increasing the rate and extent of sulfide oxidation. The objective of this study was to examine the abiotic processes that mobilize As from the aquifer solids during controlled exposure to chlorinated solutions. Thin sections made from sulfidic aquifer material were characterized by quantitative electron probe micro-analysis before and after 24 h exposure to solutions of different Cl2 concentrations. Batch experiments using crushed aquifer solids were also conducted to examine changes in solution chemistry over 24 h. Results of the combined experiments indicate that Cl2 addition affects As release and uptake in two ways. First, Cl2 increases oxidation of sulfide minerals, releasing more As from the mineral structure. Chlorine addition also increases the rate of Fe(II) oxidation and subsequent hydrous ferric oxide (HFO) precipitation, allowing for increased uptake of As onto the mineral surface. Although HFOs can act as sinks for As, they can release As if biogeochemical conditions (e.g. redox, pH) change. These results have implications not only for disinfection of drinking water wells in the study area, but also suggest that introduction of oxidants may adversely affect water quality during aquifer storage and recovery programs in aquifers containing As-bearing minerals.  相似文献   

13.
The correlation between sulfate concentrations in Finnish headwater streams and atmospheric sulfate deposition has been studied by using data from the streamwater chemistry in August–September 1990 and computed S deposition from the anthropogenic emissions. The sulfate concentrations and acidity in water are interpolated and smoothed into a deposition model grid. These data are compared with geological and pedogeochemical (glacial till) background information. The areas where the streamwater SO4 concentrations are mainly controlled by either anthropogenic S deposition or sulfur in till is estimated by applying the fuzzy Gustafsson-Kessel algorithm, which provides a soft clustering suitable for overlapping control factors. Residual areas can be well explained by the SO4-rich Littorina clay deposits. The higher overall background SO4 concentrations in streams in south Finland compared with central and northern Finland are an indisputable consequence of the heavier S deposition load in the south. However, anthropogenic sulfur deposition has a clear correlation with the sulfates in streamwaters only in northeastern Lapland impacted by the large industrial emissions in the Kola Peninsula. The secondary sulfide and sulfate minerals of marine Littorina sediments are dominating sources in the broad coastal belts, as are the primary sulfide minerals locally in the Pori-Vammala area, at the eastern end of the main sulfide ore belt between Lake Ladoga and the Gulf of Bothnia, in the Outokumpu area, and in the Peräpohja and central Lapland schist belts. Consequently, in addition to the anthropogenic deposition, there are natural sources of sulfur which cause acidity of streamwaters.  相似文献   

14.
The generation of Reactive Oxygen Species (ROS), H2O2 and OH, has been observed from sulfide mineral containing particles in acidic solutions. The implications of this phenomenon, as a potential microbial stress-causing effect, have been studied previously with respect to thermophilic bioleaching performance in the presence of finely milled pyrite and chalcopyrite concentrates. In this study, the effect of sulfide mineralogy on ROS generation in the absence of microbes under physicochemical conditions typical for the bioleach environment was investigated. The mineralogical and elemental composition of eleven different samples containing sulfide mineral was obtained. These Au, Cu and other base metal-containing sulfide mineral concentrates as well as a milled whole ore of low Cu grade were tested for ROS generation. The whole ore sample and two refractory Au concentrates containing approximately 50% pyrite, generated significantly less ROS compared to the base metal-containing concentrates when compared on a constant surface area loading basis. Sulfide mineral-related variables were correlated with ROS generation. A significant difference was observed between FeS2 and CuFeS2 grades separately, whereas a combined measure of both minerals present in samples showed a consistently strong correlation to ROS generation. The Cu grade, total Cu-containing sulfides and the chalcopyrite content of Cu-containing samples correlated well with ROS generation. However, a common deterministic variable with a strong association to increased ROS generation was not found. A sub-set of samples were subjected to QEMSCAN® for textural analysis. Results suggested that a decrease in sulfide mineral liberation, caused by gangue silicate mineral occlusion to solution, resulted in decreased reactivity as shown in one of the Au-containing samples. Well-liberated chalcopyrite and pyrite phases corresponded to increased reactivity of samples. Pyrite, which was present in all of the reactive samples, was shown to be associated with other sulfide minerals, implicating its importance in galvanic interactions. Micro-analysis of chalcopyrite and pyrite phases from highly reactive samples showed an abundance of particles with extensive cracking and the possible presence of secondary transformation phases (szomolnokite). These results suggest that sulfide mineralogy, liberation and extent of physical processing affect sulfide mineral concentrate reactivity in acidic solutions.  相似文献   

15.
Here we report the occurrence of some uncommon mineral assemblages including pääkönenite, aurostibite, native arsenic, native antimony, and native bismuth found in the Baogutu gold deposit in the western Junggar, Xinjiang, NW China. The mineralization could be generally subdivided into two types: the gold-bearing quartz-vein type mineralization and disseminated mineralization in the wall rocks. The sulfide minerals in gold lodes commonly include pyrite, arsenopyrite, marcasite, and stibnite. However, the L7 lode in No. 4 orebody and the L1 lode in No. 11 orebody of the Baogutu gold deposit are quite different in terms of their mineral assemblages. The L7 lode contains native arsenic–quartz veins in shallow levels and stibnite–quartz veins at depth. Gold-bearing minerals (electrum, native gold, and rarely aurostibite) mainly coexist with pääkönenite, stibnite, native arsenic, and native antimony. The crystallization of As- and Sb-bearing minerals was likely to have consumed H2S from the hydrothermal fluid, which probably triggered the precipitation of native gold. The L1 lode consists of several discontinuous sulfide-dominated lensoid orebodies. The massive sulfide ores that produced most of the gold resource are characterized by an intimate association between native bismuth and native gold mineralization.  相似文献   

16.
The Las Cruces VMS deposit is located at the eastern corner of the Iberian Pyrite Belt (SW Spain) and is overlain by the Neogene–Quaternary sediments of the Guadalquivir foreland Basin. The deposit is currently exploited from an open pit by Cobre Las Cruces S.A., being the supergene Cu-enriched zone the present mined resource. The Las Cruces orebody is composed of a polymetallic massive sulfide orebody, a Cu-rich stockwork and an overlying supergene profile that includes a Cu-rich secondary ore (initial reserves of 17.6 Mt @ 6.2% Cu) and a gossan cap (initial reserves of 3.6 Mt @ 3.3% Pb, 2.5 g/t Au, and 56.3 g/t Ag).The mineralogy of the Las Cruces weathering profile has been studied in this work. Textural relationships, mineral chemistry, deposition order of the minerals and genesis of the Las Cruces gossan are described and discussed in detail. A complex mineral assemblage composed by the following minerals has been determined: carbonates such as siderite, calcite and cerussite; Fe-sulfides including pyrite, marcasite, greigite and pyrrhotite; Pb–Sb sulfides and sulfosalts like galena, stibnite, fulöppite, plagionite, boulangerite, plumosite, and the jordanite–geocronite series, Ag–Hg–Sb sulfides and sulfosalts including miargyrite, pyrargyrite, sternbergite, acanthite, freibergite, cinnabar, Ag–Au–Hg amalgams; and Bi–Pb–Bi sulfides and sulfosalts such as bismuthinite, galenobismutite, others unidentified Bi–Pb-sulfosalts, native Bi and unidentified Fe–Pb–Sb-sulfosalts. Remains of the former oxidized assemblage appear as relicts comprised of hematite and goethite.Combining paragenetic information, textures and mineral chemistry it has been possible to derive a sequence of events for the Las Cruces gossan generation and subsequent evolution. In that sense, the small amount of Fe-oxyhydroxides and their relict textures replaced by carbonates and sulfides suggest that the gossan was generated under changing physico-chemical conditions. It is proposed that the Las Cruces current gossan represents the modified residue of a former gossan mineralization where prolonged weathering led to dissolution and leaching out of highly mobile elements and oxidation of the primary sulfides. Later, the gossan was subject to seawater-gossan interaction and then buried beneath a carbonated-rich cover. The basinal fluids-gossan interaction and the equilibration of fluids with the carbonated sediments brought to the carbonatization and sulfidation of the gossan, and thus to the generation of Fe-carbonates and Pb–Sb-sulfides.The Las Cruces mineral system likely represents a new category within the weathering class of ore deposits.  相似文献   

17.
The Irece Basin is a relatively small late Proterozoic basin within the São Francisco craton of northeast-central Brazil. Stratabound Zn-Pb-Ag sulfide and phosphate-rich units occur within a 50-m-thick tidal-flat sequence of dolomitic limestone and cherty dolostone within the lower Salitre Formation of the Una Group. Phosphate is concentrated in stromatolitic structures; metallic mineralization is represented by stratiform masses and disseminations of sulfide minerals in a tidal-flat sequence that has relict evaporitic structures.

Zn-Pb-Ag sulfide concentrations in the Irece area are associated with parallel laminated, silty dolostone with shallow-water sedimentary structures, including laminar stromatolites, mud cracks, tepee structures, collapse breccias, length-slow quartz nodules, and pseudomorphs after evaporitic sulfates. Sulfide minerals include pyrite, sphalerite, galena, marcasite, jordanite, tetrahedrite, and covellite, in order of decreasing abundance. Nodular and bladed sulfide forms are pseudomorphous after evaporitic sulfate minerals. Replacement textures, such as corroded grain boundaries between sulfide minerals, are common. Sulfur-isotope analysis indicates relatively uniform heavy δ34S values. Barite has a δ34S range from +25 to +31‰, CDT. Pyrite, sphalerite, galena, and jordanite-representative of a variety of textural types-have a δ34S range of +19 to + 23‰; δ34S values for Irece barite probably represent original late Proterozoic sea-water sulfate values. The consistently heavy δ34S values of the Irece sulfides likely are the result of thermochemical reduction of a limited evaporitic sulfate source by organic matter that is abundant in the Salitre carbonates.

Major Zn-Pb-Ag concentrations appear to be an overprint on the earlier iron sulfide-rich zone. Limited fluid-inclusion data suggest precipitation in the range of 140 to 200°C from formation waters with salinities ranging from 3 to 12 wt%. Deep fluid circulation may have been promoted by reactivation of basement faults originally related to the Irece Basin's development. Petrographic and fluid-inclusion data suggest that sulfide mineralization may have occurred within a mixing zone of metal-bearing, high-temperature basinal brines with meteoric water. Metallic mineralization scavenged sulfur from pre-existing sulfides or from direct reduction of evaporitic sulfate minerals.

The metal and phosphate concentrations in the Irece Basin possess some similiar geologic characteristics that result from a common host-rock depositional environment. However, existing information indicates that the two deposit types are not directly related genetically, although the origin of both is related to the organic-rich nature of the host sequence.  相似文献   

18.
We have evaluated the potential application of sulfur gas analysis to exploration for buried sulfide mineral deposits by: (1) calculating by use of equilibrium thermodynamics, the relative abundances of gases that should be given off by decomposing sulfide minerals; and (2) determining experimentally the abundances of gases that are actually given off. The calculations indicate that the gases that should be given off by decomposing sulfide minerals are (in order of decreasing abundance) H2S, COS, CS2, CH3SH, (CH3)2S2 or SO2 or S2 (depending on Eh and pH). In contrast, our experiments show that decomposing sulfide minerals evolve only CS2 and COS, in order of decreasing abundance. Pyrite produces the largest amounts of sulfur gas. Moist (rather than saturated) and non-sterile (rather than sterile) conditions enhance gas generation from pyrite, although no large difference appeared between sterile and non-sterile experiments for other sulfide minerals. These experiments indicate that the sulfur gases CS2 and COS could be useful indicators of buried metal sulfide deposits.  相似文献   

19.
Schwertmannite (ideal formula: Fe8O8(OH)6SO4) is typically found as a secondary iron mineral in pyrite oxidizing environments. In this study, geochemical constraints upon its formation are established and its role in the geochemical cycling of iron between reducing and oxidizing conditions are discussed. The composition of surface waters was analyzed and sediments characterized by X-ray diffraction, FTIR spectroscopy and determination of the Fe:S ratio in the oxalate extractable fraction from 18 acidic mining lakes. The lakes are exposed to a permanent supply of pyritegenous ferrous iron from adjacent ground water. In 3 of the lakes the suspended matter was fractionated using ultra filtration and analyzed with respect to their mineral composition. In addition, stability experiments with synthetic schwertmannite were performed. The examined lake surface waters were O2-saturated and have sulfate concentrations (10.3 ± 5.5 mM) and pH values (3.0 ± 0.6) that are characteristic for the stability window of schwertmannite. Geochemical modeling implied that i) the waters were saturated with respect to schwertmannite, which controlled the activity of Fe3+ and sulfate, and ii) a redox equilibrium exists between Fe2+ and schwertmannite. In the uppermost sediment layers (1 to 5 cm depth), schwertmannite was detectable in 16 lakes—in 5 of them by all three methods. FTIR spectroscopy also proved its occurrence in the colloidal fraction (1-10 kDa) in all of the 3 investigated lake surface waters. The stability of synthetic schwertmannite was examined as a function of pH (2-7) by a 1-yr experiment. The transformation rate into goethite increased with increasing pH. Our study suggests that schwertmannite is the first mineral formed after oxidation and hydrolysis of a slightly acidic (pH 5-6), Fe(II)-SO4 solution, a process that directly affects the pH of the receiving water. Its occurrence is transient and restricted to environments, such as acidic mining lakes, where the coordination chemistry of Fe3+ is controlled by the competition between sulfate and hydroxy ions (i.e. mildly acidic).  相似文献   

20.
A thin film of marcasite, FeS2, was synthesized under vacuum and its structure and reactivity under oxidizing conditions was investigated by means of diffraction and surface analytical techniques, respectively. Synthesis of the film was carried out by codepositing Fe and S2 onto a Ta support. The thickness of the film could be varied from approximately 10 Å to 1 μm. High-resolution S 2p synchrotron-based photoemission showed S22−, with undetectable amounts of S2− impurity that is typically present on natural sample surfaces. X-ray diffraction of the micron-thick films showed that the film crystallized in the marcasite phase of FeS2. Atomic force microscopy indicated that the thin film had a nanometer-scale roughness suggesting the film contained defects such as steps and kinks. X-ray photoelectron spectroscopy studies found the thin marcasite film to be more reactive than natural pyrite (the most ubiquitous FeS2 dimorph) after exposure to a gaseous O2/H2O environment on the basis of the amount of sulfate formation. Likely the oxidation of marcasite was dominated by its short-range order (e.g., presence of steps), because the density of nonstoichiometric defect sites (e.g., S2−) was low as assessed by photoelectron spectroscopy.  相似文献   

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