葡萄牙NeVes COrVO块状硫化物矿床锡石的微量元素地球化学

对葡萄牙Neves Corvo Cu.Sn多金属矿床锡矿石，富铜硫化物矿石和贫铜硫化物矿石中锡石的微量元素电子探针分析结果的综合研究表明，该矿床存在高温（＞300度），富W的早期锡矿化阶段，钞晚的贫W，富Cu，温度略低（245－295度）的Cu,Sn主矿化阶段，以旬晚的贫W，贫Cu温度更低（约200度）的Cu,Sn矿化阶段，结合Pb同位素研究可以推测矿床中Sn可能来源于矿体下部深处未出露的，与板块俯冲有关的富Sn古老地壳岩石，与其他类型锡矿床的微量元素对比表明，Neves Corvo矿床属于处于火山岩容矿（VHMS）型和沉积岩容矿（SHMS）型块状硫化物矿床之间的一种过渡类型－－伊比利亚型。     

Actively forming Kuroko-type volcanic-hosted massive sulfide (VHMS) mineralization at Iheya North,Okinawa Trough,Japan

Modern seafloor hydrothermal systems provide important insights into the formation and discovery of ancient volcanic-hosted massive sulfide (VHMS) deposits. In 2010, Integrated Ocean Drilling Program (IODP) Expedition 331 drilled five sites in the Iheya North hydrothermal field in the middle Okinawa Trough back-arc basin, Japan. Hydrothermal alteration and sulfide mineralization is hosted in a geologically complex, mixed sequence of coarse pumiceous volcaniclastic and fine hemipelagic sediments, overlying a dacitic to rhyolitic volcanic substrate. At site C0016, located adjacent to the foot of the actively venting North Big Chimney massive sulfide mound, massive sphalerite-(pyrite-chalcopyrite ± galena)-rich sulfides were intersected (to 30.2% Zn, 12.3% Pb, 2.68% Cu, 33.1 ppm Ag and 0.07 ppm Au) that strongly resemble the black ore of the Miocene-age Kuroko deposits of Japan. Sulfide mineralization shows clear evidence of formation through a combination of surface detrital and subsurface chemical processes, with at least some sphalerite precipitating into void space in the rock. Volcanic rocks beneath massive sulfides exhibit quartz-muscovite/illite and quartz-Mg-chlorite alteration reminiscent of VHMS proximal footwall alteration associated with Kuroko-type deposits, characterized by increasing MgO, Fe/Zn and Cu/Zn with depth. Recovered felsic footwall rocks are of FII to FIII affinity with well-developed negative Eu anomalies, consistent with VHMS-hosting felsic rocks in Phanerozoic ensialic arc/back-arc settings worldwide.Site C0013, ∼100 m east of North Big Chimney, represents a likely location of recent high temperature discharge, preserved as surficial coarse-grained sulfidic sediments (43.2% Zn, 4.4% Pb, 5.4% Cu, 42 ppm Ag and 0.02 ppm Au) containing high concentrations of As, Cd, Mo, Sb, and W. Near surface hydrothermal alteration is dominated by kaolinite and muscovite with locally abundant native sulfur, indicative of acidic hydrothermal fluids. Alteration grades to Mg-chlorite dominated assemblages at depths of >5 mbsf (metres below sea floor). Late coarse-grained anhydrite veining overprints earlier alteration and is interpreted to have precipitated from down welling seawater as hydrothermal activity waned. At site C0014, ∼350 m farther east, hydrothermal assemblages are characterized by illite/montmorillonite, with Mg-chlorite present at depths below ∼30 mbsf. Recovered lithologies from distal, recharge site C0017 are unaltered, with low MgO, Fe₂O₃ and base metal concentrations.Mineralization and alteration assemblages are consistent with the Iheya North system representing a modern analogue for Kuroko-type VHMS mineralization. Fluid flow is focussed laterally along pumiceous volcaniclastic strata (compartmentalized between impermeable hemipelagic sediments), and vertically along faults. The abundance of Fe-poor sphalerite and Mg-rich chlorite (clinochlore/penninite) is consistent with the lower Fe budget, temperature and higher oxidation state of felsic volcanic-hosted hydrothermal systems worldwide compared to Mid Ocean Ridge black smoker systems.     

Volcanic lithogeochemistry and alteration at the Delbridge massive sulfide deposit, Noranda, Quebec

The Delbridge orebody occurs within a thick sequence (> 1 km) of porphyritic to aphyric massive rhyolite and rhyolite breccia of the Archean Blake River Group. The orebody produced ≈ 370,000 tonnes grading 0.61% Cu, 9.6% Zn, 110 g/t Ag and 2.1 g/t Au (1969–1971). The footwall consists of massive quartz porphyritic rhyolite mantled by proximal rhyolite breccias. An irregular chloritic alteration pipe with mineralization is subvertical to the ore lens. The orebody occurs at a thick cherty horizon within rhyolite breccia, and is overlain by a succession of mafic debris flows, porphyritic to aphyric massive rhyolite flows, and finally andesite. The main alteration assemblage in the rhyolite units is quartz-albite-sericite-chlorite-carbonate. Immobile element plots and rare-earth element data indicate that the footwall rhyolite flows and proximal breccias are tholeiitic to transitional (Zr/Y = 3.5–5.5; La_N/Yb_N = 1.7–2.6), whereas hangingwall rhyolite flows are mildly calc-alkaline (Zr/Y = 6.5–7.5; La_N/Yb_N = 2.8–3.8). These two rhyolite types also have separate alteration lines in Ti-Zr space and in various immobile element plots. The identification of chemically different rhyolites above and below the orebody provides markers that can be identified and traced even where strongly altered. An intrusive rhyolite mass in the footwall is chemically identical to the hangingwall aphyric rhyolite flows, and is interpreted as the feeder to these flows. Calculated mass changes in the footwall rhyolite commonly are large, and result from major silica change (±30%), significant loss of Na₂O + CaO, and important additions of K₂O and FeO + MgO. The margins of the pipe show net mass gain, whereas the interior of the pipe shows net mass loss. Hangingwall rhyolite shows mass changes that generally are much smaller than in the footwall. Felsic rocks in the silica-sericite alteration zone up to ≈ 200 m from the orebody have high δ¹⁸O values of 10–12‰, reflecting low-temperature alteration. The orebody occurs near the contact between a mainly tholeiitic rhyolite footwall and an overlying sequence of mildly calc-alkaline rhyolite then andesite.     

An investigation of aspects of mine waste from a kyanite mine,Central Virginia,USA

Kyanite Mining Corporation, located in Dillwyn, Virginia has been in operation for over 50 years and their local operation is the largest kyanite mine in the world. As part of the processing at this location, a magnetic separate is generated and a minimum estimation of 3.57 million tons of waste has accumulated. Currently no use for the magnetic separate has been identified. We investigated eight representative samples of the magnetic mine waste which varied in color from a dark tan to black, to determine if the waste could be recycled as an ore or could be used as an environmental media. Mineralogical investigations indicate the composition of the magnetic mine waste is dominated by magnetite, kyanite, lesser amounts of hematite and charcoal. Magnetite occurs as fine grained crystals and as inclusions in kyanite. Hematite occurs largely as botryoidal textures, as discrete grains, and as coatings on kyanite grains. Fe-oxide spheres ranging in diameter from approximately 5–100 μm are common and may compose up to 10% in some samples. Titanium dioxide was rarely observed as coatings on silicate mineral grains. Energy dispersive spectroscopy analysis on magnetite crystals indicates they have end-member compositions. Bulk property investigations indicate that grain size distributions of samples are primarily unimodal with 20–40% of material being between 0.600 and 0.250 mm. Hydraulic conductivity values of samples investigated vary between 0.0036 and 0.0077 cm/s and are broadly consistent with those expected of sands with similar grain size distributions. In addition to the magnetic waste stream a light blue, water soluble, amorphous Cu sulfate occurs as a coating on surfaces of boulders. The coating is composed of rounded interlocking particles 5–60 μm in diameter. This material is of some environmental concern for freshwater invertebrates, but can be managed using sorption media. Hyperspectral data were gathered of the magnetic separate, kyanite ore samples, and the light blue Cu sulfate. The signatures of the kyanite ore, the blue mineral coating, and a mixture of the two provide spectral fingerprints that an imaging spectrometer could exploit for rapid detection and subsequent environmental monitoring.     

青海锡铁山块状硫化物矿床地质特征

钖铁山铅锌矿床是我国西北地区五十年代末期勘探成功的大型矿床之一。在前人工作与积累的大量资料的基础上,1981—1983年间我们通过进一步调查研究,对钖铁山矿床地质背景、矿床特征及其成因归属等方面有了一些新的认识。     

Environmental impacts of the abandoned mercury mine in Podljubelj, Slovenia

The Podljubelj mercury mine lies in the NW part of Slovenia. The ore is of hydrothermal-vein type. The ore deposit was exploited between the years 1557 and 1902. Total production of the mine was 110000 tons of ore （360 tons of Hg）. A smelter located close to the mine had been in operation since 1855. The waste material from the mine and the smelter was dumped in close vicinity of the mine. Total quantity of the waste has been estimated at 170000 tons. In order to establish environmental impacts, soil and stream sediment samples were investigated. Soil samples were collected at two different depths （horizons A and B） in a 100 m grid within an 88 ha area. In the vast area also 11 samples of stream sediments were considered. Heavy metals were determined by means of cold vapor atomic absorption spectrometry CV-AAS after aqua regia digestion. Based on the chemical analyses of samples, the estimated mercury mean for soils is 3.67 mg/kg （0.35-244 mg/kg） for horizon A and 1.39 mg/kg （0.17-71.7 mg/kg） for horizon B. The estimated mercury mean for stream sediments is 0.64 mg/kg （0.065-1.36 mg/kg）. The concentrations of mercury in soils generally decrease with depth and distance from the mine. The highest content of Hg was determined in a sample taken in the immediate vicinity of the smelter （719 mg/kg）. The results have shown that on the 9 ha of the study area, the contents of Hg in soils exceeded the officially set limit value for soils （10 mg/kg）. High contents of Hg in soil around the abandoned smelter are a consequence of former atmospheric emissions and technological losses. High contents of Hg were also found in the mine and smelter waste dump. At the edges of the study area and in the samples of stream sediments, Hg concentrations are low.     

Physicochemical parameters of magmatic and hydrothermal processes at the Yaman-Kasy massive sulfide deposit, the southern Urals

Melt and fluid inclusions in minerals have been studied and physicochemical parameters of magmatic processes and hydrothermal systems estimated at the Yaman-Kasy copper massive sulfide deposit in the southern Urals. It was established that relatively low-temperature (910–945°C) rhyodacitic melts belonging to the tholeiitic series and containing 2.7–5.2 wt % water participated in the formation of the igneous complexes that host the Yaman-Kasy deposit. As follows from ion microprobe results, these silicic magmas had a primitive character. In the distribution of trace elements, including REE, the rhyodacites are closer to basaltic rather than silicic volcanic rocks, and they are distinguished in this respect from the igneous rocks from other massive sulfide deposits of the Urals and the Rudny Altai. Two types of solutions actively took part in the formation of hydrothermal systems: (1) solutions with a moderate salinity (5–10 wt % dissolved salts) and (2) solutions with a low salinity (a value close to that of seawater or even lower). Concentrated fluids with more than 11.5 wt % dissolved salts were much less abundant. Hydrothermal solutions heated to 130–160, 160–270, or occasionally 280–310°C predominated in ore formation. The sequence of mineral-forming processes at the Yaman-Kasy deposit is demonstrated. Mineral assemblages were formed with an inversion of the parameters characterizing ore-forming solutions. An increase in the temperature and salinity of solutions at the early stages was followed by a decrease at the final stages. The evolution of the hydrothermal system at the Yaman-Kasy deposit has much in common with the parameters of black smokers in the present-day Pacific backarc basins.     

Environmental geochemistry of Zarshuran Au-As deposit, NW Iran

Zarshuran deposit is the most famous and important As-Au mine in Iran. However, there is no information on the impact of mining activity on the surrounding environment, especially on water systems. This paper attempts to document the concentration of arsenic and associated elements in waters and sediments resulting from the mining history of Zarshuran, a period covering hundreds of years. Water and sediment samples collected from Zarshuran Stream indicate high content of some potentially toxic elements, especially of As which ranges from 0.028 to 40 ng/l in water and 182 to 36,000 mg/kg in sediment samples. Mining activity, exposure of a large volume of mining wastes to weathering, and the anomalously high background of trace metals in the mining area are considered to be the main sources of heavy metal pollution.     

Environmental geochemistry of the Bingham Canyon porphyry copper deposit,Utah

At the Bingham Canyon porphyry copper deposit, sulfide mineralization progresses outward from a low-grade core through the following general zones: (1) molybdenite, (2) chalcopyrite-bornite, (3) chalcopyrite-pyrite, (4) pyrite, and (5) sphalerite-galena. The low-grade core and the molybdenite zone are composed of net neutralizing rock and will generally not acidify when exposed to surface weathering conditions. The copper-bearing zones of the orebody and the surrounding pyrite halo are net acid-generating and so will tend to acidify when exposed. Rocks in the lead-zinc halo are typically net neutralizing. In plan view, the distribution of net neutralization potential (NNP) is doughnut-shaped, with a positive (net neutralizing) 1,000-m-diameter core surrounded by a negative (net acid-generating) 3,000-m-diameter ring. Rock exposed in the lower 100 m of the current pit has a positive NNP and is overlain by 500 m of rock with a negative NNP.     

Vanadium mineralization in ore of the Vihanti massive sulfide base-metal deposit,Finland

A series of vanadium oxides—shcherbinaite, karelianite, kyzylkumite, coulsonite, and berdesinskiite—was found in association with pyrrhotite in pyrite-pyrrhotite ore from the Paleoproterozoic Vihanti massive sulfide deposit of the Kuroko-type. It is suggested that enrichment in vanadium of massive sulfide ore from the Vihanti deposit is a result of their metamorphogenic regeneration and pyrrhotinization at the expense of rocks and ore enriched in vanadium. The list of rare minerals in massive sulfide ore has been extended.     

Formation and decay of a modern massive sulfide deposit in the Indian Ocean

In December 1993, the first massive sulfides were recovered from the Indian Ocean floor, north of the Rodrigues Triple Junction. The polymetallic deposit is situated in the fourth Central Indian Ridge segment, close to the rift axis; it is hydrothermally no longer active. The deposit appears to be typical of mid-ocean ridge massive sulfide occurrences but is in a phase of disintegration and about to be buried by sediment. The chimney structures were formed by multiple hydrothermal events and are now degraded by mass wasting showing various stages of weathering. Later-stage, low-temperature hydrothermal mineralization processes led to copper and gold enrichment. Here we report on the geological setting, mineral zonation, different sulfide types and stages of formation of the “Sonne Sulfide Field”, which is part of a larger mineralized zone. Received: 20 October 1997 / Accepted: 4 December 1997     

Age and depositional environment of the Draa Sfar massive sulfide deposit, Morocco

The Draa Sfar mineralization consists of two main stratabound orebodies, Sidi M’Barek and Tazacourt, located north and south of the Tensift River (“Oued Tessift”), respectively. Each orebody is comprised by at least two massive sulfide lenses. The hosting rocks are predominantly black shales, although minor rhyolitic rocks are also present in the footwall to the southern orebody. Shales, rhyolitic volcanic rocks, and massive sulfides are all included into the Sarhlef Series, which is recognized as one of the main stratigraphic units of the Moroccan Variscan Meseta. Hydrothermal activity related with an anomalous thermal gradient, together with a high sedimentation rate in a tectonically driven pull-apart marine basin, favored the accumulation of organic-rich mud in the deepest parts of the basin and the sedimentary environment suitable for massive sulfide deposition and preservation. This took place by replacement of the hosting unlithified wet mud below the sediment–water interface. Geochemical data suggest a sedimentary environment characterized by oxic water column and anoxic sediment pile with the redox boundary below the sediment–water interface. The low oxygen availability within the sediment pile inhibited oxidation and pyritization of pyrrhotite. Biostratigraphic analysis, based on the palynological content of the hosting black shales, restricts the age of the sulfides to the Asbian substage (mid-Mississippian). This age is consistent with earlier geochronological constraints.     

云南大平掌铜多金属矿床成矿作用

云南大平掌矿床位于澜沧江火山岩带的中南段,左侧是澜沧江和酒房深大断裂。矿区内发育一套形成于岛弧环境的上石炭统细碧-石英角斑岩系,矿体产于流纹质火山岩中,产状与火山岩一致。矿体分2类,上部为块状矿体,下部为细脉-浸染状矿体。矿床内热液蚀变发育,特别是浸染状矿体中更强,并从矿体中心向外侧形成分带。具工业意义的Cu、Pb、Zn等元素以硫化物形式产出。S、Pb、Sr、Nd等同位素成分表明,成矿物质来源于地幔-下地壳。尽管矿体受后期构造破坏强烈,但综合研究表明,该矿床仍具有世界上绝大多数火山成因块状硫化物矿床的共同性。它与区内类似矿床的差异性,为在该区寻找火山成因块状硫化物矿床开辟了新方向。     

新疆阿舍勒块状硫化物矿床成矿特征及形成环境

阿舍勒块状硫化物矿床位于阿尔泰华力西地槽系南缘。容矿岩石为中、下泥盆统富钠的火山岩系，为双峰式火山岩组合，系弧后扩张背景下的产物。矿床具双层结构，并具明显的垂向分带和侧向分带。矿体下盘火山岩发生了强烈地蚀变作用，形成由石英＋绢云母＋绿泥石±黄铁矿组成的半整合蚀变带。同位素研究表明，硫由海水硫酸盐和岩石中硫化物所提供，铅具深源的特征。通过对比，认为阿舍勒矿床与矿区阿尔泰的块状硫化物矿床相似     

Mineralogical and geochemical zoning and genesis of massive sulfide ores at the Oktyabr’sky deposit

Fractional crystallization and emanation differentiation of sulfide magma and related mineralogical and geochemical zoning are exemplified in massive sulfide ores of the Oktyabr’sky deposit, Noril’sk district. The mineralogical zoning is expressed in the change of mineral types of ore from pyrrhotite (Po) to chalcopyrite (Cp) (from the flanks to the center of the ore lode). In terms of geochemistry, the Cu content, Cu/(Cu + Ni) ratio, and contents of noble metals incompatible with Mss (Pt, Pd, and Au) increase in this direction, while the S and Fe contents decrease. The distribution of elements compatible with Mss (Ir, Os, Rh, and Ru) is more complex. Their contents decrease from Po to high-Cu Cp ore, although there is a second maximum for Cb-type ore. The distribution of ore elements in the vertical and horizontal sections of massive ores at the deposit is different. The upper outer contact zone and frontal parts of massive ore lodes are enriched in all ore elements and a light sulfur isotope. The succession of enrichment is correlated with the relative affinity for sulfur and remains independent of the affinity of these elements for Mss (Pd-Rh, Os-Au). The possible role of liquid immiscibility of sulfide magma in the development of the mineralogical and geochemical zoning of massive ore is discussed.     

祁连山拉水峡铜镍硫化物矿床矿物学、地球化学及成因

拉水峡中型铜镍矿床几乎全岩矿化。矿石矿物学、矿床地球化学的研究表明,矿石中金属硫化物以紫硫镍铁矿、黄铁矿、黄铜矿为主,热液作用使原生硫化物组合发生了改变,低温热液特征的元素As、Se、Ag、Te富集; 矿石中Ni含量远高于Cu含量,不同类型矿石均属轻稀土富集型,反映了相同的岩浆成因,部分熔融来源特点。热液改造致使块状矿石中Cu/Ni、Ni/Co比值较高,REE分馏程度明显高于原生浸染状矿石;矿石中铂族元素含量平均为2460.5×10-9,具有较高的Ir含量和低的Pd/Ir比值特点,铂族元素与岩浆深部融离作用密切相关,块状矿石Pd/Ir比值和(Pt+Pd)/(Os+Ir+Ru)比值均高于原生浸染状矿石,表明热液作用对Cu、Pt、Pd金属元素富集具有一定作用;岩浆期后流体属中低温度（180～244℃）、中等盐度（8.81～14.67%NaCl）、中等密度（0.86～0.95g/cm3）范围, CH4+N2+CO2成分组合,具有岩浆流体成分特征。综合分析认为,拉水峡矿床主体成因可能仍以岩浆深部曾有过较彻底的硫化物不混熔作用为主,后期经历了热液作用改造。     

Influence of water chemistry on the distribution of an acidophilic protozoan in an acid mine drainage system at the abandoned Green Valley coal mine,Indiana, USA

Euglena mutabilis, a benthic photosynthetic protozoan that intracellularly sequesters Fe, is variably abundant in the main effluent channel that contains acid mine drainage (AMD) discharging from the Green Valley coal mine site in western Indiana. Samples of effluent (pH 3.0–4.6) taken from the main channel and samples of contaminated stream water (pH 3.3 to 8.0) collected from an adjacent stream were analyzed to evaluate the influence of water chemistry on E. mutabilis distribution. E. mutabilis communities were restricted to areas containing unmixed effluent with the thickest (up to 3 mm) benthic communities residing in effluent containing high concentrations of total Fe (up to 12110 mg/l), SO₄ (up to 2940 mg/l), Al (up to 1846 mg/l), and Cl (up to 629 mg/l). Communities were also present, but much less abundant, in areas with effluent containing lower concentrations of these same constituents. In effluent where SO₄ was most highly concentrated, E. mutabilis was largely absent, suggesting that extremely high concentrations of SO₄ may have an adverse effect on this potentially beneficial Fe-mediating, acidophilic protozoan.     

The geochemistry of mafic metavolcanics: implications for the origin of the Devonian massive sulfide deposits at Zlaté Hory,Czechoslovakia

Mafic metavolcanic rocks in the area of the Zlaté Hory massive sulfide deposits are interpreted as convergent plate-margin basalts and basaltic andesites metamorphosed to the greenschist facies. According to the major- and trace-element compositions the metabasites exhibit island-arc tholeiitic to low-K, calc-alkaline composition.Approximately 50% of samples of maifc metavolcanics studied have a salient negative anomaly of Ce in chondrite-normalized REE patterns. The Ce-depleted greenschists are thought to represent hydrothermally altered equivalents of metabasites of island-arc tholeiitic composition. The alteration was accompanied by the sulfide mineralization. That is indicated by enrichment in Ba and S together with correlation of the Ce/Ce* values and CO₂ abundances in the Ce-depleted rocks. The Ce anomaly may be caused by alteraton of ore-forming, seawaterderived solutions. The occurrence of Ce-depleted greenschists supports the hypothesis of the volcanogenic origin of the ore deposits in the Zlaté Hory area.