Isotopic evidence of TSR origin for natural gas bearing high H_2S contents within the Feixianguan Formation of the northeastern Sichuan Basin, southwestern China

Isotopic evidence of TSR origin for natural gas bearing high H2S contents 1961 As the hazardous component of natural gas, the ex-istence of H2S, due to its extremely strong toxicity and corrosivity, not only decreases the percentage of hy-drocarbon gas within natural gas and reduces its in-dustrial value, it also threatens each aspect of drilling and exploitation. It frequently causes serious safety accidents[1] and leads to the E&P cost and risk of natural gas with higher H2S contents be…     

Evolution of Hydrothermal System at the Dizon Porphyry Cu-Au Deposit, Zambales, Philippines

Abstract. Evolution of hydrothermal system from initial porphyry Cu mineralization to overlapping epithermal system at the Dizon porphyry Cu‐Au deposit in western central Luzon, Zambales, Philippines, is documented in terms of mineral paragen‐esis, fluid inclusion petrography and microthermometry, and sulfur isotope systematics. The paragenetic stages throughout the deposit are summarized as follows; 1) stockwork amethystic quartz veinlets associated with chalcopyrite, bornite, magnetite and Au enveloped by chlorite alteration overprinting biotite alteration, 2) stockwork quartz veinlets with chalcopyrite and pyrite associated with Au and chalcopyrite and pyrite stringers in sericite alteration, 3) stringer quartz veinlets associated with molybdenite in sericite alteration, and 4) WNW‐trending quartz veins associated with sphalerite and galena at deeper part, while enargite and stibnite at shallower levels associated with advanced argillic alteration. Chalcopyrite and bornite associated with magnetite in quartz veinlet stockwork (stage 1) have precipitated initially as intermediate solid solution (iss) and bornite solid solution (bnss), respectively. Fluid inclusions in the stockwork veinlet quartz consist of gas‐rich inclusions and polyphase inclusions. Halite in polyphase inclusions dissolves at temperatures ranging from 360d?C to >500d?C but liquid (brine) and gas (vapor) do not homogenize at <500d?C. The maximum pressure and minimum temperature during the deposition of iss and bnss with stockwork quartz veinlets are estimated to be 460 bars and 500d?C. Fluid inclusions in veinlet stockwork quartz enveloped in sericite alteration (stage 2) consist mainly of gas‐rich inclusions and polyphase inclusions. In addition to the possible presence of saturated NaCl crystals at the time of entrapment of fluid inclusions that exhibit the liquid‐vapor homogenization temperatures lower than the halite dissolution temperatures in some samples, wide range of temperatures of halite dissolution and liquid‐vapor homogenization of polyphase inclusions from 230d?C to >500d?C and from 270d?C to >500d?C, respectively, suggests heterogeneous entrapment of gaseous vapor and hypersaline brine. The minimum pressure and temperature are estimated to be about 25 bars and 245d?C. Fluid inclusions in veinlet quartz associated with molybdenite (stage 3) are dominated by gas‐rich inclusions accompanied with minor liquid‐rich inclusions that homogenize at temperatures between 350d?C and 490d?C. Fluid inclusions in vuggy veinlet quartz associated with stibnite (stage 4) consist mainly of gas‐rich inclusions with subordinate polyphase inclusions that do not homogenize below 500d?C. Fluid inclusions in veinlet quartz associated with galena and sphalerite (stage 4) are composed of liquid‐rich two‐phase inclusions, and they homogenize into liquid phase at temperatures ranging widely from 190d?C to 300d?C (suggesting boiling) and the salinity ranges from 1.0 wt% to 3.4 wt% NaCl equivalent. A pressure of about 15 bars is estimated for the dilute aqueous solution of 190d?C from which veinlet quartz associated with galena and sphalerite precipitated. In addition to a change in temperature‐pressure regime from lithostatic pressure during the deposition of iss and bnss with stockwork quartz veinlets to hydrostatic pressure during fracture‐controlled quartz veinlet associated with galena and sphalerite, a decrease in pressure is supposed to have occurred due to unroofing or removal of the overlying piles during the temperature decrease in the evolution of hydrothermal system. The majority of the sulfur isotopic composition of sulfides ranges from ±0 % to +5 %. Sulfur originated from an iso‐topically uniform and homogeneous source, and the mineralization occurred in a single hydrothermal system.     

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.     

基于主体功能区约束的大气污染物总量控制目标分配研究

考虑经济发展水平、污染物排放现状、污染物治理水平、空气质量,特别是国家主体功能区环境目标约束等因素,构建大气污染物排放总量分配的指标体系,用改进的等比例分配方法对2015年国家SO2,NOx总量控制目标进行区域分配。分配结果表明:SO2和NOx削减量大的省份主要集中在华北平原及其周围地区,这些地区污染物排放量大、空气质量较差;削减比例较大的地区主要集中在西部地区以及北京、天津2个直辖市,这些地区单位GDP能耗高、工业污染物去除率低、空气质量差;削减量相对较小的地区主要集中在西南和南部一些省份;削减比例较小的地区主要集中在中南部和南部几个省份,这些地区污染物排放量相对较少,空气质量好于其他省份。     

湖南宝山矿床花岗岩类硫-铅同位素和流体包裹体研究及其成因意义

宝山铜铅锌多金属矿床是湖南重要的铅锌生产基地。矿床内矽卡岩型铜(钼)矿化受侏罗纪花岗闪长斑岩的控制,而主要的铅锌矿体则产于远离岩体的碳酸盐地层中,且缺乏可靠的矿化年龄限制。为了查明宝山铅锌矿体与花岗闪长斑岩之间的成因关系,文章对宝山花岗岩类中浸染状黄铁矿的硫同位素和钾长石的铅同位素,以及铅锌矿石萤石脉石的流体包裹体进行了测试和研究,并与前人报道的铅锌硫化物矿石的硫、铅同位素进行了对比,尝试为宝山铅锌矿化的物质来源及成因提供依据。研究表明,花岗闪长斑岩中浸染状黄铁矿的δ34S值为+1.5‰~+3.5‰,与铅锌矿石硫化物(方铅矿、闪锌矿及黄铁矿)相一致;同时,花岗岩类中钾长石的铅同位素组成206Pb/204Pb、207Pb/204Pb和208Pb/204Pb分别为18.4789~18.7668、15.6835~15.7220和38.7903~39.1035,具有壳源的特征,且与铅锌矿石硫化物的铅同位素分布范围相吻合。宝山矿床的硫、铅同位素特征表明,花岗闪长斑岩应是铅锌矿化的主要硫源及金属来源。宝山矿床铅锌矿石萤石中的流体包裹体具有低温(130~150℃)、低盐度(8%)的特征,可能是岩浆热液演化到晚期的产物。结合已有的有关资料加以对比和分析,研究认为,宝山铅锌矿床的成矿物质应来源于花岗闪长岩的岩浆期后热液,在热液演化晚期迁移到远端地层中沉淀,形成了宝山的主要铅锌矿体。     

Closely related thyasirid bivalves associate with multiple symbiont phylotypes

Species of thyasirid bivalves are considered to be representative of early stages of chemosymbiosis, given that bacterial symbionts occur outside gill epithelial cells, vary among species in their abundance and nutritional importance, and are environmentally acquired. For these reasons, assessing the extent of host–symbiont specificity in thyasirids could provide valuable information on the evolution of chemosymbiosis. We show that individuals of two closely related and sympatric Thyasira cf. gouldi operational taxonomic units collected from three sites in a fjord in Newfoundland, Canada, associate with one of three distinct, closely related symbiont phylotypes. While associations show some site‐specificity, there is flexibility in host–symbiont pairings within the fjord, further supporting an early and relatively unspecific stage of chemosymbiosis in this family. Morphologic differences observed both within and among symbiont phylotypes suggest physiologic variation, possibly induced by small‐scale differences in sedimentary conditions.     

The source of sulfur in sulfide deposits in the Siberian Platform traps (from isotope data)

The source of sulfur in giant Norilsk-type sulfide deposits is discussed. A review of the state of the problem and a critical analysis of existing hypotheses are made. The distribution of δ³⁴S in sulfides of ore occurrences and small and large deposits and in normal sedimentary, metamorphogenic, and hypogene sulfates is considered. A large number of new δ³⁴S data for sulfides and sulfates in various deposits, volcanic and terrigenous rocks, coals, graphites, and metasomatites are presented. The main attention is focused on the objects of the Norilsk and Kureika ore districts. The δ³⁴S value varies from -14 to + 22.5‰ in sulfides of rocks and ores and from 15.3 to 33‰ in anhydrites. In sulfide-sulfate intergrowths and assemblages, δ³⁴S is within 4.2-14.6‰ in sulfides and within 15.3-21.3‰ in anhydrites. The most isotopically heavy sulfur was found in pyrrhotite veins in basalts (δ³⁴S = 21.6‰), in sulfate veins cutting dolomites (δ³⁴S = 33‰), and in subsidence caldera sulfates in basalts (δ³⁴S = 23.2-25.2‰). Sulfide ores of the Tsentral’naya Shilki intrusion have a heavy sulfur isotope composition (δ³⁴S = + 17.7‰ (n = 15)). Thermobarogeochemical studies of anhydrites have revealed inclusions of different types with homogenization temperatures ranging from 685 °C to 80 °C. Metamorphogenic and hypogene anhydrites are associated with a carbonaceous substance, and hypogene anhydrites have inclusions of chloride-containing salt melts. We assume that sulfur in the trap sulfide deposits was introduced with sulfates of sedimentary rocks (δ³⁴S = 22-24‰). No assimilation of sulfates by basaltic melt took place. The sedimentary anhydrites were “steamed” by hydrocarbons, which led to sulfate reduction and δ³⁴S fractionation. As a result, isotopically light sulfur accumulated in sulfides and hydrogen sulfide, isotopically heavy sulfur was removed by aqueous calcium sulfate solution, and “residual” metamorphogenic anhydrite acquired a lighter sulfur isotope composition as compared with the sedimentary one. The wide variations in δ³⁴S in sulfides and sulfates are due to changes in the physicochemical parameters of the ore-forming system (first of all, temperature and P_ch4) during the sulfate reduction. The regional hydrocarbon resources were sufficient for large-scale ore formation.     

Origin of natural sulfur-metal chimney in the Tangyin hydrothermal field,Okinawa Trough: constraints from rare earth element and sulfur isotopic compositions

For the first time, we present the rare earth element (REE) and sulfur isotopic composition of hydrothermal precipitates recovered from the Tangyin hydrothermal field (THF), Okinawa Trough at a water depth of 1206 m. The natural sulfur samples exhibit the lowest ΣREE concentrations (ΣREE= 0.65×10^–6–4.580×10^–6) followed by metal sulfides (ΣREE=1.71×10^–6–11.63×10^–6). By contrast, the natural sulfur-sediment samples have maximum ΣREE concentrations (ΣREE=11.54×10^–6–33.06×10^–6), significantly lower than those of the volcanic and sediment samples. Nevertheless, the δEu, δCe, (La/Yb)_N, La/Sm, (Gd/Yb)_N and normalized patterns of the natural sulfur and metal sulfide show the most similarity to the sediment. Most hydrothermal precipitate samples are characterized by enrichments of LREE (LREE/HREE=10.09–24.53) and slightly negative Eu anomalies or no anomaly (δEu=0.48–0.99), which are different from the hydrothermal fluid from sediment-free mid-oceanic ridges and back-arc basins, but identical to the sulfides from the Jade hydrothermal field. The lower temperature and more oxidizing conditions produced by the mixing between seawater and hydrothermal fluids further attenuate the leaching ability of hydrothermal fluid, inducing lower REE concentrations for natural sulfur compared with metal sulfide; meanwhile, the negative Eu anomaly is also weakened or almost absent. The sulfur isotopic compositions of the natural sulfur (δ³⁴S=3.20‰–5.01‰, mean 4.23‰) and metal sulfide samples (δ³⁴S=0.82‰–0.89‰, mean 0.85‰) reveal that the sulfur of the chimney is sourced from magmatic degassing.     

下庄竹山下铀矿床黄铁矿元素地球化学特征及其表征意义

竹山下铀矿床是粤北下庄铀矿田内大型铀矿床之一,铀矿化类型为"交点"型和硅化带型。在详细的野外地质调查基础上,对竹山下铀矿床4种不同类型黄铁矿进行元素含量分析及硫同位素测试,结果表明:"交点"型矿石中黄铁矿相对富集Pb、 Cu、 Co、 As、 Ni、 Se、 Bi、 U、 Sb、 Zn等微量元素;"交点"型铀矿化形成于中深部高温环境,成矿热液具有地幔流体特征,成矿过程硫来源与该区花岗岩中黄铁矿的硫来源一致或者相似,花岗岩中的黄铁矿可能为该期成矿事件的产物;竹山下矿床在垂向上表现出越往深部硫逸度越低的特征;"交点"型和硅化带型中黄铁矿具有相似的微量元素配分曲线,表明二者具有相同的成矿热液来源,且与辉绿岩中黄铁矿配分曲线相似,表明该区成矿热液具有深源性。     

陕西旬阳地区小河金矿硫铅同位素组成及地质意义

小河金矿是近年来在南秦岭中带发现的中型金矿床,矿石类型为微细浸染型,矿床受地层和构造双重控制。在野外工作基础上,根据矿物组合及穿插关系划分了4个成矿阶段:Ⅰ,成矿早期少硫化物石英脉成矿阶段;Ⅱ,石英脉、黄铁矿、毒砂成矿主阶段;Ⅲ,石英脉-多金属硫化物成矿主阶段;Ⅳ,方解石、石英脉成矿晚阶段。其中Ⅱ、Ⅲ阶段是主要金矿化阶段。不同阶段样品的原位硫同位素结果显示:成矿早阶段石英脉期的黄铁矿δ³⁴S值为20.80‰~25.77‰,均值为23.59‰;主成矿期II阶段中黄铁矿、毒砂δ³⁴S值为15.46‰~19.12‰,均值为17.5‰;主成矿期Ⅲ阶段中方铅矿、闪锌矿δ³⁴S值为11.35‰~16.78‰,均值为13.88‰。硫同位素特征指示硫以沉积硫为主,成矿过程可能存在低δ³⁴S值热液的持续加入。金属硫化物Pb同位素测试结果显示²⁰⁶Pb/²⁰⁴Pb为17.882 1~18.367 4,²⁰⁷Pb/²⁰⁴Pb为15.614 0~15.674 1,²⁰⁸Pb/²⁰⁴Pb为38.016 3~38.934 2,指示小河金矿铅主要源于地壳,同时伴随幔源铅的混入。综合矿床地质特征及硫、铅同位素地球化学特征,认为小河金矿成矿过程可能存在流体混合作用。