Isotopic Compositions of Sulfur in the Jinshachang Lead–Zinc Deposit, Yunnan, China, and its Implication on the Formation of Sulfur-Bearing Minerals

The Jinshachang lead-zinc deposit is mainly hosted in the Upper Neoproterozoic carbonate rocks of the Dengying Group and located in the Sichuan-Yunnan-Guizhou （SYG） Pb-Zn-Ag multi- metal mineralization area in China. Sulfides minerals including sphalerite, galena and pyrite postdate or coprecipitate with gangue mainly consisting of fluorite, quartz, and barite, making this deposit distinct from most lead-zinc deposits in the SYG. This deposit is controlled by tectonic structures, and most mineralization is located along or near faults zones. Emeishan basalts near the ore district might have contributed to the formation of orebodies. The j34S values of sphalerite, galena, pyrite and barite were estimated to be 3.6‰-13.4‰, 3.7‰-9.0‰, -6.4‰ to 29.2‰ and 32.1‰34.7‰, respectively. In view of the similar δ34S values of barite and sulfates being from the Cambrian strata, the sulfur of barite was likely derived from the Cambrian strata. The homogenization temperatures （T ≈ 134--383℃） of fluid inclusions were not suitable for reducing bacteria, therefore, the bacterial sulfate reduction could not have been an efficient path to generate reduced sulfur in this district. Although thermochemical sulfate reduction process had contributed to the production of reduced sulfur, it was not the main mechanism. Considering other aspects, it can be suggested that sulfur of sulfides should have been derived from magmatic activities. The δ34S values of sphalerite were found to be higher than those of coexisting galena. The equilibrium temperatures calculated by using the sulfur isotopic composition of mineral pairs matched well with the homogenization temperature of fluid inclusions, suggesting that the sulfur isotopic composition in ore-forming fluids had reached a partial equilibrium.

油气有机质与MVT铅锌矿床的成矿——以四川赤普铅锌矿为例

四川赤普MVT铅锌矿床成矿与古老油气藏关系密切。通过对矿床不同成矿阶段硫化物硫同位素和热液碳酸盐碳、氧同位素系统研究,结合沥青有机质的有机地球化学特征,探讨油气参与金属成矿的详细过程。取得主要认识如下:(1)油气系统中先存的H2S是成矿早阶段主要的硫源,TSR作用启动后还原硫酸盐,为成矿提供另一硫源。Mg2+可能是控制成矿过程中TSR作用的一个因素;(2)热液碳酸盐矿物碳(氧)同位素组成指示了TSR作用氧化的有机碳与流体溶解围岩碳酸盐岩中碳的不均匀混合作用;(3)矿床中与成矿作用有关的有机质(沥青)具有高-过成熟度特征和低芳烃含量,或是其参与了TSR作用的一个标志;(4)川滇黔地区油气成藏-破坏和赤普铅锌成矿可能是盆山演化过程中不同阶段或是同一阶段不同时代的产物,铅锌矿床形成与古老油气藏破坏密切相关。

华南地区泥盆系MVT铅锌矿床S、Pb同位素特征

华南泥盆系密西西比河谷型(MVT)铅锌矿床,受控于泥盆系海进序列的台地碳酸盐岩,大体可分为以凡口为代表的中低温热液型和以泗顶、北山为代表的低温热液型。在矿床学研究基础上,对研究区内不同类型的铅锌矿、硫铁矿开展系统的硫、铅同位素分析,收集和测定493件S和64件Pb同位素数据,总结硫、铅的来源和硫同位素分馏机制,并初步探讨了成矿机制。硫同位素研究显示,矿石硫有多种来源,主要来自于还原性卤水,部分来自氧化性卤水中ΣSO_4^(2-)的还原,少量硫来自于矿区含矿地层。不同矿床在成矿作用过程中硫同位素的分馏机制不同。在以凡口为代表的中低温热液矿床中,矿石δ^(34)S值高且相对集中,以热力学分馏为主,生物分馏作用较微弱;在以泗顶、北山为代表的低温热液矿床中,矿石δ^(34)S值低且分散,以生物分馏作用为主,仅部分中粗粒铅锌矿石以热力学分馏为主。成矿作用过程中硫同位素分馏远未达到平衡状态。不同矿床的矿石铅同位素组成呈线性分布,反映出不同来源铅的混合。古老铅来自遭剥蚀的古陆,年轻铅代表泥盆系沉积物的普通铅。二者的比例与岩石中陆源物质(Pb)的含量相对应。成矿时的铅直接来自于氧化性卤水,间接来自于卤水对流经的泥盆系含矿层(尤其是底部碎屑岩)的淋滤,更间接地来自古陆剥蚀区以及海相沉积物。金属物质的迅速沉淀成矿作用与两类流体的混合有关,氧化性卤水来自蒸发盐红层盆地,沿泥盆系底部紫色砂岩经区域性迁移,其中富含大量金属成矿元素,并含有少量呈ΣSO_4^(2-)的硫;而还原性流体中富含ΣH2S的硫。流体的混合作用局限于矿区范围内,并不存在区域性的简单大规模流体混合过程。

An experimental study on metal precipitation driven by fluid mixing: implications for genesis of carbonate-hosted lead–zinc ore deposits

A type of carbonate-hosted lead–zinc(Pb–Zn)ore deposits, known as Mississippi Valley Type(MVT)deposits, constitutes an important category of lead–zinc ore deposits. Previous studies proposed a fluid-mixing model to account for metal precipitation mechanism of the MVT ore deposits, in which fluids with metal-chloride complexes happen to mix with fluids with reduced sulfur, producing metal sulfide deposition. In this hypothesis, however, the detailed chemical kinetic process of mixing reactions, and especially the controlling factors on the metal precipitation are not yet clearly stated. In this paper, a series of mixing experiments under ambient temperature and pressure conditions were conducted to simulate the fluid mixing process, by titrating the metal-chloride solutions, doping withor without dolomite, and using NaHS solution. Experimental results, combined with the thermodynamic calculations, suggest that H_2S, rather than HS^-or S^(2-),dominated the reactions of Pb and/or Zn precipitation during the fluid mixing process, in which metal precipitation was influenced by the stability of metal complexes and the pH. Given the constant concentrations of metal and total S in fluids, the pH was a primary factor controlling the Pb and/or Zn metal precipitation. This is because neutralizing or neutralized processes for the ore-forming fluids can cause instabilities of Pb and/or Zn chloride complexes and re-distribution of sulfur species, and thus can facilitate the hydrolysis of Pb and Zn ions and precipitation of sulfides. Therefore, a weakly acidic to neutral fluid environment is most favorable for the precipitation of Pb and Zn sulfides associated with the carbonate-hosted Pb–Zn deposits.

云南乐红铅锌矿床成矿时代与成矿物质来源:Rb-Sr和S同位素制约

川滇黔交界地区是我国重要的铅锌矿产地,云南省鲁甸县乐红铅锌矿床是区内近年来探获的又一大型MVT型铅锌矿床。本文通过乐红铅锌矿床闪锌矿Rb-Sr测年获得等时线年龄为200.9±8.3 Ma,显示成矿作用发生于印支晚期。闪锌矿初始锶同位素比值特征指示了成矿金属物质为壳源,主要来自于基底地层和沉积盖层。矿床金属硫化物硫同位素特征表明乐红铅锌矿床硫源为海水硫酸盐,还原硫可能是海水硫酸盐经过热化学还原作用(TSR)而来。结合矿床地质特征与区内铅锌矿成矿地质背景,认为乐红铅锌矿床可能是在印支晚期华南板块与印支板块拼合造山作用下,引起成矿流体运移,进而在容矿构造内沉淀成矿的结果。

甘肃代家庄铅锌矿的地质特征与找矿意义

位于甘肃宕昌县的代家庄矿床曾被认为是西成矿田铅锌找矿的重大进展,矿床产于秦岭西成盆地西北端泥盆系浅海相的富含生物化石的细碎屑岩—灰岩中。矿体不规则受NW向断裂的控制,呈角砾状分布于下部碎屑岩与上部厚层灰岩界面附近灰岩一侧。矿石的矿物共生组合为闪锌矿+方铅矿+少量黄铁矿+少量白铁矿+方解石,不含石英。硫化物发育大量的胶状、球粒状、草霉状微晶结构,部分显现出微生物化石结构特点。对代家庄与西成主要类型铅锌矿床地质地球化学特征的对比发现,二者在容矿围岩沉积环境、矿石形态、结构构造以及同位素地球化学等多方面存在明显的差异,代家庄矿床成因属于碳酸盐岩容矿的低温热液矿床,不同于西成矿田的主要SEDEX类型。主要控矿因素为灰岩—碎屑界面附近、NW向断裂等。