Although molybdenum (Mo) isotopic compositions of carbonatites, phosphorites and siliceous rocks can be used as proxies to reconstruct conditions of marine chemistry throughout geological time, only a few studies have, so far, analysed these low-Mo (ng g−1) geological samples because of analytical limitations. In this study, a low blank, high yield two-column Mo purification procedure was developed for various low-Mo geological samples. The sample-standard bracketing (SSB) and double-spike (DS) methods for mass fractionation correction were used to compare the accuracy of Mo isotope ratio measurements. Six Mo reference materials, NIST SRM 3134 Mo, JMC Mo, SC+1 and SC−1 (eluted fractions of Sigma-Aldrich Mo), CRM GSR-6 limestone and USGS BCR-2 basalt, were used as quality controls. The results showed that the Mo delta values of reference materials and geological samples corrected by the SSB and DS methods were, within error, consistent with each other and the DS method was the method of choice for samples with <0.5 μg g−1 Mo. The average instrument long-term (over 1 year) external reproducibility of NIST SRM 3134 Mo was better than ±0.03‰ amu−1 (2SD, n = 288) and the analytical precision of low-Mo (101 to 103 ng g−1) geological samples was better than ±0.04‰ amu−1. This method can facilitate Mo isotope ratio measurements in geological samples with a low Mo content, offering a possibility to study a wider range of Mo reservoirs in geological processes.

This study presents chlorine isotopic composition of salt deposits recovered in a core from the Qarhan Saline Lake in the Qinghai Province of China. The δ37Cl trend has three stages, and they correspond to the upper, middle, and lower salt-bearing groups of the entire evaporite system. The δ37Cl values are between −0.22‰ and 0.13‰ with an average value of −0.02‰ in the lower salt-bearing group. It ranges between 0.14‰ and 0.76‰ (x¯ = 0.36‰) in the middle salt-bearing group, and varies between −0.35‰ to 0.35‰ (x¯ = −0.04‰) in the upper salt-bearing group. This work indicates that stratification of δ37Cl values is accompanied by stratigraphic variations in Mg/Cl and K/Cl in halite. We suggest a “evaporation cycles model” and it indicates the potential of Cl isotope as a geochemical tracer in order to understand paleoclimatic conditions during different stages of evaporite deposition.

•The polymetallic vein-type Zn-Pb deposits are indium-enriched, and have a different mineralized process from the MVT Zn-Pb deposits along the Xiangxi-Qiandong Zn-Pb metallogenic belt.•C-H-O and Pb isotopic data suggest ore-forming fluids were derived from magmatic-hydrothermal systems.Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCleqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ18OH2O SMOW = 0.2‰ to 4.2‰; δDH2O SMOW = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO32− or CO2 in ore-forming fluid (δ13CPDB = −6.9‰ to −5.7‰, δ18OSMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ34SVCDT = 8.8–14.2‰ and 206Pb/204Pb = 17.156–17.209, 207Pb/204Pb = 15.532–15.508, 208Pb/204Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ18OH2O and δDH2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ18OH2O and δDH2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.Download high-res image (199KB)Download full-size image

•Cd and S isotope compositions of sphalerites are reported for the first time.•Heavy Cd isotopes are enriched in early precipitated sphalerite.•Cd could be a potential indicator to distinguish the origin of the Zn–Pb deposits.Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ34SCDT values ranging from 0.2 to 5.0‰. Although δ34SCDT and δ114/110Cd values in sphalerites have no regular spatial variations, the δ34SCDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ34S∑S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.Download high-res image (166KB)Download full-size image

•Rare ikunolite, izoklakeite, and boulangerite were found in the deposit.•Physicochemical conditions were well constrained by logfS2, logfO2, T and pH.•Decoupled logfS2 and logfO2 is important for the origin of W–Cu deposit.The Sanjiang Tethyan domain in SE Asia is one of the most important mineral belts in China. Cu, Pb–Zn, Ag, Au and Sn are the most important resources in this domain, while the tungsten mineralization is poorly reported. In this study, we report on mineralogy in recent discovered Damajianshan (DMJS) tungsten (–Cu–As–Mo–Bi) polymetallic deposit in the southern part of Sanjiang Tethyan domain related to Triassic quartz porphyry. Studies have shown that besides common ore minerals, such as native bismuth, bismuthinite, ikunolite, some specific minerals of Pb–Bi- and Pb–Sb-sulphosalts (e.g. izoklakeite, bournonite, cosalite, and boulangerite) have also been found. Based on paragenetic mineral assemblages, fluid inclusions, and thermodynamic studies, the physicochemical conditions were evaluated for the entire metallogenic process. The sulfur fugacity (logfS2) ranges from − 9.7 to − 37 with ore-forming temperatures between 190 °C and 330 °C, and the oxygen fugacity (logfO2) ranges from − 37.5 to − 38.5 when the temperature is 250 °C. The sulfur fugacity and oxygen fugacity show strong fluctuations with broadly negative correlation, indicating that these variations in physicochemical conditions should be responsible for mineral assemblages, and are one of the most significant factors leading to the formation of the DMJS deposit. Our mineralogical studies provide new information for tungsten mineralization and further exploration of tungsten resources in the Sanjiang Tethyan mineralization domain.

•Sm–Nd and Re–Os ages favor a multistage mineralization event in the Lanping basin, China.•The Cu–Ag mineralization ages cluster into three groups, i.e. ∼56–54, 51–48, and 31–29 Ma.•The Zn–Pb mineralization ages were likely to postdate than 37 Ma, although not dated directly.•The multistage mineralization events correspond to stages of the Indo-Asian collision orogeny.The Lanping basin is a significant Pb–Zn–Cu–Ag mineralization belt of the Sanjiang Tethyan metallogenic province in China. Over 100 thrust-controlled, sediment-hosted, Himalayan base metal deposits have been discovered in this basin, including the largest sandstone-hosted Pb–Zn deposit in the world (Jinding), and several Cu ± Ag ± Co deposits (Baiyangping, Baiyangchang and Jinman). These deposits, with total reserves of over 16.0 Mt Pb + Zn, 0.6 Mt Cu, and 7000 t Ag, are mainly hosted in Meso-Cenozoic mottled clastic rocks, and strictly controlled by two Cenozoic thrust systems developed in the western and eastern segments of the Lanping basin.To define the metallogenic history of the study area, we dated nine calcite samples associated with copper sulfides from the Jinman Cu deposit by the Sm–Nd method and five molybdenite samples from the Liancheng Cu–Mo deposit by the Re–Os method. The calcite Sm–Nd age for the Jinman deposit (58 ± 5 Ma) and the molybdenite Re–Os age for the Liancheng deposit (48 ± 2 Ma), together with previously published chronological data, demonstrate (1) the Cu–Ag mineralization in the western Lanping basin mainly occurred in three episodes (i.e., ∼56–54, 51–48, and 31–29 Ma), corresponding to the main- and late-collisional stages of the Indo–Asian orogeny; and (2) the Pb–Zn–Ag (±Cu) mineralization in the eastern Lanping basin lacked precise and direct dating, however, the apatite fission track ages of several representative deposits (21 ± 4 Ma to 32 ± 5 Ma) may offer some constraints on the mineralization age.

We analyzed the Se isotopic composition of black shales and related kerogen and sulfide fractions from the Zunyi Ni–Mo–Se deposit, the La’erma Se–Au deposit and the Yutangba Se deposit in southern China to constrain metal sources and accumulation processes, both subjects of disagreement in the scientific community. Se at the Zunyi Ni–Mo–Se polymetallic deposit displayed a restricted range of δ82Se values (−1.6‰ to 2.4‰ with a mean of 0.6‰) suggesting a major hydrothermal origin where aqueous Se was probably transported as H2Se, along with H2S, and precipitated directly as selenides or in sulfides. Se at the La’erma Se–Au deposit covers a larger range in δ82Se values (−3.8‰ to 5.4‰ with a mean of 0.3‰), suggesting Se redistribution following redox transformations, leading to kinetic isotopic fractionation. The largest Se isotopic variation so far in natural terrestrial samples was found in the Yutangba Se deposit, with δ82Se values varying from −12.77‰ to 4.93‰. On the basis of variations in Se isotopes in the deposit, along with other geological and geochemical evidence, the “redox model” (supergene alteration) explains the occurrence of native Se in the deposit. Overall, hydrothermal systems may be a potentially important Se source to form economic deposits in comparison to seawater sources. Significantly, our study indicates that either secondary hydrothermal or supergene alteration is a key factor in Se enrichment in black shales. Redistribution of Se, and probably other redox-sensitive metals like Mo, Cr and V, leads to isotopic fractionation which may be used to fingerprint such alteration/precipitation processes.

To understand the impact of Selenium (Se) into the biogeochemical cycle and implications for palaeo-redox environment, a sequential extraction method was utilized for samples including black shales, cherts, a Ni–Mo–Se sulfide layer, K-bentonite and phosphorite from Lower Cambrian Se-enriched strata in southern China. Seven species (water-soluble, phosphate exchangeable, base-soluble, acetic acid-soluble, sulfide/selenide associated, residual Se) and different oxidation states (selenate Se(VI), selenite Se(IV), organic Se, Se (0) and mineral Se(-II)) were determinated in this study. We found that the Ni–Mo–Se sulfide layer contained a significantly greater amount of Se(-II) associated with sulfides/selenides than those in host black shales and cherts. Furthermore, a positive correlation between the degree of sulfidation of iron (DOS) and the percentage of the sulfide/selenide-associated Se(-II) was observed for samples, which suggests the proportion of sulfide/selenide-associated Se(-II) could serve as a proxy for palaeo-redox conditions. In addition, the higher percentage of Se(IV) in K-bentonite and phosphorite was found and possibly attributed to the adsorption of Se by clay minerals, iron hydroxide surfaces and organic particles. Based on the negative correlations between the percentage of Se(IV) and that of Se(-II) in samples, we propose that the K-bentonite has been altered under the acid oxic conditions, and the most of black shale (and cherts) and the Ni–Mo–Se sulfide layer formed under the anoxic and euxinic environments, respectively. Concerning Se accumulation in the Ni–Mo–Se sulfide layer, the major mechanism can be described by (1) biotic and abiotic adsorption and further dissimilatory reduction from oxidized Se(VI) and Se(IV) to Se(-II), through elemental Se, (2) contribution of hydrothermal fluid with mineral Se(-II).

Although molybdenum (Mo) isotopic compositions of carbonatites, phosphorites and siliceous rocks can be used as proxies to reconstruct conditions of marine chemistry throughout geological time, only a few studies have, so far, analysed these low-Mo (ng g−1) geological samples because of analytical limitations. In this study, a low blank, high yield two-column Mo purification procedure was developed for various low-Mo geological samples. The sample-standard bracketing (SSB) and double-spike (DS) methods for mass fractionation correction were used to compare the accuracy of Mo isotope ratio measurements. Six Mo reference materials, NIST SRM 3134 Mo, JMC Mo, SC+1 and SC−1 (eluted fractions of Sigma-Aldrich Mo), CRM GSR-6 limestone and USGS BCR-2 basalt, were used as quality controls. The results showed that the Mo delta values of reference materials and geological samples corrected by the SSB and DS methods were, within error, consistent with each other and the DS method was the method of choice for samples with <0.5 μg g−1 Mo. The average instrument long-term (over 1 year) external reproducibility of NIST SRM 3134 Mo was better than ±0.03‰ amu−1 (2SD, n = 288) and the analytical precision of low-Mo (101 to 103 ng g−1) geological samples was better than ±0.04‰ amu−1. This method can facilitate Mo isotope ratio measurements in geological samples with a low Mo content, offering a possibility to study a wider range of Mo reservoirs in geological processes.