Paragenesis and geochemistry of ore minerals in the epizonal gold deposits of the Yangshan gold belt,West Qinling,China

Six epizonal gold deposits in the 30-km-long Yangshan gold belt, Gansu Province are estimated to contain more than 300 t of gold at an average grade of 4.76 g/t and thus define one of China's largest gold resources. Detailed paragenetic studies have recognized five stages of sulfide mineral precipitation in the deposits of the belt. Syngenetic/diagenetic pyrite (Py₀) has a framboidal or colloform texture and is disseminated in the metasedimentary host rocks. Early hydrothermal pyrite (Py₁) in quartz veins is disseminated in metasedimentary rocks and dikes and also occurs as semi-massive pyrite aggregates or bedding-parallel pyrite bands in phyllite. The main ore stage pyrite (Py₂) commonly overgrows Py₁ and is typically associated with main ore stage arsenopyrite (Apy₂). Late ore stage pyrite (Py₃), arsenopyrite (Apy₃), and stibnite occur in quartz ± calcite veins or are disseminated in country rocks. Post-ore stage pyrite (Py₄) occurs in quartz ± calcite veins that cut all earlier formed mineralization. Electron probe microanalyses and laser ablation-inductively coupled plasma mass spectrometry analyses reveal that different generations of sulfides have characteristic of major and trace element patterns, which can be used as a proxy for the distinct hydrothermal events. Syngenetic/diagenetic pyrite has high concentrations of As, Au, Bi, Co, Cu, Mn, Ni, Pb, Sb, and Zn. The Py₀ also retains a sedimentary Co/Ni ratio, which is distinct from hydrothermal ore-related pyrite. Early hydrothermal Py₁ has high contents of Ag, As, Au, Bi, Cu, Fe, Sb, and V, and it reflects elevated levels of these elements in the earliest mineralizing metamorphic fluids. The main ore stage Py₂ has a very high content of As (median value of 2.96 wt%) and Au (median value of 47.5 ppm) and slightly elevated Cu, but relatively low values for other trace elements. Arsenic in the main ore stage Py₂ occurs in solid solution. Late ore stage Py₃, formed coevally with stibnite, contains relatively high As (median value of 1.44 wt%), Au, Fe, Mn, Mo, Sb, and Zn and low Bi, Co, Ni, and Pb. The main ore stage Apy₂, compared to late ore stage arsenopyrite, is relatively enriched in As, whereas the later Apy₃ has high concentrations of S, Fe, and Sb, which is consistent with element patterns in associated main and late ore stage pyrite generations. Compared with pyrite from other stages, the post-ore stage Py₄ has relatively low concentrations of Fe and S, whereas As remains elevated (2.05～3.20 wt%), which could be interpreted by the substitution of As^? for S in the pyrite structure. These results suggest that syngenetic/diagenetic pyrite is the main metal source for the Yangshan gold deposits where such pyrite was metamorphosed at depth below presently exposed levels. The ore-forming elements were concentrated into the hydrothermal fluids during metamorphic devolatilization, and subsequently, during extensive fluid–rock interaction at shallower levels, these elements were precipitated via widespread sulfidation during the main ore stage.     

Sulfide — carbonate relationships in the Navan (Tara) Zn-Pb deposit,Ireland

Samples from the mineralized micrite, the bottom part of the 1–5 lens were investigated. They contain Zn and Fe bearing low Mg-calcite, dolomite, Fedolomite, minrecordite-CaZn (CO₃)₂, sphalerite, pyrite, melnikovite and overgrown quartz. — Zn-dolomite consists probably of CaMg (CO₃)₂ and CaZn (CO₃)₂ domains about 10×35 nm in size. Zn-dolomite is sulfidized (replaced by ZnS) which is demonstrated by both reflected light and electron microscope methods. — CaZn (CO₃)₂ from the Navan ore has cell parameters: a₀=0.484±0.004 and c₀=1.608±0.012 nm and is rhombohedral. It forms close, tiny intergrowths with calcite. — Base metals at Navan were exhaled to form at least partly carbonate minerals which subsequently reverted to sulfides in the diagenetic environment. The reversion of base metals carbonates to sulfides is connected with reduction in volume. The reduction in volume allowed the ore zone to retain its permeability after lithification of the host rock. It allowed lateral flow of hydrothermal solutions, which deposited further generations of sulfides and increased the base metal content producing a high grade ore.     

Chemistry and Sulfur Isotopes of the Chert-Clastic Sequence Surrounding the Kajika Massive Sulfide Ores at the Ashio Copper Mine, Ashio Terrane, Central Japan

Abstract. Chemical and sulfur isotopic compositions were obtained for a series of rocks within the chert‐clastic sequence surrounding the Kajika massive sulfide ore horizon at Shibukawasawa in the Ashio copper‐mining district, Ashio Terrane, central Japan. The sequence is lithologically classified into three units: chert, siliceous shale with basic volcanics, and sandstone‐shale, in ascending stratigraphic order. The Kajika ore horizon corresponds to the lowermost part of the unit that contains siliceous shale with basic volcanics. The rocks around the Kajika ore horizon are enriched in P₂O₅ (max. 0.22 %), Ba (max. 2400 ppm), Cu (595 ppm), V (323 ppm), Pb (168 ppm), Zn (124 ppm), and Mo (24 ppm) in siliceous shale; and Ba (4220 ppm), Zr (974 ppm), Cr (718 ppm), Ni (492 ppm), V (362 ppm), Zn (232 ppm), Nb (231 ppm), and Co (71 ppm) in the basic volcanics. The siliceous shale is enriched in a number of redox‐sensitive elements such as Cu, V, Pb, Zn, and Mo, which are known to be enriched in black shale and anoxic and hydrothermal sediments. The δ³⁴S values of sulfides in the chert and sandstone‐shale lie in the range of 0±2 %, and those in the siliceous shale range from ‐5 to ‐14 %. The measured δ³⁴S values in the basic volcanics are ‐0.3, ‐2.7, and ‐31.5 %. These heavier δ³⁴S signatures (around 0 %) recorded throughout the sequence indicate that the rocks formed under anoxic bottom‐water conditions. Slightly lighter δ³⁴S values recorded in siliceous shale might reflect significant mixing of sulfides that formed by sulfate‐reducing bacteria in an overlying oxic environment. The long‐term duration of anoxic conditions indicated by the heavier δ³⁴S signature is considered to have played an important role in protecting the Kajika sulfide ores from oxidative decomposition and preserving the ores in sedimentary accumulations.     

Germanium-bearing Colusite in Siliceous Black Ore from the Ezuri Kuroko Deposit, Hokuroku District, Japan

Abstract. Germanium‐bearing colusite occurs with sphalerite, galena, tetrahedrite‐tennantite, chalcopyrite and pyrite in microdruses and veinlets in the siliceous black ore from the Ezuri Kuroko deposit in the Hokuroku district of Japan. X‐ray microdiffractometry of this mineral gives strongest lines at 1.60, 1.32 and 1.09 Å, which are consistent with the known powder diffraction data of colusite. On the basis of 32 S atoms per formula unit, electron microprobe analyses yield empirical chemical formulae of (Cu_{24 0}Fe_0.3Zn_1.0)_σ25.3V_1.9(A_s4.8Sb_0.2)_σ5.0Ge _1.3S₃₂ for Ge‐bearing colusite in close association with sphalerite, and (Cu_24.6Fe_0.9)_σ25.4V_1.8(A_s4.1 Sb_0.2)_σ4.3Ge_1.7S₃₂ for that coexisting with chalcopyrite, consistent with the ideal formula of Cu_24+xV₂(As, Sb)_6‐x(Sn, Ge)_xS₃₂ (x = 0 to 2) proposed by Spry et al. (1994) for this mineral species. The Ge‐bearing colusite mineralization is suggested to have occurred concurrently with consolidation of the siliceous black ore, possibly during hydrothermal modification in association with the igneous activity of the Ohtaki quartz diorite of the later Onnagawa stage. It is likely that biogenic siliceous ooze, a possible precursor of the siliceous black ore, may have served as an in situ source of Ge as well as other essential rare elements, leading to the formation of Ge‐bearing colusite during transformation or recrystallization of biogenic opal into a‐quartz.     

Surface analysis of pyrite in the No. 9 coal seam, Wuda Coalfield, Inner Mongolia, China, using high-resolution time-of-flight secondary ion mass-spectrometry

The chemical composition of pyrite in coal can be used to investigate its geological and mineralogical origin. In this paper, high-resolution time-of-flight secondary ion mass spectrometry (TOF-SIMS) was used to study the chemical composition of various pyrite forms in the No. 9 coal seam (S_t,d=3.46%) from the Wuda Coalfield, Inner Mongolia, northern China. These include bacteriogenic, framboidal, massive, cell-filling, fracture-filling, and nodular pyrites. In addition to Fe⁺ (⁵⁴Fe⁺, ⁵⁶Fe⁺, ⁵⁷Fe⁺), other fragment ions were detected in bacteriogenic pyrites, such as ²⁷Al⁺, Si⁺ (²⁸Si⁺, ²⁹Si⁺, ³⁰Si⁺), ⁴⁰Ca⁺, Cu⁺ (⁶³Cu⁺, ⁶⁵Cu⁺), Zn⁺ (⁶⁴Zn⁺, ⁶⁶Zn⁺, ⁶⁷Zn⁺, ⁶⁸Zn⁺), Ni⁺ (⁵⁸Ni⁺, ⁶⁰Ni⁺, ⁶²Ni⁺), and C₃H₇⁺. TOF-SIMS images show bacteriogenic pyrites are relatively rich in Cu, Zn, and Ni, suggesting that bacteria probably play an important role in the enrichment of Cu, Zn, and Ni during their formation. Intense positive secondary ion fragments from framboidal aggregates, such as ²⁷Al⁺, ²⁸Si⁺, ²⁹Si⁺, AlO⁺, CH₂⁺, C₃H₃⁺, C₃H₅⁺, and C₄H₇⁺, indicate that formation of the framboidal aggregates may have occurred together with clay mineral and organic matter, which probably serve as the binding substance. The intense ions of ²⁸Si⁺ and ²⁷Al⁺ from massive pyrites also suggest that their pores incorporated clay minerals during crystallization. Together with the lowest ²⁸Si⁺/²³Na⁺ value, the intense organic positive secondary ion peaks from cell-filling pyrites, such as C₃H₃⁺, C₃H₅⁺, C₃H₇⁺, and C₄H₇⁺, indicate that pyrite formation may have accompanied dissolution or disintegration of the cell. The intense P⁺ peak was observed only in the fracture-filling pyrite and the highest ²⁸Si⁺/²³Na⁺ value of fracture-filling pyrite reflects its epigenetic origin. Together with XRD and REEs data, the stronger ⁴⁰Ca⁺ in nodular pyrite than other pyrite forms shows seawater influence during its formation.     

Hydrothermal Fossilization of Microorganisms at the Earth's Surface in Iceland

The fossilization of biota and formation of low- and high-temperature hydrothermally altered rocks were studied in solfataric fields, artificial hot lakes, at natural hot springs, and on heated beach within the present-day rift zone at the Reykjanes, Nesjavellir, Geysir, Landmannalaugar, Namafjall, and Oxarfjodur geothermal areas. The hydrothermally altered rocks can be divided into the following mineral types: (1) smectite assemblage with iron oxides and hydroxides; (2) smectite assemblage with sulfides (pyrite); (3) kaolinite-metahalloysite assemblage with sulfates, anatase, and boehmite; and (4) siliceous assemblage. The detailed study of the hydrothermally altered rocks allowed us to elucidate some environmental features of modern fossilization and replacement of organic matter with clay minerals, iron oxyhydroxides, and silica. The fossilized microstructures have been described in rocks of the smectite and siliceous assemblages. It has been shown that the pseudobiomorphic (actually, abiogenic) micro- and nannostructures are formed in the moving water of silica deposition zone.     

Zinccopperite-A New Variety of Zinc-CopperIntermetallic Compounds Discovered in aPorphyry-Copper Deposit

Zinccopperite (tentatively named) is a rare native alloy mineral discovered in quartz monzonite-porphyry in the Xifanping area, Yanyuan County, Sichuan Province. It is a new variety of zinc-copper alloy mineral found for the first time in the porphyry-copper deposit in China. Its intergrown minerals are K-feldspar (mainly perthite), albite-oligoclase, quartz and biotite; and the associated minerals include pyrite and chalcopyrite. It is characterized by a golden reflection colour, being isotropic (isometric), with the grain size ranging from 10 to 50 μm, microhardness VHN10= 190 kg/mm2, and reflectance RVis= 67.97%. Electron microprobe (Model JXA-733) analysis shows Cu = 59.15%-62.55% and Zn= 36.32%-39.85%. The crystallochemical formula is Cu6.27-7.0Zn4.0, simplified as Cu7Zn4.     

Experimental Study on Surface Reactions of Heavy Metal Ions With Quartz—Aqueous Ion Concentration Dependence

Adsorption of divalent metal ions, including Cu²⁺, Pb²⁺, Zn²⁺, Cd²⁺ and Ni²⁺, on quartz surface was measured as a function of metal ion concentration at 30°C under conditions of solution pH= 6. 5 and ion strength I = 0. 1mol/L. Results of the experimental measurements can be described very well by adsorption isotherm equations of Freudlich. The correlation coefficients (r) of adsorption isotherm lines are > 0. 96. Moreover, the experimental data were interpreted on the basis of surface complexation model. The experimental results showed that the monodentate-coordinated metal ion surface complex species (SOM⁺) are predominant over the bidentate-coordinated metal ion surface complex species [(SO)₂M] formed only by the ions Cu²⁺, Zn²⁺ and Ni²⁺. And the relevant apparent surface complexation constants are lgK_M = 2.2–3.3 in order of K_Cd≥K_Pb > K_Zn > K_Ni≥K_Cu, and lgβ_M = 5.9-6.8 in order of β_Ni > β_Zn > β_Cu. Therefore, the reactive ability of the ions onto mineral surface of quartz follows the order of Cd > Pb > Zn > Ni> Cu under the above-mentioned solution conditions. The apparent surface complexation constants, influenced by the surface potential, surface species and hydrolysis of metal ions, depend mainly on the Born solvation coefficient of the metal ions. This project was financially supported by the National Natural Science Foundation of China (No. 49572091).     

Geochemistry of trace metals associated with reduced sulfur in freshwater sediments

Porewater concentration profiles were determined for Fe, trace elements (As, Cd, Co, Cu, Mn, Ni, Pb, Zn), sulfide, SO₄ and pH in two Canadian Shield lakes (Chevreuil and Clearwater). Profiles of pyrite, sedimentary trace elements associated with pyrite and AVS were also obtained at the same sites. Thermodynamic calculations are used, for the anoxic porewaters where sulfide was measured, to characterize diagenetic processes involving sulfide and trace elements and to illustrate the importance of sulfide, and possibly polysulfides and thiols, in binding trace elements. The ion activity products (IAP) of Fe sulfide agree with the solubility products (K_s) of greigite or mackinawite. For Co, Ni and Zn, IAP values are close to the K_S values of their sulfide precipitates; for Cu and Pb, IAP/K_s indicate large oversaturations, which can be explained by the presence of other ligands (not measured) such as polysulfides (Cu) and thiols (Pb). Cobalt, Cu, Ni and Zn porewater profiles generally display a decrease in concentration with increasing ΣH₂S, as expected for transition metals, whereas Cd, Pb and Zn show an increase (mobilisation). The results suggest that removal of trace elements from anoxic porewaters occurs by coprecipitation (As and Mn) with FeS(s) and/or adsorption (As and Mn) on FeS(s), and by formation of discrete solid sulfides (Cd, Cu, Ni, Pb, Zn and Co). Reactive Fe is extensively sulfidized (51–65%) in both lakes, mostly as pyrite, but also as AVS. Similarities between As, Co, Cu and Ni to Fe ratios in pyrite and their corresponding mean diffusive flux ratios suggest that pyrite is an important sink at depth for these trace elements. High molar ratios of trace elements to Fe in pyrite from Clearwater Lake correspond chronologically to the onset of smelting activities. AVS can be an important reservoir of reactive As, Cd and Ni and, to a lesser extent, of Co, Cu and Pb. Overall, the trace elements most extensively sulfidized were Ni, Cd and As (maximum of 100%, 81% and 49% of the reactive fraction, respectively), whereas Co, Cu, Mn, Pb and Zn were only moderately sulfidized (11–16%).     

Multiphase evolution in the black-shale-hosted Ni–Cu–Zn–Co deposit at Talvivaara,Finland

The Talvivaara deposit contains 1550 Mt of ore averaging 0.22% Ni, 0.13% Cu, 0.49% Zn and 0.02% Co. The precursors of the host rocks were deposited 2.1–1.9 Ga ago in a stratified marine basin. Fractured talc-carbonate rocks delineate the eastern border of the deposit and serpentinites and talc-carbonate rocks occur along the rift-related sequence to the north and south of Talvivaara. Characteristic features are high concentrations of organic carbon and sulphur with median values of 7.6% and 8.2%, respectively. Organic carbon is graphitic at present and a variety of sulphide textures occur, representing multiphase evolution during diagenesis, tectonic deformation and medium-grade regional metamorphism. The main sulphides of the Talvivaara ore are pyrrhotite, pyrite, sphalerite, chalcopyrite and pentlandite. Sulphides occur both as fine-grained disseminations and coarse grains or aggregates. Chalcopyrite mainly occurs in joint surfaces and quartz-sulphide veins and pentlandite occur as inclusions in pyrrhotite. Alabandite (MnS) occurs in black shales and black metacarbonate rocks. The early low-T sulphide minerals were overprinted by later stage processes. No framboidal pyrite is any longer present, but spheroidal pyrite with a grain size of < 0.01 mm and containing up to 0.7% Ni occurs. During the deposition of the organic-rich mud the anoxic/euxinic bottom waters were enriched in Ni⁺, Cu⁺ and Zn^2 +. Sulphur isotope δ³⁴S values indicate mixing of sulphur derived from different processes or fractionation by sulphate reduction in a restricted basin. Both thermochemical and bacterial sulphate reductions were important for the generation of reduced sulphur.     

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit,Inner Mongolia,China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing'an Range(S(GXR)which forms part of the eastern segment of the Central Asian Orogenic Belt(CAOB)is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo(Cu),skarn Fe(Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn± Cu± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including(i)the early porphyry mineralization stage,(ii)main porphyry mineralization stage,(iii)transition mineralization stage,(iv)vein-type mineralization stage and(v)late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites:Pyl is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium-to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Pyl to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni(0.03-10.79,average 2.13)and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ~(34)S_(cDT) values of Pyl(0.42‰-1.61‰,average1.16‰),Py2(-1.23‰to 0.82‰,average 0.35‰),Py3(—0.36‰to 2.47‰average 0.97‰).Py4(2.51‰--3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit(-5‰to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian(Jurassic-Cretaceous)magmatic-hydrothermal events.Variations of δ~(34) S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type Pb-Zn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.     

Mineralogical controls on mine drainage of the abandoned Ervedosa tin mine in north-eastern Portugal

The Ervedosa Mine, in north-eastern Portugal, has Sn-bearing quartz veins containing cassiterite and sulphides that cut Silurian schists and a Sn-bearing muscovite granite. These veins were mined for Sn and As₂O₃ until 1969. Cassiterite, the main Sn ore, has alternate lighter and darker growth-zones. The darker zones are richer in Fe, Nb, Ta and Ti, but poorer in Sn than the adjoining lighter zones. Exsolution blebs of ferrocolumbite, manganocolumbite, Ti ixiolite, rutile, ilmenite and rare wolframite were found in the darker zones. Arsenopyrite is the most abundant sulphide and contains inclusions of pyrrhotite, bismuth, bismuthinite and matildite. Other sulphides are pyrite, sphalerite, chalcopyrite and stannite. Secondary solid phases consisting mainly of hydrate sulphate complexes of Al, Fe, Ca and Mg (aluminocopiapite, copiapite, halotrichite, pickeringite, gypsum and alunogen, meta-alunogen) occur at the surface of the Sn-bearing quartz veins and their wall rocks (granite and schist), while oxides, hydroxides, arsenates and residual mineral phases (albite, muscovite and quartz) occur in mining tailings. Toxic acid mine waters (acid mine drainage AMD), which have high conductivity and significant concentrations of As, SO₄ and metal (Cu, Zn, Pb, Fe, Mn, Cd, Ni and Co), occur in an area directly affected by the mine. Surface stream waters outside this area have low conductivity and a pH that is almost neutral. Metal and As concentrations are also lower. Stream waters within the impact area have an intermediate composition, falling between that of the AMD and the natural stream waters outside impact area. Waters associated directly with mineralised veins must not be used for human consumption or agriculture.     

Behavior of mercury in the supergene zone of geothermal deposits,southern Kamchatka

Mercury distribution was determined in all types of solid materials from the supergene zone of geothermal deposits in southern Kamchatka: rocks, hydrothermally altered rocks (metasomatic rocks), soils, soil—pyroclastic cover, bottom sediments of perennial and intermittent streams, hydrothermal clays, artificial siliceous precipitates, and iron sulfides formed owing to thermal water discharge from a well. The mercury content varies from background values for the Kurile-Kamchatka region in fresh rocks to high and extremely high values in hydrothermal clays and monomineralic pyrite samples. The sources, migration conditions, and concentration mechanisms of mercury were evaluated. Mercury is supplied to the surface of geothermal deposits and thermal fields by a deep hydrothermal flow and is concentrated on thermodynamic barriers in hydrothermal clays, siliceous sinters (silica gel), and soils showing high salinity owing to the deposition in them of silica, sulfates, and other compounds from a vapor-water mixture. Newly formed clay minerals, iron sulfides (pyrite), silica gel, and biological materials (peat) can probably efficiently sorb mercury under geothermal conditions at atmospheric pressure and temperatures from 20°C to 120°C.     

Proterozoic copper deposits in NW Queensland,Australia: Sulfur isotopic data

Sulfur isotopic disequilibrium is commonly observed between associated pyrite and copper sulfides in NW Queensland. A sulfur isotopic study of copper mineralization in dolomites at Paradise Valley and arenites at Mammoth has allowed the significance of such disequilibrium to be evaluated. Copper mineralization at Paradise Valley is characterized by a greater enrichment in ³⁴S, with δ³⁴S values often greater than +30‰, for both copper sulfides and associated syngenetic/diagneetic pyrite. At Mammoth, copper sulfides have isotopic compositions (δ³⁴S=?15.9 to ?0.3‰) transitional between disseminated syngenetic/diagenetic pyrite (δ³⁴S=?5.7 to ?1.7‰) and epigenetic vein pyrite (δ³⁴S=?17.9 to ?7.1‰) suggesting progressive reaction and replacement of syngenetic/diagenetic pyrite by a copper-bearing mineralizing fluid under oxidizing conditions. The isotopic data, within the constraints imposed by geological and geochemical factors, support a model of reaction between copper-bearing mineralizing fluids and pre-existing syngenetic/diagenetic pyrite for both the carbonate- and arenite-hosted deposits.     

滇东北麻栗坪铅锌矿床微量元素分布与赋存状态:LA-ICPMS研究

位于扬子板块西南缘的"川滇黔接壤铅锌矿集区"是我国西南大面积低温成矿域的重要组成部分,麻栗坪铅锌矿床位于该矿集区昭通-曲靖成矿带中段,是近年来滇东北地区新发现的铅锌矿床。本文以麻栗坪铅锌矿不同硫化物为研究对象,通过LA-ICPMS原位点测试和元素Mapping分析,尝试揭示该矿床中Ge、Cd和In等微量元素在不同硫化物中分布规律与赋存状态。本次研究发现,麻栗坪矿床不同硫化物中富集的微量元素明显不同,闪锌矿主要富集Mn、Cu、Sn、Cd、In和Ge,而方铅矿主要富集Ag、Sb和Se,黄铁矿则富集As、Co和Ni。闪锌矿是分散元素Ge、In和Cd的主要载体矿物,且Cd、Ge、In、Mn、As、Sb和Ag以类质同象形式赋存于闪锌矿中;而Cu则主要以类质同象形式存在,部分Cu以黄铜矿的显微包裹体形式赋存于闪锌矿中,其中以类质同象赋存于闪锌矿中Cu和Ge呈现明显的相关性,可能暗示其与Zn的置换方式为:3Zn2+Ge4++2Cu+。总体上,该矿床闪锌矿以富集Cd、Ge,贫Fe、Mn、Co、Sn为特征,这些微量元素组成与典型MVT型矿床基本一致,明显有别于喷流沉积和岩浆热液型矿床,而与中低温条件下形成的闪锌矿微量元素组成相似。结合该矿床后生成矿特征明显等地质地球化学研究成果,我们认为该矿床应属于MVT型铅锌矿床。值得注意的是,该矿床闪锌矿相对富集In,可能暗示其形成具有特殊性,这可能与其成矿流体在长距离运移过程中所流经地层有关,该类流体活化萃取了基底地层的中-酸性岩浆岩或火山碎屑岩中的In,致使矿床中闪锌矿相对富集In。     

Mineralogical and chemical characterization of wastes from the sulfuric acid industry in Falun, Sweden

 Wastes from the sulfuric acid industry are an environmental concern, because of the emission of acids, heavy metals, and sulfate to the environment. The wastes in Falun consist of 70–80% iron oxides, 10–20% silicates, less than 10% residual sulfides, and small amounts of secondary precipitates (iron hydroxides and Fe-, Zn- and Cu-sulfates). Due to the different behavior of sulfides during the roasting process, pyrrhotite and sphalerite are the major sulfide residues associated with lesser amounts of pyrite, chalcopyrite, and galena. The leachates are low-pH and enriched in Zn, Fe, and SO₄. The acid ferric Fe-rich solution promotes the dissolution of sphalerite and favors the formation of Pb-sulfate coatings on galena, providing an armoring effect which slows down the further oxidation of the galena. The residual sulfides are the potential source for acid generation and metal release. During the roasting process, iron oxides retain small amounts of sulfur and sphalerite forms alteration rims containing Zn-oxides. The iron oxides and Zn-oxides are important contributors to SO₄ and Zn in the leachates. The conditions in the waste deposit are favorable for the precipitation of Zn-, Cu-Fe-sulfates (e.g. gunningite, chalcanthite, Zn-copiapite). The highly soluble sulfates play important roles in controlling the concentrations of Cd, Cu, Fe, Zn, and SO₄ in the leachates. The mineralogical and geochemical data help to develop the reclamation strategies of this type of industrial wastes. Received: 26 April 1996 · Accepted: 27 July 1996     

大横路式钴(铜)矿床地质特征及成因探讨

大横路式钴(铜)矿床产于辽吉古元古代裂谷增生地体内,是国内新近发现的新类型钴矿床,其矿化特征独特、埋藏浅、规模大,具有较高潜在经济价值.矿床赋存于老岭群富硼、碳粘土岩夹硅质岩建造之中,矿体呈层状、似层状、鞍状产出,产状与围岩一致;矿石中金属矿物以硫化物、砷化物形式存在,钴以硫钴镍矿、辉砷钴矿、方钴矿和含钴黄铁矿等形式与黄铜矿、闪锌矿、方铅矿等共生.通过对矿床地质、地球化学特征和流体特征研究,证明该矿床既具有明显的热水沉积成因特征,又受后期变质热液的强烈叠加,属海底热水沉积-变质热液叠加改造型矿床.     

Geochemical and mineralogical control of different genetic types of deep-sea nodules from the Pacific Ocean

Deep-sea nodules from the Northeast Pacific nodule belt and the Southeast Pacific (Sonne Basin), being formed in areas bordering the equatorial zone of high biological productivity, accumulate by two basically different growth processes: (A) early diagenetic growth by supply from pore water and (B) hydrogenetic growth by supply from near-bottom sea-water. These growth processes lead to different genetic types of nodules: early diagenetic type A, hydrogenetic type B, and mixed-type AB; a further type A_C, very rich in Mn, is being formed by increasing influence of early diagenesis. These types can clearly be distinguished by their shapes, surface textures, mineral constituents of oxide fraction, internal microstructures, and geochemistry. A genetical classification is being proposed on the basis of statistically computed interelement relationships. Todorokite, very poor in Fe, is the main Mn phase in the early diagenetic substance; -MnO₂ intimately intergrown with FeOOH · xH₂O is the main phase in the hydrogenetic substance. Consequently an important difference can be pointed out: the metal supply for the growth of the early diagenetic nodules is based on an ionic solution of Me²⁺ (e. g. Mn²⁺, Ni²⁺, Cu²⁺, Zn²⁺), whereas the supply for the hydrogenetic nodules is caused by transport of colloidal particles. Mobilization of Mn²⁺ and fractionation from Fe is controlled by the amount of decomposing organic matter in the "peneliquid" layer of the sediments. The main factor controlling the intensity of early diagenesis is the biological productivity in surface waters. The crucial "point of reversal" at a Mn/Fe ratio of about 5, obtained by hyperbolical regression of the analyses of nodules from the Southeast Pacific, represents best concentrations in Ni and Cu. Mn/Fe quotients greater than 5 cause a decrease of Ni and Cu content. Nodules from the Northeast Pacific nodule belt generally contain higher concentrations in Cu than nodules from the Southeast Pacific. This can be explained by an additional supply of Cu transported below CCD by siliceous plankton.     

Cation segregation and the O-H stretching vibration of the olivenite-adamite series

The behaviour of the O-H stretching infrared spectra of the synthetic olivenite-adamite series described by Brathwaite (1983) is accounted for in terms of the crystal structure and cation distribution. There are three absorption bands: Two at 3,540 and 3,510 cm^?1 correspond to OH groups bonded to Zn₃ and CuZn₂ respectively. The third band corresponds to OH groups bonded to both combinations Cu₂Zn and Cu₃ and its frequency varies with the proportions of those two combinations. Preferential occupation of the five-fold site by Zn is confirmed from its effect on the infrared spectra, the ratio Zn^V/Zn^VI being roughly 4:1. There is evidence for clustering of Zn into Zn₃ groups around OH. Differences in the degree of segregation and clustering of Zn will affect the infrared spectra of natural olivenites and adamites and this may limit the usefulness of infrared spectroscopy as a determinative method.