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1.
The aim of the study was to determine whether the application of phosphate compounds (phosphorite rock, phosphate fertilizer) to polyminerallic waste rocks can inhibit sulfide oxidation and metal mobility (Cu, Pb, Zn, Cd, Ni, Mn, Mg). Waste rocks comprised sulfidic carbonaceous shales and were sourced from the Century Pb-Zn mine, NW Queensland, Australia. The acid producing, Pb-Zn rich rocks consisted of major quartz, muscovite/illite, dolomite, siderite and kaolinite as well as smaller amounts of sulfide minerals (e.g. galena, sphalerite, pyrite). Laboratory leach experiments were conducted on finely granulated phosphate-treated waste rocks (>2 to <30 mm) over 13 weeks, whereas phosphate amendment of coarsely granulated waste rocks (sand to boulder size) was investigated using heap leach piles at the mine site over an 11 months period. Results of the laboratory experiments demonstrate that the treatment of finely granulated waste rocks with phosphorite rock produced leachates with near-neutral pH values due to calcite dissolution. This in turn did not allow the leaching of apatite, formation of secondary phosphate phases and phosphate stabilization to occur. Metal mobility in these amended wastes was restricted by the dissolution of calcite and the resultant near-neutral pH conditions. By contrast, the application of the water-soluble phosphate fertilizer MKP (KH2PO4) to polyminerallic sulfidic waste rocks during the short-term laboratory experiments led to the formation of phosphate coatings and precipitates and inhibited acid and metal release (Cd, Mn, Ni, Pb, Zn). At least in the short term, the application of phosphate fertilizers proved to be an effective method. However, results of the long-term field trials demonstrate that coarsely granulated waste rocks were not coated by secondary phosphate phases and that amendment by phosphorite rock or superphosphate fertilizer did not improve leachate quality compared to the unamended waste. Thus, phosphate stabilization appears ineffective in suppressing oxidation of sulfides in coarsely granulated mine wastes.  相似文献   

2.
《Chemical Geology》2006,225(3-4):278-290
The thermodynamic mixing properties of As into pyrite and marcasite have been investigated using first-principles and Monte Carlo calculations in order to understand the incorporation of this important metalloid into solid solution. Using quantum-mechanical methods to account for spin and electron transfer processes typical of sulfide minerals, the total energies of different As–S configurations were calculated at the atomic scale, and the resulting As–S interactions were incorporated into Monte Carlo simulations. Enthalpies, configurational entropies and Gibbs free energies of mixing show that two-phase mixtures of FeS2 (pyrite or marcasite) and FeAsS (arsenopyrite) are energetically more favorable than the solid solution Fe(S,As)2 (arsenian pyrite or marcasite) for a wide range of geologically relevant temperatures. Although miscibility gaps dominate both solid solution series, the solubility of As is favored for XAs < 0.05 in iron disulfides. Consequently, pyrite and marcasite can host up to ∼6 wt.% of As in solid solution before unmixing into (pyrite or marcasite) + arsenopyrite. This finding is in agreement with previously published HRTEM observations of As-rich pyrites (> 6 wt.% As) that document the presence of randomly distributed domains of pyrite + arsenopyrite at the nanoscale. According to the calculations, stable and metastable varieties of arsenian pyrite and marcasite are predicted to occur at low (XAs < 0.05) and high (XAs > 0.05) As bulk compositions, respectively.  相似文献   

3.
The Pb–Zn–Ag quartz vein from Terramonte cuts the Neoproterozoic–Cambrian schist–greywacke complex. This orebody was partially exploited. The paragenetic sequence consists of four stages containing quartz accompanied mainly by arsenopyrite and pyrite in the first stage, sphalerite in the second stage, galena showing many inclusions of several sulphosalts in the third stage and carbonates in the fourth remobilization stage. Several sulphide and sulphosalt grains are oscillatory zoned. The chemical distinction between lighter and darker zones in backscattered images of arsenopyrite, pyrite, sphalerite and freibergite is due to substitutions in the mineral lattices. But the distinction between these zones in semseyite is due to a higher Pb content and a lower Sb content in the lighter zone than in the darker zone and the metal and metalloid are the main constituents in the solid solution, but are not correlated. The Sb, Ag and Bi substitute for Pb in galena, but did not cause any zoning. Ore deposition was possible due to mixing of a hypersaline fluid with up to 26 wt.% NaCl equivalent (and occasionally with CaCl2 up to 17 wt.%), which carried the metallic content of the fluid, with an extremely low salinity fluid of presumed meteoric origin that percolated down into the basement. The metals could have been leached from a mixture of mainly metasediments and also previous Sb–Au deposits by fluids that acquire high salinity in one of two probable ways: leaching of salt beds or following seawater evaporation. The entire mineralizing event probably occurred at a relatively low temperature, possibly between 120 and 230 °C. Remobilization of Pb, Zn, Ag, As, Sb and Cu will be due to the tectonic evolution of the opening of the Atlantic Ocean. This vein is probably of Alpine age.  相似文献   

4.
《Applied Geochemistry》2005,20(3):639-659
The oxidation of sulfide minerals from mine wastes results in the release of oxidation products to groundwater and surface water. The abandoned high-sulfide Camp tailings impoundment at Sherridon, Manitoba, wherein the tailings have undergone oxidation for more than 70 a, was investigated by hydrogeological, geochemical, and mineralogical techniques. Mineralogical analysis indicates that the unoxidized tailings contain nearly equal proportions of pyrite and pyrrhotite, which make up to 60 wt% of the total tailings, and which are accompanied by minor amounts of chalcopyrite and sphalerite, and minute amounts of galena and arsenopyrite. Extensive oxidation in the upper 50 cm of the tailings has resulted in extremely high concentrations of dissolved SO4 and metals and As in the tailings pore water (pH < 1, 129,000 mg L−1 Fe, 280,000 mg L−1 SO4, 55,000 mg L−1 Zn, 7200 mg L−1 Al, 1600 mg L−1 Cu, 260 mg L−1 Mn, 110 mg L−1 Co, 97 mg L−1 Cd, 40 mg L−1 As, 15 mg L−1 Ni, 8 mg L−1 Pb, and 3 mg L−1 Cr). The acid released from sulfide oxidation has been extensive enough to deplete carbonate minerals to 6 m depth and to partly deplete Al-silicate minerals to a 1 m depth. Below 1 m, sulfide oxidation has resulted in the formation of a continuous hardpan layer that is >1 m thick. Geochemical modeling and mineralogical analysis indicate that the hardpan layer consists of secondary melanterite, rozenite, gypsum, jarosite, and goethite. The minerals indicated mainly control the dissolved concentrations of SO4, Fe, Ca and K. The highest concentrations of dissolved metals are observed directly above and within the massive hardpan layer. Near the water table at a depth of 4 m, most metals and SO4 sharply decline in concentration. Although dissolved concentrations of metals and SO4 decrease below the water table, these concentrations remain elevated throughout the tailings, with up to 60,600 mg L−1 Fe and 91,600 mg L−1 SO4 observed in the deeper groundwater. During precipitation events, surface seeps develop along the flanks of the impoundment and discharge pore water with a geochemical composition that is similar to the composition of water directly above the hardpan. These results suggest that shallow lateral flow of water from a transient perched water table is resulting in higher contaminant loadings than would be predicted if it were assumed that discharge is derived solely from the deeper primary water table. The abundance of residual sulfide minerals, the depletion of aluminosilicate minerals in the upper meter of the tailings and the presence of a significant mass of residual sulfide minerals in this zone after 70 a of oxidation suggest that sulfide oxidation will continue to release acid, metals, and SO4 to the environment for decades to centuries.  相似文献   

5.
《Applied Geochemistry》2007,22(4):821-836
High-resolution sampling (every 3 h) of SPM was performed during a major flood event in a heterogeneous, medium scale watershed of the Garonne-Gironde fluvial-estuarine system (the Lot River; A = 10,700 km2; Q = 151 m3/s). Particulate metal and metalloid (Cd, Zn, Pb, Co, Cr, Ni, Mo, V, U, As, Sb, Th) concentrations were compared with monthly data of the same site (Temple site) obtained during 1999–2002. During the flood event, suspended particulate matter (SPM) concentrations closely followed river discharge with a maximum value (1530 mg/L) coinciding with the discharge peak (2970 m3/s). Trace metal/metalloid concentrations showed significant temporal variations and very contrasted responses. Particulate concentrations were similar to baseline values at the beginning of the flood and mostly increased during the event, showing anticlockwise and complex shape hystereses. Comparison of SPM yield (440,000 t) and particulate metal/metalloid fluxes during the flood with annual fluxes (1999–2002) highlights the great importance of major flood events in fluvial transport. Adequate sampling frequency during floods is necessary for reliable annual flux estimates and provides geochemical signals that may greatly improve our understanding of fluvial transport processes. The scenario of SPM and metal and metalloid transport during the flood are reconstructed by combining variations of Zn, Cd and Sb concentrations, concentration ratios (e.g. Zn/Cd, As/Th, Cd/Th) and hysteresis loops. Changes in SPM and metal/metalloid transport during distinct key stages of the flood were attributed to successive dominance of different water masses transporting material from different sources (e.g. industrial point source, bed sediment from reservoirs, plain erosion). Flood management (dam flushing) clearly enhanced the remobilization of up to 30-a old polluted sediment from reservoir lakes. Sediment remobilization accounted for ∼185,000 t of SPM (i.e. 42% of the total SPM fluxes during the flood) and strongly contributed to particulate metal/metalloid transport for Cd (90%), Zn (83%) and Pb (61%). Therefore, flood management needs to be taken into consideration in future models for erosion and pollutant transport.  相似文献   

6.
《Applied Geochemistry》2006,21(8):1259-1273
Grains of naturally oxidized arsenopyrite [FeAsS] collected from the oxidation zone in W-mine tailings were investigated, primarily using transmission electron microscopy. The grains are severely pitted and are surrounded by secondary minerals. The pitted nature of the grains is related to mechanisms governing the electrochemical oxidation of sulfide minerals, with prominent cusp-like features occurring at cathodic regions of the surface, and pits occurring at anodic regions. In general, the oxidation of arsenopyrite leads to the formation of an amorphous (or nanocrystalline) Fe–As–O-rich coating that contains small amounts of Si, Ca, Cu, Zn, Pb and Bi; nanoscale variation in the As, Pb, Bi and Zn contents of the coating was noted. Secondary Cu sulfides, thought to be chalcocite [Cu2S] and (or) djurleite [Cu31S16], occur as a layer (generally <500 nm thick) along the arsenopyrite grain boundary, and also within the coating as aggregates, and as layers that parallel the grain boundary. Although the precipitation of secondary Cu minerals along the grain boundary is a nanoscale feature, the process of formation is thought to be analogous to the supergene enrichment that occurs in weathered sulfide deposits. As the oxidation of arsenopyrite proceeds, layers and clusters of secondary Cu sulfides become isolated in the Fe–As–O coating. Secondary wulfenite [PbMoO4] and an unidentified crystalline Bi–Pb–As–O mineral occur in voids within the coating, suggesting that these minerals precipitated from the local pore-water. Small and variable amounts of W, Ca, Bi, As and Zn are associated with the wulfenite, and Zn, Fe and Ca are associated with the Bi–Pb–As–O mineral. Some of the wulfenite is in contact with inclusions of molybdenite [MoS2], suggesting that the oxidation of molybdenite in the presence of aqueous Pb(II) led to the formation of wulfenite. Mineralogical analyses at the nanoscale have improved the understanding of geochemical sources and sinks at this location. The results of this study indicate that the mineralogical controls on aqueous elemental concentrations at this tailings site are complex and are not predicted by thermodynamic calculations.  相似文献   

7.
The Yinchanggou Pb-Zn deposit, located in southwestern Sichuan Province, western Yangtze Block, is stratigraphically controlled by late Ediacaran Dengying Formation and contains >0.3 Mt of metal reserves with 11 wt% Pb + Zn. A principal feature is that this deposit is structurally controlled by normal faults, whereas other typical deposits nearby (e.g. Maozu) are controlled by reverse faults. The origin of the Yinchanggou deposit is still controversial. Ore genetic models, based on conventional whole-rock isotope tracers, favor either sedimentary basin brine, magmatic water or metamorphic fluid sources. Here we use in situ Pb and bulk Sr isotope features of sulfide minerals to constrain the origin and evolution of hydrothermal fluids. The Pb isotope compositions of galena determined by femtosecond LA-MC-ICPMS are as follows: 206Pb/204Pb = 18.17–18.24, 207Pb/204Pb = 15.69–15.71, 208Pb/204Pb = 38.51–38.63. These in situ Pb isotope data overlap with bulk-chemistry Pb isotope compositions of sulfide minerals (206Pb/204Pb = 18.11–18.40, 207Pb/204Pb = 15.66–15.76, 208Pb/204Pb = 38.25–38.88), and both sets of data plotting above the Pb evolution curve of average upper continental crust. Such Pb isotope signatures suggest an upper crustal source of Pb. In addition, the coarse-grained galena in massive ore collected from the deep part has higher 206Pb/204Pb ratios (18.18–18.24) than the fine-grained galena in stockwork ore sampled from the shallow part (206Pb/204Pb = 18.17–18.19), whereas the latter has higher 208Pb/204Pb ratios (38.59–38.63) than the former (208Pb/204Pb = 38.51–38.59). However, both types of galena have the same 207Pb/204Pb ratios (15.69–15.71). This implies two independent Pb sources, and the metal Pb derived from the basement metamorphic rocks was dominant during the early phase of ore formation in the deep part, whereas the ore-hosting sedimentary rocks supplied the majority of metal Pb at the late phase in the shallow part. In addition, sphalerite separated from different levels has initial 87Sr/86Sr ratios ranging from 0.7101 to 0.7130, which are higher than the ore formation age-corrected 87Sr/86Sr ratios of country sedimentary rocks (87Sr/86Sr200 Ma = 0.7083–0.7096), but are significantly lower than those of the ore formation age-corrected basement rocks (87Sr/86Sr200 Ma = 0.7243–0.7288). Again, such Sr isotope signatures suggest that the above two Pb sources were involved in ore formation. Hence, the gradually mixing process of mineralizing elements and associated fluids plays a key role in the precipitation of sulfide minerals at the Yinchanggou ore district. Integrating all the evidence, we interpret the Yinchanggou deposit as a strata-bound, normal fault-controlled epigenetic deposit that formed during the late Indosinian. We also propose that the massive ore is formed earlier than the stockwork ore, and the temporal-spatial variations of Pb and Sr isotopes suggest a certain potential of ore prospecting in the deep mining area.  相似文献   

8.
《Applied Geochemistry》2006,21(11):1969-1985
Gossan Creek, a headwater stream in the SE Upsalquitch River watershed in New Brunswick, Canada, contains elevated concentrations of total Hg (HgT up to 60 μg/L). Aqueous geochemical investigations of the shallow groundwater at the headwaters of the creek confirm that the source of Hg is a contaminated groundwater plume (neutral pH with Hg and Cl concentrations up to 150 μg/L and 20 mg/L, respectively), originating from the Murray Brook mine tailings, that discharges at the headwaters of the creek. The discharge area of the contaminant plume was partially delineated based on elevated pH and Cl concentrations in the groundwater. The local groundwater outside of the plume contains much lower concentrations of Hg and Cl (<0.1 μg/L and 3.8 mg/L, respectively) and displays the chemical characteristics of an acid-sulfate weathering system, with low pH (4.1–5.5) and elevated concentrations of Cu, Zn, Pb and SO4 (up to 5400 μg Cu/L, 8700 μg Zn/L, 70 μg Pb/L and 330 mg SO4/L), derived from oxidation of sulfide minerals in the Murray Brook volcanogenic massive sulfide deposit and surrounding bedrock. The HgT mass loads measured at various hydrologic control points along the stream system indicate that 95–99% of the dissolved HgT is attenuated in the first 3–4 km from the source. Analyses of creek bed sediments for Au, Ag, Cu, Zn, Pb and Hg indicate that these metals have partitioned strongly to the sediments. Mineralogical investigations of the contaminated sediments using analytical scanning electron microscopy (SEM), transmission electron microscopy (TEM) and scanning transmission electron microscopy (STEM), reveal discrete particles (<1–2 μm) of metacinnabar (HgS), mixed Au–Ag–Hg amalgam, Cu sulfide and Ag sulfide.  相似文献   

9.
The Xishan deposit, located in the western Guangdong Province in South China, is a quartz-vein type W-Sn deposit with an average Sn grade of 0.1–0.4 wt%. The deposit is temporally and spatially associated with Xishan alkali feldspar granite. The W–Sn mineralization is present mainly as veins that are hosted by the granite. In this paper we present new zircon U–Pb age, whole-rock geochemical data, Sr–Nd–Pb–Hf isotopic data and Re–Os age in order to constrain the nature and timing of magmatism and mineralization in the Xishan mining district with implications on geodynamic settings. LA–ICP–MS zircon U–Pb analyses yielded an age of 79.14 ± 0.31 Ma for the alkali feldspar granite, consistent with the molybdenite Re–Os age of 79.41 ± 1.11 Ma. The alkali feldspar granite shows high contents of SiO2 (71.52–76.25 wt%), high total alkalis (Na2O + K2O = 9.35–13.51 wt%), high field strength elements (e.g. Zr = 95.4–116 ppm, Y = 97.1–138 ppm, Nb = 36.1–55.5 ppm, Ga = 97.1–138 ppm), and rare earth elements (total REE = 171.8–194.0 ppm) as well as high Ga/Al ratios (10,000 × Ga/Al = 3.23–3.82) suggesting that it has the geochemical characteristics of A-type granite and shows an A2 subtype affinity. Sr–Nd isotopes of the alkali feldspar granite show that (87Sr/86Sr)i values range from 0.7111 to 0.7183, and the εNd(t) values and Nd model ages (T2DM) vary from −6.8 to −6.5 and 1414 to 1433 Ma, respectively. The Pb isotopic compositions are variable, with 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values ranging from 18.783 to 18.947, 15.709 to 15.722 and 38.969 to 39.244, respectively, indicating that the alkali feldspar granite was derived from a mantle-crust mixed source. In situ Hf isotopic analyses reveal that the alkali feldspar granite has εHf(t) values ranging from −9.69 to −0.04 and two-stage Hf model ages from 1145 Ma to 1755 Ma, indicating that the alkali feldspar granite was formed by the partial melting of Mesoproterozoic crusts of the Cathaysia Block with additions of mantle-derived materials. These results, together with previously presented regional geological relationships, suggest that the formation of the Xishan granite and associated W–Sn mineralization is related to lithospheric extension and asthenospheric upwelling that are attributed to a directional change of Pacific plate motion.  相似文献   

10.
Three large-scale experimental waste rock piles (test piles) were constructed and instrumented at the Diavik Diamond Mine in the Northwest Territories, Canada, as part of an integrated field and laboratory study to measure and compare physical and geochemical characteristics of experimental, low sulfide waste rock piles at various scales. This paper describes the geochemical response during the first season from a test pile containing 0.053 wt.% S. Bulk drainage chemistry was measured at two sampling points for pH, Eh, alkalinity, dissolved cations and anions, and nutrients. The geochemical equilibrium model MINTEQA2 was used to interpret potential mineral solubility controls on water chemistry. The geochemical response characterizes the initial flushing response of blasting residues and oxidation products derived from sulfides in waste rock exposed to the atmosphere for less than 1 year. Sulfate concentrations reached 2000 mg L−1 when ambient temperatures were >10 °C, and decreased as ambient temperatures declined to <0 °C. The pH decreased to <5, concomitant with an alkalinity minimum of <1 mg L−1 (as total CaCO3), suggesting all available alkalinity is consumed by acid-neutralizing reactions. Concentrations of Al and Fe were <0.36 and <0.11 mg L−1, respectively. Trends of pH and alkalinity and the calculated saturation indices for Al and Fe (oxy)hydroxides suggest that dissolution of Al and Fe (oxy)hydroxide phases buffers the pH. The effluent water showed increased concentrations of dissolved Mn (<13 mg L−1), Ni (<7.0 mg L−1), Co (<1.5 mg L−1), Zn (<0.5 mg L−1), Cd (<0.008 mg L−1) and Cu (<0.05 mg L−1) as ambient temperatures increased. Manganese is released by aluminosilicate weathering, Ni and Co by pyrrhotite [Fe1−xS] oxidation, Zn and Cd by sphalerite oxidation, and Cu by chalcopyrite [CuFeS2] oxidation. No dissolved metals appear to have discrete secondary mineral controls. Changes in SO4, pH and metal concentrations indicate sulfide oxidation is occurring and effluent concentrations are influenced by ambient temperatures and, possibly, increasing flow path lengths that transport reaction products from previously unflushed waste rock.  相似文献   

11.
Toxic metalliferous mine-tailings pose a significant health risk to ecosystems and neighboring communities from wind and water dispersion of particulates containing high concentrations of toxic metal(loid)s (e.g., Pb, As, Zn). Tailings are particularly vulnerable to erosion before vegetative cover can be reestablished, i.e., decades or longer in semi-arid environments without intervention. Metal(loid) speciation, linked directly to bioaccessibility and lability, is controlled by mineral weathering and is a key consideration when assessing human and environmental health risks associated with mine sites. At the semi-arid Iron King Mine and Humboldt Smelter Superfund site in central Arizona, the mineral assemblage of the top 2 m of tailings has been previously characterized. A distinct redox gradient was observed in the top 0.5 m of the tailings and the mineral assemblage indicates progressive transformation of ferrous iron sulfides to ferrihydrite and gypsum, which, in turn weather to form schwertmannite and then jarosite accompanied by a progressive decrease in pH (7.3–2.3).Within the geochemical context of this reaction front, we examined enriched toxic metal(loid)s As, Pb, and Zn with surficial concentrations 41.1, 10.7, 39.3 mmol kg−1 (3080, 2200, and 2570 mg kg−1), respectively. The highest bulk concentrations of As and Zn occur at the redox boundary representing a 1.7 and 4.2-fold enrichment relative to surficial concentrations, respectively, indicating the translocation of toxic elements from the gossan zone to either the underlying redox boundary or the surface crust. Metal speciation was also examined as a function of depth using X-ray absorption spectroscopy (XAS). The deepest sample (180 cm) contains sulfides (e.g., pyrite, arsenopyrite, galena, and sphalerite). Samples from the redox transition zone (25–54 cm) contain a mixture of sulfides, carbonates (siderite, ankerite, cerrusite, and smithsonite) and metal(loid)s sorbed to neoformed secondary Fe phases, principally ferrihydrite. In surface samples (0–35 cm), metal(loid)s are found as sorbed species or incorporated into secondary Fe hydroxysulfate phases, such as schwertmannite and jarosites. Metal-bearing efflorescent salts (e.g., ZnSO4·nH2O) were detected in the surficial sample. Taken together, these data suggest the bioaccessibility and lability of metal(loid)s are altered by mineral weathering, which results in both the downward migration of metal(loid)s to the redox boundary, as well as the precipitation of metal salts at the surface.  相似文献   

12.
The Ta Nang gold deposit is localized in Middle Jurassic black shales. The ore zone is a series of layer-by-layer crush zones and zones of hydrothermal rock alteration, < 10 m in thickness and > 2 km in length. It consists of quartz-sulfide veins, sulfidized black shales, and their hydrothermally altered varieties. Sulfide mineralization occurs as two assemblages: early pyrite-arsenopyrite and late chalcopyrite-sphalerite- galena. The pyrite-arsenopyrite assemblage is composed of different morphogenetic varieties. Coarse-crystalline arsenopyrite and pyrite aggregates and metacrystals of different orientations, 0.1 to 10 mm in size, are the most widespread. The chalcopyrite-sphalerite-galena assemblage is scarce. Along with the main ore minerals, it includes more rare minerals: pyrrhotite, lead sulfosalts (tsugaruite), and gold, which form a spatial assemblage with the main minerals or small inclusions in them. Gold occurs mainly as fine dissemination in cracks in pyrite, arsenopyrite, chalcopyrite, and quartz. Gold content in sulfidized carbonaceous shales is no more than tenths of ppm, averaging 0.38 ppm. This content in the quartz veins is considerably higher, averaging 3.92 ppm. Silver contents in the shales and quartz veins are similar and equal to 2.68 and 5.30 ppm, respectively. Also, the sulfidized rocks and veins have elevated contents of Fe, As, Pb, Zn, Cu, Cd, Ni, and Co; most of these elements (Fe, As, Pb, Zn, and Cu) make up their own sulfide minerals, and the others are trace elements. According to 39Ar/40Ar dating of sericite from the quartz-sulfide veins, their age is 129.3 ± 5.6 Ma, which is close to the age of the Cretaceous granite intrusions of the Deo Ca complex. These veins formed from moderately strong solutions (11.7-6.4 wt.% NaCl equiv) with the CH4 + N2 + CO2 gas phase at 340–130 °C. Judging from the S isotope composition (534S = 1.6-4.3%c), predominantly deep-seated endogenic sulfur participated in the formation of ore sulfide associations. Analysis of the distribution of gold shows that it was deposited together with sulfide minerals (galena, sphalerite, and chalcopyrite) at a later stage.  相似文献   

13.
The Fairview and Sheba mines are two of the major gold mines in the Paleoarchean Barberton Greenstone Belt of Southern Africa. At these mines, gold is associated with quartz–carbonate ± rutile veins and occurs both as “invisible” gold finely dispersed in sulfides (primarily pyrite and arsenopyrite), and as visible electrum grains hosted in pyrite. Up to approximately 1000 ppm Au are contained in pyrite, and up to approximately 1700 ppm in arsenopyrite. Mapping of trace element distribution in sulfide minerals using electron microprobe and proton probe techniques revealed multiple events of ore formation and Au mineralisation. At Fairview mine, three stages of pyrite formation were identified, the last of which is associated with arsenopyrite, electrum and other sulfide minerals (sphalerite, chalcopyrite, galena, gersdorffite, and Sb-sulfides). At Sheba mine, pyrite was deposited in two stages, and electrum is associated with the second stage. At both mines, the last stage of sulfide formation is the main stage of Au deposition, and is associated with mobilisation of Au, As, Sb, Cu, Zn, and Ni. The host rock composition seems to have affected the composition of pyrite, since higher Ni and Co concentrations (up to 1.4 and 1.6 wt.%, respectively) have been measured in meta-(ultra)mafic host rocks in comparison with chert and metagreywacke. Arsenopyrite is chemically zoned, and has Sb- and S-rich cores and As- and Ni-rich rims. This zoning indicates variations in fluid compositions (decreasing Sb and increasing Ni), and crystallisation conditions (increasing As content for increasing temperature). Geothermometric estimates based on the As content of arsenopyrite (As ≤ 32 at.%) indicate temperatures up to ~ 420 °C for the crystal rims. Petrographic and cathodoluminescence observations of quartz associated with gold mineralisation show only local brittle deformation, and no plastic deformation. This supports the notion that the ore-transporting veins were emplaced late in the deformation history. Variations of cathodoluminescence of quartz are correlated with changing Al contents (Al ≤ 0.16 wt.%), and can be related to fluctuations in the pH of the mineralising fluids.  相似文献   

14.
The Beiya deposit, located in the Sanjiang Tethyan tectonic domain (SW China), is the third largest Au deposit in China (323 t Au @ 2.47 g/t). As a porphyry-skarn deposit, Beiya is related to Cenozoic (Himalayan) alkaline porphyries. Abundant Bi-minerals have been recognized from both the porphyry- and skarn- ores, comprising bismuthinite, Bi–Cu sulfosalts (emplectite, wittichenite), Bi–Pb sulfosalts (galenobismutite, cosalite), Bi–Ag sulfosalt (matildite), Bi–Cu–Pb sulfosalts (bismuthinite derivatives), Bi–Pb–Ag sulfosalts (lillianite homologs, galena-matildite series), and Bi chalcogenides (tsumoite, the unnamed Bi2Te, the unnamed Ag4Bi3Te3, tetradymite, and the unnamed (Bi, Pb)3(Te, S)4). Native bismuth and maldonite are also found in the skarn ores. The arsenopyrite geothermometer reveals that the porphyry Au mineralization took place at temperatures in the range of 350–450 °C and at log fS2 in the range of − 8.0 to − 5.5, respectively. In contrast, the Beiya Bi-mineral assemblages indicate that the skarn ore-forming fluids had minimum temperatures of 230–175 °C (prevailing temperatures exceeding 271 °C) and fluctuating fS2fTe2 conditions. We also model a prolonged skarn Au mineralization history at Beiya, including at least two episodes of Bi melts scavenging Au. We thus suggest that this process was among the most effective Au-enrichment mechanisms at Beiya.  相似文献   

15.
The leaching behaviour of electrostatic precipitator dust from the Mufulira Cu smelter (Copperbelt, Zambia) was studied using a 48-h pH-static leaching experiment (CEN/TS 14997). The release of metals (Cd, Co, Cu, Ni, Pb and Zn) and changes in mineralogical composition using X-ray diffraction and PHREEQC-2 modelling were investigated in the pH range of 3–7. The highest concentrations of metals were released at pH 3–4.5, which encompasses the natural pH of the dust suspension (~4.3). About 40% of the total Cu was leached at pH 3, yielding 107 g/kg. Chalcanthite (CuSO4·5H2O), magnetite (Fe3O4) and delafossite (CuFeO2) represented the principal phases of the studied dust. In contact with water, chalcanthite was dissolved and hydrated Cu sulphates precipitated at pH 4–7. Gypsum (CaSO4·2H2O) and secondary Fe or Al phases were observed in the leached residues. Serious environmental impact due to leaching may occur in dust-contaminated soil systems in the vicinity of the smelting plants.  相似文献   

16.
Contaminated drainage related to the leaching of soluble metals under near-neutral conditions, known as contaminated neutral drainage (CND), may arise when metal species are soluble at neutral pH. Such a phenomenon has been sporadically observed in effluent from the Tio mine waste-rock pile in Quebec, Canada, particularly from older sections of the pile, where Ni concentrations are increasing with time. It has been postulated that Ni is retained within the fresh waste rock as sorbed species, but as the rock ages, sorption sites become saturated and more Ni is released to the effluent. A field test program was initiated to evaluate the geochemical behavior of the waste rock. This paper presents a numerical analysis of CND generation from waste-rock field test cells including water flow and multi-component transport with geochemical reactions (e.g. sulfide oxidation, pH neutralization, and Ni sorption), using the code MIN3P. The model was able to represent the delay before Ni is seen in the effluent, as caused by sorption of Ni onto Fe-oxide particles. Once the sorption sites are saturated, the model allows Ni release into the effluent by millerite dissolution, expressed by the shrinking core model. A sensitivity analysis indicated that sorption parameters significantly affected the simulated results, so their selection should be based on sound independent field or experimental data.  相似文献   

17.
The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive εNd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ34S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (206Pb/204Pb = 18.310–18.656, 207Pb/204Pb = 15.489–15.643 and 208Pb/204Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ13CPDB and δ18OSMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ13CPDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ18O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.  相似文献   

18.
Several occurrences of gold-bearing quartz veins are situated along the east–northeast-trending Barramiya–Um Salatit ophiolitic belt in the central Eastern Desert of Egypt. In the Barramiya mine, gold mineralization within carbonaceous, listvenized serpentinite and adjacent to post-tectonic granite stocks points toward a significant role of listvenitization in the ore genesis. The mineralization is related to quartz and quartz–carbonate lodes in silicified/carbonatized wallrocks. Ore minerals, disseminated in the quartz veins and adjacent wallrocks are mainly arsenopyrite, pyrite and trace amounts of chalcopyrite, sphalerite, tetrahedrite, pyrrhotite, galena, gersdorffite and gold. Partial to complete replacement of arsenopyrite by pyrite and/or marcasite is common. Other secondary phases include covellite and goethite. Native gold and gold–silver alloy occur as tiny grains along micro-fractures in the quartz veins. However, the bulk mineralization can be attributed to auriferous arsenopyrite and arsenic-bearing pyrite (with hundreds of ppms of refractory Au), as evident by electron microprobe and LA-ICP-MS analyses.The mineralized quartz veins are characterized by abundant carbonic (CO2 ± CH4 ± H2O) and aqueous-carbonic (H2O–NaCl–CO2 ± CH4) inclusions along intragranular trails, whereas aqueous inclusions (H2O–NaCl ± CO2) are common in secondary sites. Based on the fluid inclusions data combined with thermometry of the auriferous arsenopyrite, the pressure–temperature conditions of the Barramiya gold mineralization range from 1.3 to 2.4 kbar at 325–370 °C, consistent with mesothermal conditions. Based on the measured δ34S values of pyrite and arsenopyrite intimately associated with gold, the calculated δ34SΣs values suggest that circulating magmatic, dilute aqueous-carbonic fluids leached gold and isotopically light sulfur from the ophiolitic sequence. As the ore fluids infiltrated into the sheared listvenite rocks, a sharp decrease in the fluid fO2 via interaction with the carbonaceous wallrocks triggered gold deposition in structurally favorable sites.  相似文献   

19.
The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270 km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7 million tonnes of sulfide ores grading 0.54 to 8.94 wt.% Pb and 1.09 to 26.64 wt.% Zn. Calcite samples have δ13CPDB and δ18OSMOW values ranging from − 3.1 to + 2.5‰ and + 18.8 to + 26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ13CPDB vs. δ18OSMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ34SCDT values of sphalerite and galena samples range from + 18.9 to + 20.3‰ and + 15.6 to + 17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ34SCDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292 °C, consistent with previous fluid inclusion studies. Temperatures above 100 °C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ66Zn values ranging from 0.00 to + 0.55‰ (mean + 0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ66Zn values ranging from 0.00 to + 0.07‰, + 0.12 to + 0.23‰, and + 0.29 to + 0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a 207Pb/204Pb vs. 206Pb/204Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have 87Sr/86Sr200 Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.  相似文献   

20.
The unusually high grade hypogene zinc ore at Angouran in northwestern Iran (40.4% Zn, 1.9% Pb in the sulfide ore, 28.1% Zn, 4.4% Pb in the carbonate ore, and 110 g/t Ag) formed from an initially highly saline, reduced, relatively acid hydrothermal brine at two successive sulfide and carbonate ore stages. The early ore stage consists of multiple phases of sphalerite dominated sulfide ore breccia with subordinate amounts of galena (± Pb sulfosalts), minor pyrite, and abundant barite. Sphalerite precipitated at moderate temperatures (≥ 155 °C) because of pH increase in the presence of hangingwall marble. Smithsonite precipitated at a higher pH value (≥ 7) and at lower temperatures (≤ 120 °C) from dilute solutions (salinities close to zero) by mixing of the Zn bearing brines with cool, HCO3 bearing waters. The first melting points of the primary (LV) fluid inclusions in sphalerite and in hydrothermal quartz are unusually low (≤  60 °C), close to the eutectic point of the ZnCl2–H2O system (− 62 °C). Total salinities taken from the ZnCl2–H2O system as a best approximation correspond to 26–41 eq mass % ZnCl2. The initial brine evolved to a CaCl2–NaCl rich solution with 27 eq mass % salinity. Gas densities (≤ 0.1 g cm 3 for water vapor and ≤ 0.18 g cm 3 for CO2) in the fluid inclusions indicate low pressure (≤ 5 bar for water vapor, and ≤ 100 bar for CO2) at the entrapment temperatures.At the first carbonate ore stage sulfides continued to precipitate characteristically as arsenopyrite with minor amounts of galena and pyrite. The abrupt change of the fluid composition at the sulfide–carbonate boundary was accompanied by a change of the fluid temperature and pressure that produced brecciation of the sulfide ore matrix and an almost total dissolution of barite and replacement by the hypogene smithsonite. Alteration is restricted to ore deposition and consists of weak sericitization and silicification with local dolomitization at the sulfide ore stage, and pervasive dissolution of the hangingwall marble, in particular at the carbonate ore stage.The breccia orebody at Angouran is sited at the crestal portion of a domed antiform at the lithological and thrust boundary of Neoproterozoic–Lower Cambrian footwall schists and the hangingwall marble in rapidly uplifted and exhumated Angouran Block east of the Geynardjeh Thrust Fault. The footwall schists occupy a detachment fault zone above imbricated nappe sheets of the basement metamorphic complex of the Sanandaj–Sirjan zone. During the Pliocene, the nappe sheets were thrust toward the southwest onto the Miocene felsic volcanic rocks of the Urumieh Dokhtar Volcanic Belt that are intruded by 10 Ma late Miocene basalts. The 11.9 Ma and 18.4 Ma zircon ages of the felsic volcanic rocks indicate the lower age limit of the ore body emplacement.The associations with large scale, mid-late Miocene, felsic volcanism along the active Tethyan belt, as well as the ubiquitous presence of the volcanic rock clasts in the sphalerite ore matrix, provide strong evidence of the involvement of hydrothermal processes at Angouran. Ore fluids were successively and pulsatorily generated within the seismically active region. A following geothermal activity appears to have had a significant input in the formation of the carbonate ore of the hypogene, as well as the supergene stage. Stable isotope data suggest complex interaction of element sources and processes. Allowing a broad interpretation, the sulfur isotopic composition of the sulfides δ34S (3.9 to 7.4‰) suggests that the sulfur could be sourced from evolving, mixed magmatic–basinal brine. The isotopic composition of the hypogene smithsonites (δ13C: 2.72 to 5.51‰, δ18O: 18.4 to 22.8‰) broadly supports the local geology and field relationships, which comply with a marble wallrock source for the carbonate ores. They lend support to the assumption that smithsonite was deposited from solutions with isotopic composition similar to those involved in the hydrothermal dolomitization of the marbles. The excess of dissolved marble precipitated as large volumes of travertine and as late calcite veins (δ13C: 18.8 to 20.3‰, δ18O: 3.1 to 6.4‰) at the mineralization site. Isotope values of the travertine (δ13C: 4.5 to 6.6‰, δ18O: 20.1 to 21.1‰ V-SMOW) are consistent with the involvement of CO2 derived from thermogenic decarbonization of the host marble by waters of dominantly meteoric origin, most likely concomitantly with ore forming processes.The Angouran deposit is the only reported case of a two stage, hypogene zinc sulfide–zinc carbonate mineralization, and represents a new style of nonsulfide zinc mineralization.  相似文献   

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