Brine pool deposition for the Zn–Pb–Cu massive sulphide deposits of the Bathurst mining camp, New Brunswick, Canada. I. Comparisons with the Iberian pyrite belt

The Ordovician Zn–Pb–Cu massive sulphide ore deposits of the Bathurst mining camp share many features with those of the Devonian/Carboniferous Iberian pyrite belt, particularly the tendency to large size (tonnage and metal content); shape, as far as can be determined after allowing for deformation; metal content, particularly Fe/Cu, Pb/Zn and Sn; mineral assemblages (pyrite + arsenopyrite ± pyrrhotite and lack or rarity of sulphates); sulphide textures (particularly framboidal pyrite); lack of chimney structures and rubble mounds; irregular metal or mineral zoning; and the low degree of zone refining compared to Hokuroku ores. The major differences between the provinces are the lack of vent complexes and the presence of Sn–Cu ores in the Iberian pyrite belt. There are also similarities in the geological setting of the two camps: both lie within continental terranes undergoing arc-continent and continent–continent collision, and in each case massive sulphide mineralisation followed ophiolite obduction; the ore deposits are associated with bimodal volcanic rocks derived from MORB and continental crust and marine shales; and mineralisation was locally accompanied or followed by deposition of iron formations.Fluid inclusion data from veins in stockworks from at least six of the Iberian massive sulphide deposits point to sulphide deposition having taken place in basins containing mostly spent saline, ore-forming fluids (brine pools), and it is suggested that most of the major features of the Bathurst deposits can be explained by similar processes. The proposed model is largely independent of ocean sulphate and O₂ content, whereas low values of each are requisites for the current, spreading-plume model of sulphide deposition in the Bathurst camp.     

A major sulphur isotope event at c. 510 Ma: a possible anoxia–extinction–volcanism connection during the Early–Middle Cambrian transition?

A new approach to constraining seawater δ³⁴S and sulphate concentration using francolite‐bound sulphate reveals an abrupt increase in δ³⁴S to +50‰ around the Early–Middle Cambrian boundary. Such high δ³⁴S values are best explained by increased rates of pyrite burial due to ocean anoxia coupled with an increased sensitivity of the ocean sulphate reservoir to perturbations due to low sulphate concentrations of 500–700 μgL^?1. We argue that the spread of anoxic waters at this time was partly the result of greenhouse warming related to the eruption of the Kalkarindji Large Igneous Province of northern Australia and that it triggered the collapse of early metazoan reef ecosystems during the latest Early Cambrian. Mass extinctions of the last 260 Myr have all coincided with enhanced volcanic activity, while several are also associated with positive shifts in seawater δ³⁴S. Extending this correlation back in time further implicates volcanically induced climate change as a major determining factor in biosphere evolution. Terra Nova, 18, 257–263, 2006     

二叠纪茅口晚期锰矿成矿作用的地球化学约束--以遵义市南茶锰矿为例

遵义锰矿是我国二叠纪时期一种重要的锰矿类型。南茶锰矿床是近年来在遵义锰矿区发现的又一中型隐伏锰矿床,是遵义锰矿的典型代表。南茶锰矿含锰岩系的微量元素、稀土元素、碳同位素研究结果表明:南茶锰矿成锰期前样品V/（V+Ni）值在0.6与0.65之间或与0.60接近,V/Cr值在0.71~2.05之间,均值为1.34,Ce呈中等程度的负异常,说明该期沉积环境属贫氧环境;成锰期样品V/（V+Ni）值接近0.45,V/Cr值为0.28、1.30,Ce呈轻微的负异常,反映此时属氧化-贫氧的沉积环境;成锰期后样品中,V/（V+Ni）值则介于0.65~0.88,均值为0.76,大部分样品V/Cr值>4.18,Ce呈轻微的正异常,说明成锰期后可能处于缺氧环境;含锰岩系δEu值均显示为弱的正Eu异常（成锰期前、成锰期以及成锰期后Eu/Eu*均值分别为0.88、1、0.85）,反应含锰岩系沉积时期受到热水作用的影响较弱;锰碳酸盐岩地层的碳同位素具有一次明显的负偏,至锰矿层达最低（-12.5‰ V-PDB）,显示与有机质的降解有关。综上所述,南茶锰矿的形成经历了前期氧化锰沉淀和之后氧化锰沉淀被还原形成碳酸锰的过程。     

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.     

Chemistry and Sulfur Isotopes in a Chert-dominant Sequence around the Stratiform Manganese Deposit of the Noda-Tamagawa Mine, Northern Kitakami Terrane, Northeast Japan: Implication for Paleoceanographic Environmental Setting

Abstract. Chemistry and sulfur isotopes are analyzed for a series of rocks in the chert‐dominant sequence around the stratiform manganese ore deposit of the Noda‐Tamagawa mine in the northern Kitakami Terrane, northeast Japan. The sequence is litholog‐ically classified into six units in ascending order: lower bedded chert, lower black shale, massive chert, manganese ore, upper black shale, and upper bedded chert. The rocks around the manganese ore deposit exhibit anomalous enrichment in Ni (max. 337 ppm), Zn (102) and U (30) in the upper part of lower bedded chert, Mo (122), Tl (79) and Pb (33) in the lower black shale, MnO, Cu (786) and Co (62) in the manganese ore, and As (247) and Sb (17) in the upper black shale. The aluminum‐normalized profiles reveal zonal enrichment of redox‐sensitive elements around the manganese bed: Zn‐Ni‐Fe‐Mo‐U(‐Co), Tl‐Pb(‐Mo), Mn‐Fe‐Cu‐V‐Cr‐Co(‐Zn) and As‐Sb in ascending order. The uppermost part of the lower bedded chert and black shale exhibit negative Ce/Ce* values, whereas the massive chert, manganese ore and lower part of the upper bedded chert display positive values. The isotopic δ³⁴S values are 0±6 % in the lower part of the lower bedded chert, ‐19 to ‐42 % in the upper part of the lower bedded chert, ‐36 to ‐42 % in the lower black shale, ‐28 to ‐35 % in the massive chert, manganese ore and upper black shale, and ‐23±5 % in the upper bedded chert. Thus, there is a marked negative shift in δ³⁴S values in the lower bedded chert, and an upward‐increasing trend in δ³⁴S through the manganese ore horizon. The present data provide evidence for a change in the paleoceanographic environmental resulting from inflow of oxic deepwater into the stagnant anoxic ocean floor below the manganese ore horizon. This event is likely to have triggered the precipitation of manganese oxyhydroxides. The redistribution of redox‐sensitive elements through the formation of metalliferous black shale and manganese carbonate ore may have occurred in association with bacterial decomposition of organic matter during early diagenesis of initial manganese oxyhydroxides.     

川东北地区晚埃迪卡拉纪灯影期海水氧化还原环境重建

晚埃迪卡拉纪全球海洋发生了大面积的缺氧,海洋化学结构呈现明显的非均质性,直接影响了埃迪卡拉型生物的演化与分布。四川盆地发育完整的晚埃迪卡拉系地层,以灯影组巨厚层碳酸盐岩沉积为代表。但是对于该套巨厚层碳酸盐岩沉积时的古海水氧化还原性质备受争议。为了解决这一问题,对川东北地区鹿池剖面的灯影组地层开展了系统的沉积学和稀土元素地球化学分析。该地区灯影组的岩石类型主要为泥微晶白云岩、黏连白云岩、叠层/层纹白云岩,以及溶蚀白云岩,沉积环境为开阔碳酸盐岩台地相。地球化学数据结果显示灯影组碳酸盐岩普遍具有较低的稀土总量(∑REE+Y值为0.4～3.3μg/g)、较低的Mn/Sr值(0.2～2.8)和较高的Fe含量(55.9～1 772.6μg/g)。灯影组的REE+Y配分曲线(经页岩标准化)可划分为四个阶段,且Ce异常指示该地区经历了弱氧化到弱还原再到缺氧状态,表明埃迪卡拉纪晚期海洋浅部水体也发生了缺氧现象。     

Transient States in Diagenesis Following the Deposition of a Gravity Layer: Dynamics of O<Subscript>2</Subscript>, Mn,Fe and N-Species in Experimental Units

Biogeochemical processes induced by the deposition of gravity layer in marine sediment were studied in a 295-day experiment. Combining voltammetric microelectrode measurements and conventional analytical techniques, the concentrations of C, O₂, N-species, Mn and Fe have been determined in porewaters and sediments of experimental units. Dynamics of the major diagenetic species following the sudden sediment deposition of few cm-thick layer was explained by alternative diagenetic pathways whose relative importance in marine sediments is still a matter of debate. Time-series results indicated that the diffusion of O₂ from overlying waters to sediments was efficient after the deposition event: anoxic conditions prevailed during the sedimentation. After a few days, a permanent oxic horizon was formed in the top few millimetres. At the same time, the oxidation of Mn²⁺ and then Fe²⁺, which diffused from anoxic sediments, contributed to the surficial enrichment of fresh Mn(III/IV)- and Fe(III)-oxides. Vertical diffusive fluxes and mass balance calculations indicated that a steady-state model described the dynamic of Mn despite the transitory nature of the system. This model was not adequate to describe Fe dynamics because of the multiple sources and phases of Fe²⁺. No significant transfer of Mn and Fe was observed between the underlying sediment and the new deposit: Mn- and Fe-oxides buried at the original interface acted as an oxidative barrier to reduced species that diffused from below. Nitrification processes led to the formation of a NO₃⁻/NO₂⁻ rich horizon at the new oxic horizon. Over the experiment period, NO₃⁻ concentrations were also measured in the anoxic sediment suggesting anaerobic nitrate production.     

The mineralogy and chemical composition of the Woodlawn massive sulphide orebody

The main Woodlawn ore lens is a polymetallic, massive sulphide deposit’ with pyrite the major constituent, variable sphalerite, galena and chalcopyrite, and minor arsenopyrite, tetrahedrite‐tennantite, pyrrhotite and electrum. The silicate gangue minerals are chlorite, quartz, talc and sericitic mica. Other mineralization in the vicinity consists of footwall copper ore in chlorite schist and several smaller massive sulphide lenses. The predominant country rocks are felsic volcanics and shales, with abundant quartz, chlorite and mica, and talc in mineralized zones.

An important textural feature of the massive ore is the fine compositional banding. Bands, which vary in thickness from a few tens of micrometres to several millimetres, are produced by variations in the sulphide content. Post‐depositional metomorphism and minor fracturing have only slightly modified this banding.

Apart from the major element constituents—Pb, Zn, Fe, Cu and S—the ore is characterized by significant (100–1000 ppm) values for Ag, As, Cd, Mn, Sb and Sn, and lower (1–100 ppm) values of Au, Bi, Co, Ga, Hg, Mo, Ni, Tl. In and Ge. Variations in the base‐metal sulphide content, the gangue mineralogy, and trace elements, are used to separate the orebody into hanging‐wall and footwall zones. The hanging‐wall zone shows a more variable trace element content, with higher Tl, Sn, Ni, Mn, Ge and Sb, but lower Ag, Cd, and Mo, than the footwall zone.

In general style of mineralization, mineralogy, and chemistry, the Woodlawn deposit resembles other volcanogenic massive sulphide deposits in eastern Australia, in New Brunswick in Canada, and the Kuroko deposits of Japan.     

Genesis of proterozoic iron-formation: sulphur isotope evidence

Seven units of carbonaceous shale or sulphide-facies iron-formation have been sampled. They are associated with Proterozoic iron-formations that range in age from ~ 1.9 to ~2.5 Ga: Sokoman and Gunflint (Canada), Riverton (United States), Penge (South Africa) and Brockman (Australia). Sulphur isotope ratios have been determined on the sulphides removed from these shales by both physical and chemical means.The mean δ³⁴S composition of the seven units varies between ?4.9%. and +6.6%. and the sample variance is low within each unit. These distributions are more characteristic of hydrothermal sulphide than sulphide produced by biogenic reduction. This hydrothermal sulphide is believed to have originated from high temperature reduction of seawater sulphate and from magmatic sulphide. A model is suggested whereby this sulphide was exhaled into stratified anoxic/oxic basins. The sulphide and associated base metals were deposited in the reduced sediments beneath the anoxic waters, while some iron and manganese was deposited on oxygenated shelves.The data support, but do not prove, a hydrothermal exhalative origin for lower Proterozoic iron-formation.     

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.     

Origine du soufre associé aux minéralisations Pb-Zn de type Mississippi Valley de la chaîne des Beni Snassen orientaux (Maroc nord-oriental)

Sulfur isotope data measured on samples of galena from the main Mississippi Valley-type prospects of the eastern Beni Snassen belt preclude an igneous source for sulfur, pointing instead to a sedimentary source. Negative δ³⁴S values are interpreted to being derived from bacteriogenic reduction of Jurassic seawater sulphate. Positive δ³⁴S values are considered to be hydrothermal sulfide transported with metal-bearing fluid. Mixing of these two fluids resulted in the deposition of the Pb ore.     

山东昌邑莲花山铁矿矿床地质与矿石稀土、微量元素特征

莲花山铁矿位于昌邑-安丘铁成矿带的中部,铁矿体赋存于古元古代粉子山群小宋组中。本文通过矿石地球化学特征及其与矽卡岩矿物组合和赋矿围岩结构特征的对比研究,证明了莲花山铁矿与条带状铁矿相似。莲花山铁矿矿石稀土元素含量较低,经页岩标准化的稀土元素配分模式呈现轻稀土元素亏损、重稀土元素富集的特征,具有明显的Eu、Y、La异常,为无明显Ce异常,Y/Ho比值反映了在其沉积时受到海水作用的影响,表明莲花山铁矿的稀土元素来源于火山热液和海水的混合溶液。微量元素中Ti、V、Co、Ni、Mn、Sr、Ba等含量较低,原始地幔标准化的微量元素配分曲线显示,U、La、Hf呈正异常,Ba、Nb、Ta、Sr呈负异常,SiO2/Al2O3、Ti/V、Ni/Co、和Sr/Ba的比值指示了莲花山铁矿成矿物质来源于火山物质的沉积。研究结果表明,莲花山铁矿成矿作用源于火山热液与海水的混合,成矿物质来自火山沉积物,其地质与地球化学特征与五台山铁矿一致,为火山沉积变质型铁矿床。     

Geochemical Characteristics and Genetic Significance of Datangpo‐Type Manganese Ore Deposits during the Cryogenian Period

The Datangpo‐type manganese ore deposits, which formed during the Nanhuan (Cryogenian) period and are located in northeastern Guizhou and adjacent areas, are one of the most important manganese resources in China, showing good prospecting potential. Many middle‐to‐large deposits, and even super‐large mineral deposits, have been discovered. However, the genesis of manganese ore deposits is still controversial and remains a long‐standing source of debate; there are several viewpoints including biogenesis, hydrothermal sedimentation, gravity flows, cold‐spring carbonates, etc. Geochemical data from several manganese ore deposits show that there are positive correlations between Al₂O₃ and TiO₂, SiO₂, K₂O, and Na₂O, and strong negative correlations between Al₂O₃ and CaO, MgO, and MnO in black shales and manganese ores. U, Mo, and V show distinct enrichment in black shales and inconspicuous enrichment in Mn ores. Ba and Rb show strong positive correlations with K₂O in manganese ores. Cu, Ni, and Zn show clear correlations with total iron in both manganese ores and black shales. ∑REE of manganese ores has a large range with evident positive Ce anomalies and positive Eu anomalies. The Post Archean Australian Shale (PAAS) normalized rare earth element (REE) distribution patterns of manganese ores present pronounced middle rare earth element (MREE) enrichment, producing “hat‐shaped” REE plots. ∑REE of black shales is more variable compared with PAAS, and the PAAS‐normalized REE distribution patterns appear as “flat‐shaped” REE plots, lacking evident anomaly characteristics. δ¹³C values of carbonate in both manganese ores and the black shales show observable negative excursions. The comprehensive analysis suggests that the black shales formed in a reducing and quiet water column, while the manganese ores formed in oxic muddy seawater, which resulted from periodic transgressions. There was an oxidation–reduction cycle of manganese between the top water body and the bottom water body caused by the transgressions during the early Datangpo, which resulted in the dissolution of manganese. Through the exchange of the euphotic zone water and the bottom water, and episodic inflow of oxygenated water, the manganese in the bottom water was oxidized to Mn‐oxyhydroxides and rapidly buried along with algae. In the early diagenetic stage, Mn‐oxyhydroxides were reduced and dissolved in the anoxic pore water and then transformed into Mn‐carbonates by reacting with HCO₃^? from the degradation of organic matter or from seawater. In the intervals between transgressions, continuous supplies of terrigenous clastics and the high productive rates of organic matter in the euphotic zone resulted in the deposition of the black shales enriched in organic matter.     

Sulphur‐isotope study of the massive sulphide orebody at Woodlawn,New South Wales

³⁴S/³²S ratios have been measured in a suite of samples from the stratabound, volcanogenic massive sulphide deposit at Woodlawn, N.S.W. ³⁴S values for the sulphides vary as follows: in the ore horizon, pyrite +6.7 to +9.2%. (mean +8.1‰), sphalerite +5.2 to +8.6‰. (mean +6.9‰), chalcopyrite +6.4 to +7.0‰ (mean +6.7‰) and galena +2.8 to +5.5‰ (mean +4.4‰); in the vein mineralization, the host volcanics—pyrite +8.7 to +11.4%. (mean +9.8‰), sphalerite +7.8 to + 10.3‰ (mean +9.2‰), chalcopyrite; +8.8 to +10.1‰ (mean +9.2‰) and galena +6.9 to +7.2‰ (mean +7.1‰). Barite from the upper ore horizon levels has an isotopic composition of +30.0‰, consistent with its having originated from Silurian ocean sulphate. The general order of ³⁴S enrichment in the sulphides is pyrite > chalcopyrite ～ sphalerite > galena. Isotopic fractionations in the systems galena/sphalerite/pyrite and chalcopyrite/pyrite indicate an equilibration temperature of 275–300°C. This temperature is considered to represent that of sulphide deposition.     

Geology, mineralogy and stable isotope geochemistry of the Kabwe carbonate-hosted Pb–Zn deposit, Central Zambia

The carbonate-hosted Kabwe Pb–Zn deposit, Central Zambia, has produced at least 2.6 Mt of Zn and Pb metal as well as minor amounts of V, Cd, Ag and Cu. The deposit consists of four main epigenetic, pipe-like orebodies, structurally controlled along NE–SW faults. Sphalerite, galena, pyrite, minor chalcopyrite, and accessory Ge-sulphides of briartite and renierite constitute the primary ore mineral assemblage. Cores of massive sulphide orebodies are surrounded by oxide zones of silicate ore (willemite) and mineralized jasperoid that consists largely of quartz, willemite, cerussite, smithsonite, goethite and hematite, as well as numerous other secondary minerals, including vanadates, phosphates and carbonates of Zn, Pb, V and Cu.Galena, sphalerite and pyrite from the Pb–Zn rich massive orebodies have homogeneous, negative sulphur isotope ratios with mean δ³⁴S_CDT permil (‰) values of − 17.75 ± 0.28 (1σ), − 16.54 ± 0.0.27 and − 15.82 ± 0.25, respectively. The Zn-rich and Pb-poor No. 2 orebody shows slightly heavier ratios of − 11.70 ± 0.5‰ δ³⁴S for sphalerite and of − 11.91 ± 0.71‰ δ³⁴S for pyrite. The negative sulphur isotope ratios are considered to be typical of sedimentary sulphides produced through bacterial reduction of seawater sulphate and suggest a sedimentary source for the sulphur.Carbon and oxygen isotope ratios of the host dolomite have mean δ¹³C_PDB and δ¹⁸O_SMOW values of 2.89‰ and 27.68‰, respectively, which are typical of marine carbonates. The oxygen isotope ratios of dolomite correlate negatively to the SiO₂ content introduced during silicification of the host dolomite. The depletion in ¹⁸O in dolomite indicates high temperature fluid/rock interaction, involving a silica- and ¹⁸O-rich hydrothermal solution.Two types of secondary fluid inclusions in dolomite, both of which are thought to be related to ore deposition, indicate temperatures of ore deposition in the range of 257 to 385 and 98 to 178 °C, respectively. The high temperature fluid inclusions contain liquid + vapour + solid phases and have salinities of 15 to 31 eq. wt.% NaCl, whereas the low temperature inclusions consist of liquid + vapour with a salinity of 11.5 eq. wt.% NaCl.Fluid transport may have been caused by tectonic movements associated with the early stages of the Pan-African Lufilian orogeny, whereas ore deposition within favourable structures occurred due to changes in pressure, temperature and pH in the ore solution during metasomatic replacement of the host dolomite. The termination of the Kabwe orebodies at the Mine Club fault zone and observed deformation textures of the ore sulphides as well as analysis of joint structures in the host dolomite, indicate that ore emplacement occurred prior to the latest deformation phase of the Neoproterozoic Lufilian orogeny.     

华南李家沱剖面寒武纪纽芬兰世海水氧化还原性质演化及其驱动因素

大气-海洋含氧量的演化对埃迪卡拉纪-寒武纪转折期的后生动物大爆发事件具有重要影响.为探讨寒武纪纽芬兰世中国南方海洋氧化还原性质的演化及其初级生产力、海水硫酸盐浓度等演化驱动因素, 分析了李家沱剖面纽芬兰世留茶坡组和小烟溪组微量元素、有机碳含量、有机碳同位素、总硫含量、黄铁矿硫同位素等.该剖面沉积于斜坡-盆地环境且出露齐全.该剖面上V/Sc、Th/U及Mo、U、V、Ni、Cu等元素的富集系数呈现出5个变化旋回, 其中留茶坡组中上部和小烟溪组中部各存在一氧化环境段, 其余层段处于缺氧环境, 而Re/Mo则显示仅在小烟溪组中部水体出现过短暂的氧化环境和含有游离H₂S的硫化环境, 其余层段处于没有游离H₂S的缺氧非硫化环境.Ba、Ni、Cu、Zn、Cd等微量元素的富集系数及TOC表明: 留茶坡组的有机质沉降量和埋藏量都明显小于上覆小烟溪组; 而在小烟溪组中, 其中部有机质的沉降量和埋藏量最低, 下部最高, 上部次之.TOC/TS、TS以及黄铁矿硫同位素的垂向演化趋势等都显示李家沱剖面纽芬兰世大都处于低海水硫酸盐浓度环境.低海水硫酸盐浓度是造成李家沱剖面纽芬兰世缺氧水体未富集游离H₂S的主要原因.大气含氧量的升高是导致李家沱剖面小烟溪组中部出现短暂氧化环境以及近硫化环境的主要原因.      

The Marl Slate: a model for the precipitation of calcite, dolomite and sulphides in a newly formed anoxic sea

Detailed studies of a new, complete Marl Slate core in South Yorkshire have provided information on isotopic (δ¹³C, δ¹⁸O, δ³⁴S) and geochemical variations (trace elements and C/S ratio) which enable the formulation of a model for carbonate and sulphide precipitation in the Late Permian Zechstein Sea. Calcite and dolomite are intimately associated; the fine lamination, organic character and absence of benthos in the sediments are indicative of anoxic conditions. Lithologically the core can be divided into a lower, predominantly sapropelic Marl Slate (2 m) and an upper Transition Zone (0·65 m) of alternating sapropel and calcite-rich and dolomite-rich carbonates. C/S ratios are 2·22 for the Marl Slate and 1·72 for the Transition Zone respectively, both characteristic of anoxic environments. δ¹⁸O in the carbonates shows a large and systematic variation closely mirrored by variations in calcite/dolomite ratio. The results suggest a fractionation factor equivalent to a depletion of 3·8% for ¹⁸O and 1·5% for ¹³C in calcite. The δ³⁴S values of pyrite are isotopically light (mean value = - 32·7%) suggesting a fractionation factor for the Marl Slate of almost 44%, typical of anoxic basins. The results are related to stratification in the early Zechstein Sea. Calcite was precipitated in oxic upper layers above the halocline. Below the oxic/anoxic boundary framboidal pyrite was precipitated, resulting in lower sulphate concentration and elevated Mg/Ca ratio (due to calcite precipitation). As a result of this, dolomite formation occurred below the oxic/anoxic interface, within the anoxic water column and in bottom sediments. Variations in calcite/dolomite ratios, and isotopic variations, are thus explained by fluctuations in the relative level of the oxic/anoxic boundary in the Zechstein Sea.     

贵州遵义二叠纪锰矿地球化学特征与沉积环境分析：以遵义谢家坝富锰矿床为例

为分析贵州遵义二叠纪锰矿的沉积环境,对谢家坝锰矿床进行常量元素、微量和稀土元素地球化学研究。研究认为：谢家坝锰矿赋存于茅口组顶部含锰岩系中,可分为下矿层豆状、角砾状菱锰矿、似层状菱锰矿,以及上矿层碎屑状、块状菱锰矿的二元结构矿石类型组合,可广泛代表遵义锰矿的矿石特征。谢家坝锰矿上下矿层之间主量元素和稀土元素含量差异较大,常量元素SiO2、TiO2、S、Fe2O3含量上矿层均大于下矿层,MnO、MgO与 Al2O3之间均呈负相关关系;上矿层Fe/Mn值较高,属高Fe低P型锰矿,而下矿层Fe/Mn值较低,属中低Fe低P型锰矿。上矿层稀土元素PAAS标准化配分后呈现较明显的重稀土亏损、弱的轻稀土富集、右倾配分的特征,具有弱的Ce正异常,类似海底铁锰结核稀土元素特征;下矿层呈现弱的中稀土富集,轻、重稀土亏损,弱的帽式分配特征,具明显的Ce负异常,类似典型深部海水沉积稀土元素特征。微量元素Th/U、Ni/Co、V/Cr、V/（V+Ni）、AU等沉积环境古氧相分析指标和稀土元素PAAS标准化配分模式指示,谢家坝锰矿下矿层是在贫氧-厌氧条件下Mn2+与CO32-直接形成菱锰矿,上矿层在常氧-贫氧环境下Mn3+、Mn4+以氧化物或氢氧化物形式沉淀。     

A sulphur isotopic study of the Bleikvassli Zn-Pb-Cu deposit,Nordland, northern Norway

The Bleikvassli Zn-Pb-Cu deposit occurs in the Uppermost Allochthon in the Caledonides of northern Norway. The orebody is enclosed in amphibolite-facies schists and gneisses, underlain by amphibolites, and it has been classified as a sediment-hosted massive sulphide (SEDEX) deposit. The stratiform ore is dominantly pyritic, with a basal layer of pyrrhotitic ore. Sulphide veins occur in the footwall. The orebody generally has a limited range of ³⁴S, from 0.3 to 4.5% (x = 2.4 ± 1.2, 1 , n = 26). The lowest ³⁴S values (0.3–2.3) were found in sulphide veins in the footwall and vent proximal stratiform ore. More distal pyritic Zn-Pb ore has heavier average ³⁴S values (up to 4.5). The ore sulphides were deposited from a hydrothermal solution with ³⁴S about 2 perhaps with the incorporation of a minor portion of sulphide from the ambient seawater. The hydrothermal solution probably acquired most of its sulphide from the underlying mixed lithology; notably basaltic rocks. Sulphide produced by thermochemical reduction of seawater in the deep conduit system may also have been incorporated. Bacteriogenic sulphide is not likely as a major source of ore sulphur in the massive ore. Sulphide incorporated in distal pyrite, which have ³⁴S from -12 to-10, could have formed either by oxidation of the hydrothermal sulphide, or by bacterial reduction of seawater sulphate in the depositional environment. Exchange of sulphur isotopes probably took place only on a localized scale during Caledonian metamorphism, the bulk sulphur isotopic composition of the ore being preserved in a hand specimen scale.     

Rise in seawater sulphate concentration associated with the Paleoproterozoic positive carbon isotope excursion: evidence from sulphate evaporites in the ∼2.2–2.1 Gyr shallow‐marine Lucknow Formation,South Africa

Abstract Past oceanic sulphate concentration is important for understanding how the oceans’ redox state responded to atmospheric oxygen levels. The absence of extensive marine sulphate evaporites before ～1.2 Gyr probably reflects low seawater sulphate and/or higher carbonate concentrations. Sulphate evaporites formed locally during the 2.22–2.06 Gyr Lomagundi positive δ¹³C excursion. However, the ～2.2–2.1 Gyr Lucknow Formation, South Africa, provides the first direct evidence for seawater sulphate precipitation on a carbonate platform with open ocean access and limited terrestrial input. These marginal marine deposits contain evidence for evaporite molds, pseudomorphs after selenite gypsum, and solid inclusions of Ca‐sulphate in quartz. Carbon and sulphur isotope data match the global record and indicate a marine source of the evaporitic brines. The apparent precipitation of gypsum before halite requires ≥2.5 mm L^?1 sulphate concentration, higher than current estimates for the Paleoproterozoic. During the Lomagundi event, which postdates the 2.32 Gyr initial rise in atmospheric oxygen, seawater sulphate concentration rose from Archean values of ≤200 μm L^?1, but dropped subsequently because of higher pyrite burial rates and a lower oceanic redox state.