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1.
The Pingshui Cu–Zn deposit is located in the Jiangshan–Shaoxing fault zone, which marks the Neoproterozoic suture zone between the Yangtze block and Cathaysia block in South China. It contains 0.45 million tons of proven ore reserves with grades of 1.03 wt.% Cu and 1.83 wt.% Zn. This deposit is composed of stratiform, massive sulfide ore bodies, which contain more than 60 vol.% sulfide minerals. These ore bodies are hosted in altered mafic and felsic rocks (spilites and keratophyres) of the bimodal volcanic suite that makes up the Neoproterozoic Pingshui Formation. Metallic minerals include pyrite, chalcopyrite, sphalerite, tennantite, tetrahedrite and magnetite, with minor galena. Gangue minerals are quartz, sericite, chlorite, calcite, gypsum, barite and jasper. Three distinct mineralogical zones are recognized in these massive sulfide ore bodies: a distal zone composed of sphalerite + pyrite + barite (zone I); an intermediate zone characterized by a pyrite + sphalerite + chalcopyrite assemblages (zone II); and a proximal zone containing chalcopyrite + pyrite + magnetite (zone III). A thin, layer of exhalative jaspilite overlies the sulfide ore bodies except in the proximal zone. The volcanic rocks of the Pingshui Formation are all highly altered spilites and keratophyres, but their trace element geochemistry suggests that they were generated by partial melting of the depleted mantle in an island arc setting. Homogenization temperatures of the primary fluid inclusions in quartz from massive sulfide ores are between 217 and 328 °C, and their salinities range from 3.2 to 5.7 wt.% NaCl equivalent. Raman spectroscopy of the fluid inclusions showed that water is the dominant component, with no other volatile components. Fluid inclusion data suggest that the ore-forming fluids were derived from circulating seawater. The δ34S values of pyrite from the massive sulfide ores range from − 3.6‰ to + 3.4‰, indicating that the sulfur was primarily leached from the arc volcanic rocks of the Pingshui Formation. Both pyrite from the massive sulfide ores and plagioclase from the spilites have similar lead isotope compositions, implying that the lead was also derived from the Pingshui Formation. The low lead contents of the massive sulfide ores and the geochemistry of their host rocks are similar to many VMS Cu–Zn deposits in Canada (e.g., Noranda) and thus can be classified as belonging to the bimodal-mafic subtype. The presence of magnetite and the absence of jaspilite and barite at the − 505 m level in the Pingshui deposit suggest that this level is most likely the central zone of the original lateral massive sulfide ore bodies. If this interpretation is correct, the deep part of the Pingshui Cu–Zn deposit may have significant exploration potential.  相似文献   

2.
《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   

3.
The Huangshaping Pb–Zn–W–Mo polymetallic deposit, located in southern Hunan Province, China, is one of the largest deposits in the region and is unique for its metals combination of Pb–Zn–W–Mo and the occurrence of significant reserves of all these metals. The deposit contains disseminated scheelite and molybdenite within a skarn zone located between Jurassic granitoids and Carboniferous sedimentary carbonate, and sulfide ores located within distal carbonate-hosted stratiform orebodies. The metals and fluids that formed the W–Mo mineralization were derived from granitoids, as indicated by their close spatial and temporal relationships. However, the source of the Pb–Zn mineralization in this deposit remains controversial.Here, we present new sulfur, lead, and strontium isotope data of sulfide minerals (pyrrhotite, sphalerite, galena, and pyrite) from the Pb–Zn mineralization within the deposit, and these data are compared with those of granitoids and sedimentary carbonate in the Huangshaping deposit, thereby providing insights into the genesis of the Pb–Zn mineralization. These data indicate that the sulfide ores from deep levels in the Huangshaping deposit have lower and more consistent δ34S values (− 96 m level: + 4.4‰ to + 6.6‰, n = 13) than sulfides within the shallow part of the deposit (20 m level: + 8.3‰ to + 16.3‰, n = 19). The δ34S values of deep sulfides are compositionally similar to those of magmatic sulfur within southern Hunan Province, whereas the shallower sulfides most likely contain reduced sulfur derived from evaporite sediments. The sulfide ores in the Huangshaping deposit have initial 87Sr/86Sr ratios (0.707662–0.709846) that lie between the values of granitoids (0.709654–0.718271) and sedimentary carbonate (0.707484–0.708034) in the Huangshaping deposit, but the ratios decreased with time, indicating that the ore-forming fluids were a combination of magmatic and formation-derived fluids, with the influence of the latter increasing over time. The lead isotopic compositions of sulfide ores do not correlate with sulfide type and define a linear trend in a 207Pb/204Pb vs. 206Pb/204Pb diagram that is distinct from the composition of the disseminated pyrite within sedimentary carbonates and granitoids in the Huangshaping deposit, but is similar to the lead isotopic composition of sulfides within coeval skarn Pb–Zn deposits in southern Hunan Province. In addition, the sulfide ores have old signatures with relative high 207Pb/206Pb ratios, suggesting that the underlying Paleoproterozoic basement within southern Hunan Province may be the source of metals within the Huangshaping deposit.The isotope geochemistry of sulfide ores in the Huangshaping deposit shows a remarkable mixed source of sulfur and ore-forming fluids, and the metals were derived from the basement. These features are not found in representative skarn-type Pb–Zn mineralization located elsewhere. The ore-forming elements (S, Pb, and Zn) from the granitoids made an insignificant contribution to sulfide precipitation in this deposit. However, the emplacement of granitoids did provide large amounts of heat and fluids to the hydrothermal system in this area and extracted metals from the basement rocks, indicating that the Jurassic magmatism associated with the Huangshaping deposit was crucial to the Pb–Zn mineralization.  相似文献   

4.
Apparent Re–Os ages of some magmatic sulfide ore deposits are older than the zircon and baddeleyite U–Pb ages which are interpreted as the formation age of the host intrusions. The Jinchuan Ni–Cu–PGE deposit of China, the world's third largest, is such a case. We report apparent Re–Os isochron ages of 1117 ± 67 Ma, 1074 ± 120 Ma and 867 ± 75 Ma with initial 187Os/188Os ratios of 0.120 ± 0.012, 0.162 ±0.017 and 0.235 ± 0.027 for disseminated ores, sulfides from the disseminated ores and massive ores from Jinchuan, respectively. Using these data and Re–Os ages from the literature, we find that the oldest apparent Re–Os age and lowest initial Os isotope ratio are from disseminated ores which contain small amounts of sulfide minerals, the highest initial Os isotope ratios and youngest apparent Re–Os ages, consistent with the zircon and baddeleyite U–Pb ages, are from massive ores containing 90–100 modal% sulfide, and net-textured ores with about 25 modal% sulfides yield apparent Re–Os ages and initial Os ratios intermediate between those of the disseminated and massive ores.Because Os diffusion between sulfides is inhibited by the intervening silicates even at high temperatures, re-equilibration did not occur in the disseminated ore and the samples retained the Os ratios of the contaminated magma, leading to geologically meaningless ages that are older than the formation age of the rocks. While Os-bearing sulfide minerals and magnetite show low closure temperatures of Os diffusion and the sulfide minerals in the massive ore are closely connected with each other, facilitating fast diffusion of Os, re-equilibration of Os was achieved during cooling of the ore from about 850 °C after the segregation to about 400 °C. Thus, an age corresponding to the formation time and an elevated initial Os ratio were yielded by the massive ore. Os isotopes in the net-textured ore behave in the way intermediate between the disseminated and massive ores. Pb isotope data support the Os results. Disseminated ores have heterogeneous Pb isotope ratios whereas Pb in the massive ores is more uniform, consistent with Pb isotopic equilibration in the massive ores, but not in the disseminated ores.  相似文献   

5.
Trace element geochemistry was studied in geothermal fluids in Iceland. The major and trace element compositions of hot springs, sub-boiling, and two-phase (liquid and vapor) wells from 10 geothermal areas were used to reconstruct the fluid composition in the aquifers at depth. Aquifer fluid temperatures ranged from 4 to 300 °C, pH values between 4.5 and 9.3, and fluids typically contained total dissolved solids <1000 ppm, except in geothermal areas that have seawater and seawater-meteoric water mixtures. Trace alkali elements Li, Rb and Cs are among the most mobile elements in aquifer fluids, with concentrations in the range of <1 ppb to 3.49 ppm Li, <0.01 to 57 ppb Cs, and <1 ppb to 3.77 ppm Rb. Their chemistry is thought to be dominated by rock leaching and partitioning into Na- and K-containing major alteration minerals. Arsenic, Sb, Mo and W are typically present in concentrations in the range of 1–100 ppb. They are relatively mobile, yet Mo may be limited by molybdenite solubility. The alkaline earth elements Ba and Sr are quite immobile with concentrations in the range of <0.1–10 ppb Ba and <1–100 ppb Sr in the dilute fluids, but up to 5.9 ppm Ba and 8.2 ppm Sr in saline fluids. These elements show a systematic relationship with Ca, possibly due to substitution for Ca in Ca-containing major alteration minerals like calcite, epidote and anhydrite. Incorporation into major Ca-minerals may also be important for Mn. Many metals including Fe, Cr, Ni, Zn, Cu, Co, Pb and Ag have low mobility and concentrations, typically <1 ppb for Ag, Cd, Co, Cr, Cu, Ni, and Pb, <10 ppb for Zn and < 100 ppb for Fe, although for some metals higher concentrations are associated with saline fluids. Based on the metals assessed, saturation is approached with respect to many sulfide minerals and in some cases oxide minerals but Cu, Ni and Pb minerals are slightly but systematically undersaturated, and Ag phases significantly undersaturated. Evaluation of mineral-fluid equilibria for these metals is problematic due to their low concentrations, problems associated with assessing the aqueous species distribution by thermodynamic calculations, and uncertainties concerning the exact minerals possibly involved in such reactions. Reaction path calculations, poor comparison of concentrations measured in the samples collected at the wellhead and published downhole data as well as boiling, cooling and mass precipitation calculations suggest removal of many metals due to changes upon depressurization boiling and conductive cooling of the aquifer fluids as they ascend in wells. These results imply that processes such as mass precipitation upon fluid ascent may be highly important and emphasize the importance of considering mass movement in geothermal systems.  相似文献   

6.
The W Horizon, Marathon Cu-Pd deposit in the Mesoproterozoic Midcontinent rift is one of the highest grade PGE repositories in magmatic ore deposits world-wide. The textural relationships and compositions of diverse platinum-group mineral (PGM) and sulfide assemblages in the extremely enriched ores (>100 ppm Pd-Pt-Au over 2 m) of the W Horizon have been investigated in mineral concentrates with ∼10,000 PGM grains and in situ using scanning electron microprobe and microprobe analyses.Here we show, from ore samples with concentrations up to 23.1 Pd ppm, 8.9 Pt ppm, 1.4 Au ppm and 0.73 Rh ppm, the diversity of minerals (n = 52) including several significant unknown minerals and three new mineral species marathonite (Pd25Ge9; McDonald et al., 2016), palladogermanide (Pd2Ge; IMA 2016-086, McDonald et al., 2017), kravtsovite (PdAg2S, IMA No 2016-092, Vymazalová et al., 2017). The PGM are distributed as PG-, sulfides (52 vol%), -arsenides (34 vol%), -intermetallics of Au-Ag-Pd-Cu and Pd-Ge(10 vol%) and -bismuthides and tellurides (4 vol%). The discovery of abundant (>330 grains) large unknown sulfide minerals with Rh allows us to present analyses three significant potentially new minerals (WUK-1, WUK-2, WUK-3) that are all clearly enriched in Rh (averaging 4.2, 8.5 and 28.21 wt% Rh respectively). Several examples of paragenetic sequences and mineral chemical changes for enrichment of Cu, Pd and Rh with time are revealed in the PGM and base-metal sulfides. We suggest this enhanced metal enrichment formed in response to increasing fO2 causing the oxidation of Fe2+ to Fe3+ and to a lesser extent, S.Phase relations in the Ag-Pd-S, Rh-Ni-Fe-S, Pd-Ge, Au-Pd-Cu-Ag, Pd-Ag-Te systems help constrain the crystallization temperatures of the majority of ore minerals in the W Horizon at ∼500 °C or moderate to high subsolidus temperatures (400–600 °C). Local transport by aqueous fluids becomes evident as minerals recrystallize down to <300 °C. The PGE-enriched W Horizon ores exhibit a complex post-magmatic history dominated by the effects of oxidation during cooling of a Cu-PGE enriched magma source from a deep reservoir.  相似文献   

7.
《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   

8.
The Kalatag Cu–Zn–Au district contains a number of economically important Cu deposits in eastern Tianshan in Xinjiang, NW China. Due to the lack of precise mineralization ages, the metallogenesis of this area has long been a matter of debate. In this study, chalcopyrite Re–Os isotope methods are used to date the South Meiling Cu–Zn and Hongshi Cu deposits in the eastern part of Kalatag area.The South Meiling Cu–Zn deposit is hosted in volcanic-sedimentary rocks of the Late Ordovician to Early Silurian Daliugou Formation. The deposit consists of two parts: a concordant massive sulfide ores and discordant vein-type ores located in the footwall strata. The principal ore minerals are pyrite, chalcopyrite, sphalerite, minor tetrahedrite, galena and pyrrhotite. Gangue minerals include quartz, sericite and barite, and minor chlorite, plagioclase and carbonate minerals. The Hongshi Cu deposit represents a hydrothermal vein system hosted in the mafic volcanic rocks of Daliugou Formation. The orebodies are associated with quartz veins and controlled by subsidiary faults of the Kalatag fault. The ore-forming process can be divided into the early, middle and late stages and is characterized by quartz–pyrite, quartz–chalcopyrite–pyrite and quartz–carbonate–gypsum veins, respectively.Re–Os analyses of chalcopyrite from the South Meiling Cu–Zn deposit yield an isochron age of 434.2 ± 3.9 Ma and initial 187Os/188Os ratio of 0.647 ± 0.098 (MSWD = 0.59). Re–Os analyses of chalcopyrite from the Hongshi Cu deposit yield an isochron age of 431.8 ± 2.7 Ma and initial 187Os/188Os ratio of − 0.165 ± 0.075 (MSWD = 0.77). Since chalcopyrite is the primary copper mineral, we interpret these isochron ages as the timing of Cu mineralization, based on field geology and petrographic evidence. These results suggest that the Re–Os ages presented here provide, for the first time, a direct constraint on an early Paleozoic Cu mineralization event of the eastern Tianshan Orogen. The high initial 187Os/188Os ratios (0.647 ± 0.098) ratio of ~ 434 Ma chalcopyrite from the South Meiling deposit suggest that the metal was sourced from a two end-member mixing of crust and mantle materials. Moreover, we propose that the VMS mineral system and hydrothermal vein system of the Kalatag district were related to the south-dipping subduction of the Kalamaili oceanic plate during the Late Ordovician–Silurian.  相似文献   

9.
Re–Os dating of disseminated ore from the Kalatongke Cu–Ni sulfide mineral deposit, Xinjiang, Northwest (NW) China, yields an apparent isochron age of 433 ± 31 Ma with an apparent initial 187Os/188Os (433 Ma) ratio of 0.197 ± 0.027. This apparent age is older than not only the zircon U–Pb age of the host intrusion (287 ± 5 Ma, Han et al., 2004) but also the stratigraphic age of the intruded country rock. Thus, the regression line is a pseudo-isochron. However, previous Re–Os dating of massive ores of the same deposit yielded an age that is consistent, within analytical uncertainty, with the zircon U–Pb age (Zhang et al., 2008). This relationship is similar to that observed in the Jinchuan deposit, NW China. Therefore, we suggested that the same mechanism, post-segregation diffusion of Os (Yang et al., 2008), is applicable to the Kalatongke deposit.Re–Os isotopic studies of Kalatongke, Jinchuan and representative magmatic Cu–Ni sulfide deposits suggest that the massive ores of mafic–ultramafic-rock-associated Cu–Ni sulfide deposits would yield geologically meaningful Re–Os age, whereas a pseudo-isochron would be obtained for the disseminated ores. Therefore, to obtain a geologically meaningful Re–Os age, the type of the deposit, the type of the ore and the ore-forming process should be taken into account.  相似文献   

10.
The Early Cambrian black shale sequence of the Niutitang Formation in South China hosts a synsedimentary, organic carbon-rich, polymetallic sulfide layer with extreme metal concentrations, locally mined as polymetallic Ni–Mo–PGE–Au ore. In combination with previously reported data, we present Mo isotope, platinum-group element (PGE), and trace and rare-earth element (REE) data for the polymetallic sulfide ores and host black shales from four mine sites (Dazhuliushui and Maluhe in Guizhou Province, and Sancha and Cili in Hunan Province, respectively), several hundred kilometers apart. The polymetallic sulfide ores have consistently heavy δ98/95Mo values of 0.94 to 1.38‰ (avg. 1.13 ± 0.14‰, 1σ, n = 11), and the host black shale and phosphorite have slightly more variable δ98/95Mo values of 0.81‰ to 1.70‰ (n = 14). This latter variation is due to variable paleoenvironmental conditions from suboxic to euxinic, and partly closed-system fractionation in isolated marine sedimentary basins. Both the polymetallic sulfides and host black shales show PGE distribution patterns similar to that of present-day seawater, but different from those of ancient submarine-hydrothermal deposits and modern submarine hydrothermal fluids. The polymetallic sulfide bed has a generally consistent metal enrichment by a factor of 107 compared to present-day seawater. PAAS-normalized REE + Y patterns of the polymetallic sulfide bed are characterized by a remarkably positive Y anomaly, consistent with an origin of the REE predominantly from seawater. Small positive Eu anomalies in some of the sulfide ores could reflect minor hydrothermal components involved. The Mo isotope, PGE, and trace and rare-earth element geochemical data suggest that metals in the polymetallic Ni–Mo–PGE–Au sulfide ore layer were scavenged mostly from Early Cambrian seawater, by both in-situ precipitation and local re-deposition of sulfide clasts.  相似文献   

11.
《Applied Geochemistry》2005,20(5):907-917
Solutions draining the Alta Mine, Jefferson County, MT, were contaminated by acid sulfate waters (ASW) generated from anthropogenic exposure of meteoric waters to sulfidic underground mine workings and a waste-rock pile. In 1999, a remediation effort was initiated in an attempt to improve the quality of water draining the site through removal of the waste-rock pile with which these solutions come in contact. ASW were sampled in the mineshaft prior to entering the waste-rock pile and upon discharge from the waste-rock pile aquifer near the pile toe. ASW composition changed as solutions flowed through the waste-rock pile due to sulfide and silicate weathering and schwertmannite precipitation.Schwertmannite and goethite were both sampled in the waste-rock pile where a distinct field relation was observed between the two minerals. Schwertmannite was always in contact with actively flowing ASW, while goethite was never in direct contact with ASW and was generally above the waste-rock water table. Goethite is hypothesized to be re-dissolved/re-precipitated schwertmannite that was deposited under higher flow conditions and subsequently transformed to goethite through exposure to wet/dry cycling associated with seasonal fluctuations in the amount of water moving through the hydrogeologic system. Trace metal concentrations in ammonium oxalate extracts of these minerals provides the first published data on the behavior of multiple trace metals through this phase transformation, which has important ramifications for considering schwertmannite as a long term metal sink due to its known metastability with respect to goethite. A relative retention scale through this phase transformation of Pb > Zn, Mn > As, Al, Cu is potentially applicable to other ASW systems.  相似文献   

12.
The Tuwu porphyry Cu deposit in the eastern Tianshan Orogenic Belt of southern Central Oceanic Orogen Belt contains 557 Mt ores at an average grade of 0.58 wt.% Cu and 0.2 g/t Au, being the largest porphyry Cu deposit in NW China. The deposit is genetically related to dioritic and plagiogranitic porphyries that intruded the Carboniferous Qieshan Group. Ore minerals are dominantly chalcopyrite, pyrite and enargite. Porphyric diorites have Sr/Y and La/YbN ratios lower but Y and Yb contents higher than plagiogranites. Diorites have highly variable Cu but nearly constant PGE contents (most Pd = 0.50–1.98 ppb) with Cu/Pd ratios ranging from 10,900 to 8,900,000. Plagiogranites have PGEs that are positively correlated with Cu and have nearly uniform Cu/Pd ratios (5,100,000 to 7,800,000). Diorites have concentrations of Re (0.73–15.18 ppb), and 187Re/188Os and 187Os/188Os ratios lower but common Os contents (0.006–0.097 ppb) higher than plagiogranites. However, both the diorites and plagiogranites have similar normalized patterns of rare earth elements (REE), trace element and platinum-group elements (PGEs). All the samples are characterized by the enrichments of LREE relative to HREE and display positive anomalies of Pb and Sr but negative anomalies of Nb and Ta in primitive-mantle normalized patterns. In the primitive mantle-normalized siderophile element diagrams, they are similarly depleted in all PGEs but slightly enriched in Au relative to Cu.Our new dataset suggests that both the diorite and plagiogranite porphyries were likely evolved from magmas derived from partial melting of a wet mantle wedge. Their parental magmas may have had different water contents and redox states, possibly due to different retaining time in staging magma chambers at the depth, and thus different histories of magma differentiation. Parental magmas of the diorite porphyries are relatively reduced with less water contents so that they have experienced sulfide saturation before fractional crystallization of silicate minerals, whereas the relatively more oxidized parental magmas with higher water contents of the plagiogranite porphyries did not reach sulfide saturation until the magmatic-hydrothermal stage. Our PGE data also indicates that the Cu mineralization in the Tuwu deposit involved an early stage with the enrichments of Au, Mo and Re and a late stage with the enrichment of As but depletion of Au–Mo. After the formation of the Cu mineralization, meteoric water heated by magmas penetrated into and interacted with porphyritic rocks at Tuwu, which was responsible for leaching Re from hosting rocks.  相似文献   

13.
Fluorite-leucophane-melinophane-eudidymite ores of zone XVIII of the Ermakovka F-Be deposit were studied by geological, mineralogical, and thermobarogeochemical methods. Contents of Be and impurity elements (Li, Na, Mg, Al, Si, Cl, K, Mn, Fe, Cu, Zn, Nb, Mo, Ag, Sn, W, and Pb) in fluid inclusions in fluorite of this zone have been first determined by LA-ICP-MS. It is shown that fluorite-leucophane-melinophane-eudidymite ores were formed by alkaline high-F low-salt (6.0-12.5 wt.% NaCl equiv) solutions with a relatively low content of Be (0.0002-1.04 g/kg of solution). Fluorite and beryllium minerals were deposited in ores in a wide range of P-T conditions. The early fluorite-phenakite paragenesis formed at high temperatures (480-650 °C) and high pressures (> 3 kbar). At the late low-temperature stage, phenakite was replaced by Na-Be silicates (eudidymite and melinophane-leucophane) at < 220 °C and < 770 bars. The Be-ore deposition was due to the destruction of a predominant beryllium fluoride-carbonate complex as a result of the crystallization of fluorite during the metasomatic replacement of limestones. Eudidymite and melinophane-leucophane formed at low temperatures under high activity of Na and Ca and low activity of Be and F in highly alkaline solutions.  相似文献   

14.
Kafang is one of the main ore deposits in the world-class Gejiu polymetallic tin district, SW China. There are three main mineralization types in the Kafang deposit, i.e., skarn Cu–Sn ores, stratiform Cu ores hosted by basalt and stratiform Cu–Sn ores hosted by carbonate. The skarn mainly consists of garnet and pyroxene, and retrograde altered rocks. These retrograde altered rocks are superimposed on the skarn and are composed of actinolite, chlorite, epidote and phlogopite. Major ore minerals are chalcopyrite, pyrrhotite, cassiterite, pyrite and scheelite. Sulfur and Pb isotopic components hint that the sources of different types of mineralization are distinctive, and indicate that the skarn ore mainly originated from granitic magma, whereas the basalt-hosted Cu ores mainly derived from basalt. Microthermometry results of fluid inclusions display a gradual change during the ore-forming process. The homogenization temperature of different types of inclusions continuously decreases from early to late mineralization stages. The salinities and freezing temperatures exhibit similar evolutionary tendencies with the T homogenization, while the densities of the different types keep constant, the majority being less than 1. Oxygen and hydrogen isotopic values (δ18O and δD) of the hydrothermal fluids fall within ranges of 3.1 to 7.7‰ with an average of 6.15‰, calculated at the corresponding homogenization temperature, and − 73 and − 98‰ with an average of − 86.5‰, respectively. Microthermometry data and H–O isotopes indicate that the ore-forming fluid of the Kafang deposit is mainly derived from magma in the early stage and a mixture of meteoric and magmatic water in late stage. Molybdenite Re–Os age of the skarn type mineralization is 83.4 ± 2.1 Ma, and the stratiform ores hosted by basalt is 84.2 ± 7.3 Ma, which are consistent with the LA-ICP-MS zircon age of the Xinshan granite intrusion (83.1 ± 0.4 Ma). The evidence listed above reflects the fact that different ore styles in the Kafang deposit belong to the same mineralization system.  相似文献   

15.
Development of unconventional shale gas wells can generate significant quantities of drilling waste, including trace metal-rich black shale from the lateral portion of the drillhole. We carried out sequential extractions on 15 samples of dry-drilled cuttings and core material from the gas-producing Middle Devonian Marcellus Shale and surrounding units to identify the host phases and evaluate the mobility of selected trace elements during cuttings disposal. Maximum whole rock concentrations of uranium (U), arsenic (As), and barium (Ba) were 47, 90, and 3333 mg kg−1, respectively. Sequential chemical extractions suggest that although silicate minerals are the primary host for U, as much as 20% can be present in carbonate minerals. Up to 74% of the Ba in shale was extracted from exchangeable sites in the shale, while As is primarily associated with organic matter and sulfide minerals that could be mobilized by oxidation. For comparison, U and As concentrations were also measured in 43 produced water samples returned from Marcellus Shale gas wells. Low U concentrations in produced water (<0.084–3.26 μg L−1) are consistent with low-oxygen conditions in the wellbore, in which U would be in its reduced, immobile form. Arsenic was below detection in all produced water samples, which is also consistent with reducing conditions in the wellbore minimizing oxidation of As-bearing sulfide minerals.Geochemical modeling to determine mobility under surface storage and disposal conditions indicates that oxidation and/or dissolution of U-bearing minerals in drill cuttings would likely be followed by immobilization of U in secondary minerals such as schoepite, uranophane, and soddyite, or uraninite as conditions become more reducing. Oxidative dissolution of arsenic containing sulfides could release soluble As in arsenate form under oxic acidic conditions. The degree to which the As is subsequently immobilized depends on the redox conditions along the landfill flow path. The results suggest that proper management of drill cuttings can minimize mobilization of these metals by monitoring and controlling Eh, pH and dissolved constituents in landfill leachates.  相似文献   

16.
Stratabound massive sulfide deposits are widespread along the Middle-Lower Yangtze Metallogenic Belt (MLYMB) and serve as an important copper producer in China. Two contrasting genetic models have been proposed, interpreting the stratabound massive sulfide deposits as a Carboniferous SEDEX protore overprinted by Cretaceous magmatic-hydrothermal system or an Early Cretaceous carbonate replacement deposit. These two contrasting models have been applied to the Xinqiao stratabound Cu-Au sulfide deposit, which is dominated by massive sulfide ores hosted in marine carbonates of the Carboniferous Chuanshan and Huanglong Formations, with minor Cu-Au skarn ores localized in the contact zone between the Cretaceous diorite Jitou stock and the Carboniferous carbonate rocks. New SIMS zircon U-Pb dating suggests that the Jitou stock formed at 138.5 ± 1.1 Ma (2σ, MSWD = 0.6). Pyrite Re-Os dating yields an imprecise date of 142 ± 47 Ma (2σ, MSWD = 7.8). The geochronological data thus constrain the mineralization of the Xinqiao deposit at Early Cretaceous.Fluid inclusions in prograde skarn diopside have homogenization temperatures of 450–600 °C and calculated salinities of 13–58 wt.% NaCl equiv. Quartz from the stratabound ores and pyrite-quartz vein networks beneath the stratabound ores have homogenization temperatures of 290–360 and 200–300 °C, with calculated salinities of 5–12 and 2–10 wt.% NaCl equiv., respectively. Quartz from the skarn ores and veins beneath the stratabound ores have δ18O values of 12.32 ± 0.55 (2 SD, n = 22) and 15.57 ± 1.92‰ (2 SD, n = 60), respectively, corresponding to calculated δ18O values of 6.22 ± 1.59 (2σ) and 6.81 ± 2.76‰ (2σ) for the equilibrated ore-forming fluids. The fluid inclusion and oxygen isotope data thus support a magmatic-hydrothermal origin rather than a SEDEX system for the stratabound ores, with the hydrothermal fluids most likely being derived from the Jitou stock or associated concealed intrusion. Results from this study have broad implications for the genesis and exploration of other stratabound massive sulfide deposits along the MLYMB.  相似文献   

17.
The Cihai iron skarn deposit is located in the southern part of the eastern Tianshan, Xinjiang, northwestern China. The major iron orebodies are banded and nearly parallel to each other. The iron ores are hosted in an early diabase dike and in skarn. Post-ore diabase dikes cut the iron ores and their hosting diabase. Hydrothermal activity can be divided into four stages based on geological and petrographic observations: initial K–Na alteration (stage I), skarn-minor magnetite event (II), retrograde skarn-magnetite main ore event (III), and quartz–calcite–sulfide veining (IV). Zircon U–Pb dating yields ages of 286.5 ± 1.8 Ma for early diabase and 275.8 ± 2.2 Ma for post-ore diabase dikes. Amphibole separated from massive magnetite ore gives a 40Ar–39Ar plateau age of 281.9 ± 2.2 Ma and is the time of ore formation. Formation of the Cihai iron deposit is closely related to post-collisional magmatism and associated Cu–Ni–Au polymetallic mineralization in the eastern Tianshan.  相似文献   

18.
The Dalucao deposit in western Sichuan Province, southwest China, is one of the largest and most extensive rare earth element (REE) deposits in the Himalayan Mianning–Dechang REE Belt. Moreover, this is the only deposit identified in the southern part of the belt. The deposit contains the No. 1, 2, and 3 orebodies. The No. 1 and 3 orebodies are hosted in two breccia pipes within syenite–carbonatite rocks that intrude a Proterozoic quartz–diorite pluton. Both breccia pipes have elliptical horizontal cross-sections at the surface, being 200–400 m long, 180–200 m wide, and extending to > 450 m depth. The No. 1 and No. 3 orebodies have total thicknesses of 55–175 m and 14–58 m, respectively. REE mineralization is associated with four brecciation events that are recorded in both pipes. The ore grades in the No. 1 and 3 orebodies are similar, with the rocks containing 1.0–4.5% rare earth oxides (REOs). The No. 1 orebody is characterized by a mineral assemblage comprising fluorite + barite + celestite + bastnäsite (i.e., Type I), whereas the No. 3 orebody is characterized by an assemblage comprising fluorite + celestite + pyrite + muscovite + bastnäsite + strontianite (i.e., Type II). Significant amounts of weathered high-grade REE ore (up to 60 wt.% of the rock mass) is mainly present in the No. 1 orebody. This is the main ore-type targeted for exploration within the Dalucao deposit, but is rarely present in other deposits in the Mianning–Dechang REE Belt.Faulting and cryptoexplosive breccia events, possibly linked to movement on the Panxi Fault, were more common in the No. 1 orebody than in the No. 3 orebody. This facilitated the introduction of ore-forming hydrothermal fluids and provided space for the precipitation of REE minerals. Based on the present results, we infer that the Dalucao deposit was the product of multiple stages of ore formation. REE minerals formed in envelopes around, or fractures within, quartz, fluorite, calcite, barite, and celestite in the brecciated ores. The main REE minerals were deposited from hydrothermal fluids within cryptoexplosive breccia, followed by weathering that increased the ore grade. Petrographic studies and X-ray powder diffraction (XRD) analyses indicate that the weathered ore contains 5–60% REE minerals (including bastnäsite, parisite, and monazite), together with gangue (quartz, barite, celestite, and fluorite), large amount of clay minerals (smectite, illite, kaolinite, and sepiolite), and relict igneous minerals (quartz, albite, and K-feldspar). The weathered samples are strongly enriched in La (up to 92,390 ppm), Ce (up to 103,500 ppm), Pr (up to 8006 ppm), and Nd (up to 16,690 ppm) compared with the unweathered brecciated ores. Conversely, Sr concentrations are significantly more enriched in the brecciated ores (up to 256,500 ppm) than in the weathered ores (generally less than 2671 ppm with one exception of 37,850 ppm) due to less celestite. Calcite is largely absent from the weathered ores (except one sample with up to 30% mode), which contrasts with the brecciated ores that contain up to 75% calcite. The effects of weathering, oxidation, loss of ions, and hydration on the brecciated ores led to the refertilization of the REEs and an increase in the grade of the ore deposit.  相似文献   

19.
The Hongtoushan volcanogenic massive sulfide (VMS) deposit is the largest Archean Cu–Zn deposit in China, located in the Qingyuan greenstone belt on the northern margin of the North China Craton. The Cu–Zn mineralization was stratigraphically controlled by the interbeds (~ 100 m in thickness) of mafic–felsic volcanic sets and overlain by banded iron layers. However, the relationship between VMS deposits and associated volcanics has not been examined. This study ultimately clarifies the times and sources of the volcanics and mineralization. Based on in situ zircon U–Pb and O isotope on VMS-hosting mafic, felsic volcanic rocks, banded and massive sulfide ores and postmineralization pegmatite vein, we considered that there were two main formation stages for the Qingyuan Cu–Zn deposits; one was exhalative-hydrothermal sedimentation and another was further Cu–Zn enriched by later hydrothermal processes. The timing of the first stage occurred at 2571 ± 6 Ma based on the magmatic zircons in the VMS-hosting mafic volcanic rocks, from which the inherited zircons also indicate the existence of 2.65–3.12 Ga ancient supercrustal rocks in the Qingyuan district. A modern mantle-like δ18Ozircon value of 5.5 ± 0.1‰ (2SD) for this volcanism was well preserved in the inherited core domains of ore samples. It suggests that the mafic volcanics was most likely sourced from partial melting of juvenile crust, e.g., TTG granites. A large-scale metamorphic or hydrothermal event is documented by the recrystallized zircons in sulfide ores. The timing is tightly constrained by the hydrothermal zircon U–Pb ages. They are 2508 ± 4 Ma for the banded ore, 2507 ± 4 Ma for the massive ore and 2508 ± 2 Ma for the postmineralization pegmatite vein. These indistinguishable ages indicate that the 2507 Ma hydrothermal systems played a significant role in the upgrading of the VMS Cu–Zn orebodies. The weighted δ18O values of hydrothermal zircons show a successively increasing trend from 6.0 ± 0.1‰ (2σ) for the banded ore, 6.6 ± 0.2‰ (2σ) for the massive ore to 7.3 ± 0.2‰ (2σ) for the later pegmatite vein. This variation might be induced by gradual inputting of the δ18O-rich oceanic crust and/or oceanic sediment during the hydrothermal cycling system. Considering its modern mantle-like oxygen isotope composition of 2571 Ma volcanism, a submarine volcanic hydrothermal system involving mantle plumes is a preferred setting for the Neoarchean VMS Cu–Zn deposits in the Qingyuan greenstone belt.  相似文献   

20.
The Huangshannan magmatic Ni-Cu sulfide deposit is one of a group of Permian magmatic Ni-Cu deposits located in the southern Central Asian Orogenic belt in the Eastern Tianshan, northwest China. It is characterized by elevated Ni tenor (concentrations in recalculated 100% sulfide) in sulfide within ultramafic rocks (9–19 wt%), with values much higher than other deposits in the region. Sulfides of the Huangshannan deposit are composed of pentlandite, chalcopyrite, and pyrrhotite and the host rock is relatively fresh, indicating that the high-Ni tenor is a primary magmatic feature rather than formed by alteration processes. It is shown that sulfides with high-Ni tenor can be generated by sulfide-olivine equilibrium at an oxygen fugacity of QFM +0.5, for magmas containing 450 ppm Ni and 20% olivine. Ores with >10 wt% sulfur have relatively low PGE and Ni tenors compared to other ores, R factor (mass ratio of silicate to sulfide liquid) modeling of Ni indicates that they formed at moderate R values (150–600). Based on this constraint on R values, ores with <10 wt% sulfides in the Huangshannan deposit can be segregated from a similar parental magma with 0.05 ppb Os, 0.023 ppb Ir, and 0.5 ppb Pd at R values between 600 and 3000. This, coupled with the supra-cotectic proportions of sulfide liquid to cumulus silicates in the Huangshannan ores imply mechanical transport and deposition of sulfide liquid in a magma pathway or conduit, in which sulfides must have interacted with large volumes of silicate magma. Platinum and Pd depletion relative to other platinum group elements (PGEs) are observed in fresh and sulfide-rich samples (S > 4.5 wt%). As sulfide-rich samples are also depleted in Cu, and as interstitial sulfides in those samples are physically interconnected at a scale of several cms, the low Pt and Pd anomalies are attributed to solid Pt and Pd phases crystallization and retention with the monosulfide solid solution (MSS) and Cu-rich sulfide liquid percolation during MSS fractionation. This finding indicates that Pt anomalies in sulfide-rich rocks from magmatic Ni-Cu deposits in the Eastern Tianshan are the result of sulfide fractionation rather than a hydrothermal effect. 187Os/188Os(278Ma) values of the lherzolite samples vary from 0.27 to 0.37 and γOs(278Ma) values vary from 110 to 189, indicating significant magma interaction with crustal sulfides, rich in radiogenic Os. Well constrained γOs values and δ34S values (−0.4 to 0.8‰) indicate that crustal contamination occurred at depth before the arrival of the magma in the Huangshannan chamber. Regionally, deposits with high-Ni tenor have not been reported other than the Huangshannan deposit; however, many intrusions with high-Ni contents in olivine are present in NW China, such as the Erhongwa, Poyi and Poshi intrusions. Those intrusions are capable of forming high-Ni tenor sulfides due to olivine-sulfide-silicate equilibrium and relative high-Ni content in parent magma, making them attractive exploration targets.  相似文献   

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