Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Stable oxygen and carbon isotopes of carbonate concretions of the Miocene Yeonil Group in the Pohang Basin,Korea: Types of concretions and formation condition

Carbonate concretions in the Miocene sedimentary rocks of the Yeonil Group in the Pohang Basin (Korea) were investigated in terms of stable oxygen and carbon isotope composition to delineate the origin and associated diagenetic environment for their formation. Carbonate concretions are widely distributed in all the sedimentary rocks in the Pohang Basin, showing that the calcitic concretions are preserved within the mass-flow deposits and the dolomitic ones mostly in the hemipelagic siliceous rocks (diatomites). Concretions can be classified into four different types, on the basis of the stable isotopic signatures, each of which represents its own geochemical range.Type I concretions are calcitic and are composed of micrite to microspar. They occur in the conglomerates and sandstones which were deposited by mass flows (debris flow to turbidity current). It shows relatively lower δ¹⁸O (− 14.0 to − 9.3‰) and δ¹³C (− 19.6 to − 8.4‰) values. These concretions grew in a sulfate reducing zone under the influence of residual ambient seawater which had been significantly modified by volcanogenic sediments. Type II concretions are also calcitic, composed mostly of micrite with minor microspar and found in the sandstones. These concretions are characterized by relatively high δ¹⁸O (+ 1.8 to + 2.4‰) and variable δ¹³C (− 17.3 to − 0.4‰) values. These isotopic signatures reflect that Type II concretions formed from just beneath the sediment/water interface down to the sulfate reducing zone through the early stage of methanogenesis. Type III concretions are also calcitic, and composed largely of micrite with a minor contribution of microspar. They are observed in hemipelagic mudrocks which were deposited under the influence of mass flows. They are characterized by intermediate to high δ¹⁸O (− 4.6 to + 1.6‰) and high δ¹³C (− 1.3 to + 8.8‰) values. These concretions grew in a methanogenic zone by residual ambient seawater and/or seawater slightly modified by reaction with volcanogenic sediments. Type IV concretions are dolomite with calcite inclusion, and occur in hemipelagic siliceous rocks. These concretions are mostly composed of micrite and characterized by variable δ¹⁸O (− 9.1 to + 0.7‰) and high δ¹³C (+ 3.1 to + 17.9‰) values, suggesting formation in the methanogenic zone, although the residual ambient seawater is slightly modified by volcanogenic sediments.The same type of the concretions is widely distributed throughout the basin and always shows its own distinctive stable isotopic signature. This means that the formation of the given type depends upon the lithology and composition of host sediments that are closely related to the depositional process of the fan-delta systems regardless of their localities. Further, the different types of concretions are also found at the different, but closely spaced stratigraphic levels in the same locality, displaying the distinctive diagenetic conditions for each type. Such preservation of the unique diagenetic signatures in individual type of concretion suggests that the concretions formed in a completely closed diagenetic system. Therefore, caution should be made to simplify and generalize the diagenetic condition for the formation of any concretions in a large sedimentary basin.     

Nakhlak carbonate-hosted Pb(Ag) deposit,Isfahan province,Iran: a geological,mineralogical, geochemical,fluid inclusion,and sulfur isotope study

The Upper Cretaceous Nakhlak epigenetic vein-type Pb(Ag) deposit is located 55 km northeast of the town of Anarak in Isfahan Province, Iran. The deposit contains 7 Mt of galena-barite ore with an average grade of 8.33% Pb, 0.38% Zn, and 72 ppm Ag. The ore mineralization occurs as stratabound, epigenetic, steeply dipping, east-west–trending veins in faulted- or fracture-controlled Upper Cretaceous Sadar carbonates. Galena and barite are the primary minerals. Minor sphalerite, tennantite-tetrahedrite, pyrite, and chalcopyrite occur as inclusions in galena. Cerussite with minor amounts of anglesite and plattnerite formed in the oxidized supergene zone. The ore and ore-related minerals were deposited in the hydrothermally dolomitized carbonate host rock containing saddle-shaped dolomite. Geochemically, the dolomitized carbonate host rocks are enriched in MgO, Fe₂O₃, MnO, Pb, Zn, and Ba, but depleted in CaO. The galena concentrate contains high values of Ag (932 ppm), Sb (342 ppm), Cu (422 ppm), As (91 ppm), and Zn (296 ppm); the presence of these trace elements indicates a low-temperature type of galena mineralization. This interpretation is corroborated by fluid inclusions containing 12.98 wt.% NaCl equivalent salinity; the inclusions homogenize at the low temperature of about 152.1 °C. The similarity between δ³⁴S_(V-CDT) values in Nakhlak barite and Permian–Triassic δ³⁴S marine sulfate values indicates that the Nakhlak sulfur was probably provided from evaporates of Permian–Triassic age. The δ³⁴S_(V-CDT) values of galena and barite samples occupy the ranges of − 1.04‰ to + 8.62‰ and + 10.95‰ to + 13.71‰, respectively, and are similar to Mississippi Valley–type (MVT) deposits. The low-temperature basinal fluids, evaporate-originated sulfur, and fault- or fracture-controlled galena-rich veins in the Nakhlak deposit resemble the type of geological features documented in Pb-rich MVT deposits.     

Origins of non-equilibrium lithium isotopic fractionation in xenolithic peridotite minerals: Examples from Tanzania

Olivine, clinopyroxene and orthopyroxene in variably metasomatised peridotite xenoliths from three lithospheric mantle sections beneath the East African Rift in Tanzania (Lashaine, Olmani, Labait) show systematic differences in their average Li concentrations (2.4 ppm, 2.0 ppm and 1.5 ppm, respectively) and intermineral isotopic fractionations, with olivine being heaviest (δ⁷Li = + 2.3 to + 13.9‰, average + 5.0‰), followed by orthopyroxene (? 4.1 to + 6.5‰, average + 0.8‰) and clinopyroxene (? 6.7 to + 4.1‰, average ? 1.6‰). These features are ascribed to the effects of kinetic Li isotope fractionation combined with different Li diffusivities in mantle minerals.Two main mechanisms likely generate diffusion-driven kinetic Li isotope fractionation in mantle xenoliths (1) Li diffusion from grain boundary melt into minerals during recent metasomatism or entrainment in the host magma and (2) subsolidus intermineral Li-redistribution. The latter can produce both isotopically light (Li-addition) and heavy (Li-loss) minerals and may occur in response to changes in pressure and/or temperature.Modelling shows that non-mantle-like δ⁷Li in clinopyroxene (< + 2‰), combined with apparent equilibrium olivine-clinopyroxene elemental partitioning in most peridotite xenoliths from all three Tanzanian localities probably reflects incipient Li addition during interaction with the host magma. Low δ⁷Li (< ? 3‰), combined with high Li concentrations (> 3 ppm) in some clinopyroxene may require very recent (minutes) Li ingress from a Li-rich melt (100s of ppm) having mantle-like δ⁷Li. This might happen during late fragmentation of some mantle xenoliths caused by a volatile- (and Li-) rich component exsolved from the host basalt. In contrast, high Li concentrations (> 2 ppm) and δ⁷Li (> 4‰) in olivine from many Labait and Olmani samples are attributed to an older, pre-entrainment enrichment event during which isotopic equilibrium was attained and whose signature was not corrupted during xenolith entrainment. Low Li concentrations and mantle-like isotopic composition of olivine from most Lashaine xenoliths indicate limited metasomatic Li addition.Thus, Li concentrations and isotope compositions of mantle peridotites worldwide may reflect two processes, with olivine mainly preserving a signature of depletion in refractory samples (low Li contents and δ⁷Li) or of older (precursory) melt addition in metasomatised samples (high Li contents and δ⁷Li), while non mantle-like, low δ⁷Li in almost all clinopyroxene can be due to Li ingress during transport in the host magma and/or slow cooling, if the samples were erupted in lavas. In Tanzania, the peridotites experienced rift-related heating prior to entrainment and were quenched upon eruption, so Li ingress is the most likely process responsible for the isotopically light clinopyroxene here.     

Geology and genesis of the Xiaguan Ag–Pb–Zn orefield in Qinling orogen,Henan province,China: Fluid inclusion and isotope constraints

The Xiaguan Ag–Pb–Zn orefield (Neixiang County, Henan Province), hosting the Yindonggou, Zhouzhuang, Yinhulugou and Laozhuang fault-controlled lode deposits, is situated in the Erlangping Terrane, eastern Qinling Orogen. The quartz-sulfide vein mineralization is dominated by main alteration styles of silicic-, sericite-, carbonate-, chlorite- and sulfide alteration. Major Ag-bearing minerals are freibergite, argentite and native Ag. The deposits were formed by a CO₂-rich, mesothermal (ca. 250–320 °C), low-density and low salinity (< 11 wt.% NaCl equiv.), Na⁺–Cl⁻-type fluid system. Trapping pressures of the carbonic-type fluid inclusions (FIs) decreased from ca. 280–320 MPa in the early mineralization stage to ca. 90–92 MPa in the late mineralization stage, indicating that the ore-forming depths had become progressively shallower. This further suggests that the metallogenesis may have occurred in a tectonic transition from compression to extension. Geological- and ore fluid characteristics suggest that the Xiaguan Ag–Pb–Zn orefield belongs to orogenic-type systems.The δ¹⁸O_H2O values change from the Early (E)-stage (7.8–10.8 ‰), through Middle (M)-stage (6.0–9.4 ‰) to Late (L)-stage (− 1.5–3.3 ‰), with δD values changing from E-stage − 95 to − 46 ‰, through M-stage − 82 to − 70 ‰ to L-stage − 95 to − 82 ‰. δ¹³C_CO2 values of the ore fluids in the E- and M-stage quartz vary between 0.1 ‰ and 0.9 ‰ (average: 0.3 ‰); δ¹³C_CO2 values of L-stage FIs are − 0.2–0.1 ‰ in quartz and − 6.8 ‰ to − 3.5 ‰ in calcite. The H–O–C isotopic data indicate that the initial ore fluids were sourced from the underthrusted Qinling Group marine carbonates, and were then interacted with the ore-hosting Erlangping Group metasedimentary rocks. Inflow of circulated meteoric water may have dominated the L-stage fluid evolution.Sulfur (δ³⁴S = 1.9–8.1 ‰) and lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.202–18.446, ²⁰⁷Pb/²⁰⁴Pb = 15.567–15.773 and ²⁰⁸Pb/²⁰⁴Pb = 38.491–39.089) of sulfides suggest that the ore-forming materials were mainly sourced from the ore-hosting metasedimentary strata. The stepped heating sericite ⁴⁰Ar/³⁹Ar detection suggests that the mineralization occurred in the Middle Jurassic to Early Cretaceous (ca. 187 − 124 Ma). Considering the regional tectonic evolution of the Erlangping Terrane, we propose that the Xiaguan Ag–Pb–Zn orefield was formed in a continent–continent collisional tectonic regime, in accordance with the tectonic model for continental collision, metallogeny and fluid flow (CMF).     

The nappe-hosted Hoshbulak MVT Zn–Pb deposit,Xinjiang, China: A review of the geological,elemental and stable isotopic constraints

The Hoshbulak Zn–Pb deposit is located in South Tianshan, Xinjiang, China. The Zn–Pb orebody is tabular and stratoid in form and it is hosted in calcareous rocks of the Upper Devonian Tan'gaitaer Formation which were thrust over the Carboniferous system. The ores are mineralogically simple and composed mainly of sphalerite, galena, pyrite, calcite, dolomite and exhibit massive, banded, veinlets, colloidal, metasomatic, eutectic, concentric ring and microbial-like fabrics. The Co/Ni ratios of pyrite in the ores range from 0.46 to 0.90 by electron microprobe, which suggested that the Hoshbulak Zn–Pb mineralization was formed in a sedimentary environment. The REE patterns of the hydrothermal calcite coincide well with those of recrystallized micritic limestones, suggesting that the Hoshbulak Pb–Zn mineralization was closely genetically related to limestones of the Tan'gaitaer Formation. The C-, H- and O-isotopic compositions of hydrothermal calcite and dolomite in the ores yield δ¹³C(VPDB) values ranging from − 1.9‰ to + 2.6‰ (mean 0.79‰), δ¹⁸O(VSMOW) values from 22.41‰ to 24.67‰ (mean 23.04‰) and δD values from − 77‰ to − 102‰ for fluid inclusions. It is suggested that the ore-forming fluids, including CO₂, were derived from the calcareous strata of the Tan'gaitaer Formation in association with hydrocarbon brines. The δ³⁴S(VCDT) ranges from − 22.3‰ to − 8.5‰ for early ore-stage sulfides and from 5.9‰ to 24.2‰ with a cluster between 14.4‰ and 24.2‰ for the sulfides (pyrite, sphalerite, galena) in the main ore-stage. The ore sulfur may have been derived from evaporite rocks by thermochemical sulfate reduction (TSR) as the predominant mechanism for H₂S generation. The Pb-isotopic compositions of the sulfide minerals from the Hoshbulak ores yield ²⁰⁶Pb/²⁰⁴Pb ratios from 17.847 to 18.173, ²⁰⁷Pb/²⁰⁴Pb ratios from 15.586 to 15.873 and ²⁰⁸Pb/²⁰⁴Pb ratios from 37.997 to 38.905, which indicate that the metals were sourced mainly from the Tan'gaitaer Formation. We conclude that the genesis of the Hoshbulak Mississippi Valley-type deposit was closely related to thrust faulting in the South Tianshan orogen of China.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) deposit.     

Hydrothermalism in the Tyrrhenian Sea: Inorganic and microbial sulfur cycling as revealed by geochemical and multiple sulfur isotope data

The Palinuro volcanic complex and the Panarea hydrothermal field, both located in the Tyrrhenian Sea (Italy), are associated with island arc magmatism and characterized by polymetallic sulfide mineralization. Dissolved sulfide concentrations, pH, and Eh measured in porewaters at both sites reveal a variable hydrothermal influence on porewater chemistry.Multiple sulfur isotopic measurements for disseminated sulfides (CRS: chromium reducible sulfur) extracted from sediments at Palinuro yielded a broad range in δ³⁴S range between ?29.8 and + 10.2‰ and Δ³³S values between + 0.015 and + 0.134‰. In contrast, sediments at Panarea exhibit a much smaller range in δ³⁴S_CRS with less negative values between ?11.3 and ?1.8‰. The sulfur isotope signatures are interpreted to reflect a mixture between hydrothermal and biogenic sulfide, with a more substantial biogenic contribution at Panarea.Multiple sulfur isotope measurements were performed on sulfides and elemental sulfur from drill core material from the Palinuro massive sulfide complex. δ³⁴S and Δ³³S values for pyrite between ?32.8 and ?1.1‰ and between ?0.012 to + 0.042‰, respectively, as well as for elemental sulfur with δ³⁴S and Δ³³S values between ?26.7 and ?2.1‰ and between + 0.035 and + 0.109‰, respectively, point to a microbial origin for much of the sulfide and elemental sulfur studied. Moreover, data suggest a coupling of bacterial sulfate reduction, sulfide oxidation and sulfur disproportionation. In addition, δ³⁴S values for barite between + 25.0 and + 63.6‰ are also in agreement with high microbial turnover of sulfate at Palinuro.Although a magmatic SO₂ contribution towards the formation of the Palinuro massive sulfide complex is very likely, the activity of different sulfur utilizing microorganisms played a fundamental role during its formation. Thus, porewater and multiple sulfur isotope data reveal differences in the hydrothermal activity at Palinuro and Panarea drill sites and underline the importance of microbial communities for the origin of massive sulfide mineralizations in the hydrothermal subsurface.     

Geology,isotope geochemistry and ore genesis of the Shanshulin carbonate-hosted Pb–Zn deposit,southwest China

The Shanshulin Pb–Zn deposit occurs in Upper Carboniferous Huanglong Formation dolomitic limestone and dolostone, and is located in the western Yangtze Block, about 270 km west of Guiyang city in southwest China. Ore bodies occur along high angle thrust faults affiliated to the Weishui regional fault zone and within the northwestern part of the Guanyinshan anticline. Sulfide ores are composed of sphalerite, pyrite, and galena that are accompanied by calcite and subordinate dolomite. Twenty-two ore bodies have been found in the Shanshulin deposit area, with a combined 2.7 million tonnes of sulfide ores grading 0.54 to 8.94 wt.% Pb and 1.09 to 26.64 wt.% Zn. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 3.1 to + 2.5‰ and + 18.8 to + 26.5‰, respectively. These values are higher than mantle and sedimentary organic matter, but are similar to marine carbonate rocks in a δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, suggesting that carbon in the hydrothermal fluid was most likely derived from the carbonate country rocks. The δ³⁴S_CDT values of sphalerite and galena samples range from + 18.9 to + 20.3‰ and + 15.6 to + 17.1‰, respectively. These values suggest that evaporites are the most probable source of sulfur. The δ³⁴S_CDT values of symbiotic sphalerite–galena mineral pairs indicate that deposition of sulfides took place under chemical equilibrium conditions. Calculated temperatures of S isotope thermodynamic equilibrium fractionation based on sphalerite–galena mineral pairs range from 135 to 292 °C, consistent with previous fluid inclusion studies. Temperatures above 100 °C preclude derivation of sulfur through bacterial sulfate reduction (BSR) and suggest that reduced sulfur in the hydrothermal fluid was most likely supplied through thermo-chemical sulfate reduction (TSR). Twelve sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.55‰ (mean + 0.25‰) relative to the JMC 3-0749L zinc isotope standard. Stages I to III sphalerite samples have δ⁶⁶Zn values ranging from 0.00 to + 0.07‰, + 0.12 to + 0.23‰, and + 0.29 to + 0.55‰, respectively, showing the relatively heavier Zn isotopic compositions in later versus earlier sphalerite. The variations of Zn isotope values are likely due to kinetic Raleigh fractional crystallization. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios of the sulfide samples fall in the range of 18.362 to 18.573, 15.505 to 15.769 and 38.302 to 39.223, respectively. The Pb isotopic ratios of the studied deposit plot in the field that covers the upper crust, orogenic belt and mantle Pb evolution curves and overlaps with the age-corrected Proterozoic folded basement rocks, Devonian to Lower Permian sedimentary rocks and Middle Permian Emeishan flood basalts in a ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb diagram. This observation points to the derivation of Pb metal from mixed sources. Sphalerite samples have ⁸⁷Sr/⁸⁶Sr_200 Ma ratios ranging from 0.7107 to 0.7115 similar to the age-corrected Devonian to Lower Permian sedimentary rocks (0.7073 to 0.7111), higher than the age-corrected Middle Permian basalts (0.7039 to 0.7078), and lower than the age-corrected Proterozoic folded basement (0.7243 to 0.7288). Therefore, the Sr isotope data support a mixed source. Studies on the geology and isotope geochemistry suggest that the Shanshulin deposit is a carbonate-hosted, thrust fault-controlled, strata-bound, epigenetic, high grade deposit formed by fluids and metals of mixed origin.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

S,O and Pb isotopic evidence on the origin of the İnkaya (Simav-Kütahya) Cu–Pb–Zn–(Ag) Prospect,NW Turkey

The İnkaya Cu–Pb–Zn–(Ag) prospect is a typical example of the hydrothermal mineralization occurring in the Menderes Massif, which crop out in Western Anatolia. The prospect located approximately 20 km west of Simav (Kütahya-Turkey) in northern part of the Menderes Massif have been characterized through the detailed examinations involving geological, mineralogical, whole-rock geochemistry, fluid inclusion, stable isotope and lead isotope.The İnkaya Cu–Pb–Zn–(Ag) prospect is located along an E–W-trending fault in the Cambrian Simav Metamorphics, which consist of quartz–muscovite schist, quartz–biotite schist, muscovite schist, biotite schist and the Arıkayası Formation, which is composed of marbles. Galena, sphalerite, chalcopyrite, pyrite and fahlore are the main minerals, and they are accompanied by small amounts of cerussite, anglesite, digenite, enargite, chalcocite, covellite, bornite, and Fe-oxides with gangue quartz. In addition to Pb, Zn, Cu, Ag, the ore samples contain substantial quantities of As, Cd and Bi and small amount of Au. Average contents of Cu, Pb, Zn and Ag are 77,400 ppm, 102,600 ppm, 6843 ppm and 203 ppm, respectively.The δ³⁴S values for galena, chalcopyrite and pyrite formed in the same stage vary in the range from − 1.7 to − 2.1‰ (average − 2.0), 0.1 to 0.3‰ (average 0.2) and − 1.5 to 2.6‰ (average + 1.5), respectively.δ³⁴S values for H₂S, representing the composition of the fluids responsible for the sulfide mineral formations and calculated from the δ³⁴S value are between − 2.77 and 1.33‰; it is consistent with the sulfur in sulfide minerals. δ¹⁸O_quartz values range from 11.3 to 16.4‰ and estimated δ¹⁸O_fluid values range from 5.4 to 10.6‰.Pyrite–galena and pyrite–chalcopyrite pairs calculated to determine equilibrium isotope temperatures based on δ³⁴S values are between 254.6 and 277.4 °C for pyrite–galena and 274.7 °C for pyrite–chalcopyrite. Sulfur and oxygen isotope values similar to the values for fluid equilibrated with an felsic magmatic source.Fluid inclusion studies on quartz of the same silicification stage coexisting with galena, sphalerite and chalcopyrite collected from the mineralized vein indicate that the temperature range of the fluids is 235 °C to 340 °C and that the salinities are 0.7 to 4.49 wt.% NaCl equivalent. The wide range of homogenization temperatures and relatively lower salinities of the fluid inclusions indicate that at least two different fluid generations were trapped in the quartz from only one fluid type. Also, lower salinities of fluid inclusion probably indicate mixing of meteoric water and magmatic fluid.The galena has ²⁰⁶Pb/²⁰⁴Pb values of 18.862–18.865, ²⁰⁷Pb/²⁰⁴Pb values of 15.707–15.711, and ²⁰⁸Pb/²⁰⁴Pb values of 39.033–39.042. The lead isotope values show a similarity with upper crustal values.     

Geological and isotopic constraints on the origin of the Anle carbonate-hosted Zn–Pb deposit in northwestern Yunnan Province,SW China

The Anle Zn–Pb deposit, hosted by Upper Cambrian dolostone, is located in the southern Songpan–Ganzi Block in southwest China. In this deposit, ore bodies occur as stratiform lenses and consist of galena, sphalerite and pyrite as ore minerals, and quartz, dolomite and calcite as gangue minerals. The mineralization shows mainly vein, banded and brecciated structures. Four ore bodies have been found in the Anle deposit, with a combined 2.0 million tonnes (Mt) of sulfide ores at average grades of 1.64 wt.% Pb, 6.64 wt.% Zn and 45 g/t Ag. Brown, brownish-yellow and yellow sphalerite samples have δ⁶⁶Zn values ranging from + 0.08 to + 0.10‰ (average + 0.09‰, n = 3), + 0.12 to + 0.38‰ (average + 0.24‰, n = 8) and + 0.40 to + 0.50‰ (average + 0.46‰, n = 3), respectively. We interpret the progressively heavier Zn isotopes from brown to yellow sphalerite as being led by kinetic Raleigh fractional crystallization. Calcite samples have δ¹³C_PDB and δ¹⁸O_SMOW values ranging from − 4.8 to − 0.2‰ (average − 1.7‰, n = 7) and + 17.9 to + 21.4‰ (average + 19.6‰, n = 7), respectively. Whole-rock δ¹³C_PDB and δ¹⁸O_SMOW values of the Cambrian ore-hosting dolostone range from + 0.1 to + 1.1‰ (average + 0.6‰, n = 3) and + 23.2 to + 24.1‰ (average + 23.6‰, n = 3), respectively. This suggests that carbon in the ore-forming fluids was provided by the host dolostone through carbonate dissolution. δ³⁴S_CDT values of sulfide samples range between − 1.3‰ and + 17.8‰ with an average value of + 6.3‰ (n = 25), lower than evaporites (such as barite + 19.8‰) in the overlaying Lower Ordovician sedimentary strata. The data suggest that sulfur in the hydrothermal fluids were derived from evaporites by thermo-chemical sulfate reduction (TSR). ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios for sulfide minerals range from 17.63 to 17.86, 15.58 to 15.69 and 37.62 to 37.95, respectively. The data are similar to those of the age-corrected Cambrian ore-hosting dolostone (²⁰⁶Pb/²⁰⁴Pb = 17.70–17.98, ²⁰⁷Pb/²⁰⁴Pb = 15.58–15.65 and ²⁰⁸Pb/²⁰⁴Pb = 37.67–38.06), but lower than those of age-corrected Ordovician sandstone and slate (²⁰⁶Pb/²⁰⁴Pb = 18.54–19.58, ²⁰⁷Pb/²⁰⁴Pb = 15.73–15.81 and ²⁰⁸Pb/²⁰⁴Pb = 38.44–39.60). This indicates that ore Pb was most likely to be derived from the Cambrian ore-hosting dolostone. Therefore, our new geological and isotopic evidence suggests that the Anle Zn–Pb deposit is best classified to be an epigenetic carbonate-hosted Mississippi Valley-type (MVT) deposit.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

Insights into ore genesis of the Jinding Zn–Pb deposit,Yunnan Province,China: Evidence from Zn and in-situ S isotopes

The Jinding Zn–Pb deposit located in the Mesozoic-Cenozoic Lanping Basin of southwest China has ore reserves of ∼ 220 Mt with an average grade of 6.1% Zn and 1.3% Pb. The mineralization is hosted by sandstone in the Early Cretaceous Jingxing Formation and limestone breccia in the Paleocene Yunlong Formation. Mineralization in both types of host rocks is characterized by a paragenetic sequence beginning with marcasite–sphalerite (Stage 1) followed by pyrite–marcasite–sphalerite–galena (Stage 2), and then galena–sphalerite–pyrite–sulfate–carbonate (Stage 3). Pyrite from these stages have different δ³³S compositions with pyrite from Stage 1 averaging − 9.6‰, Stage 2 averaging − 8.9‰, and Stage 3 averaging + 0.3‰. Sphalerite hosted by the sandstone has similar δ⁶⁶Zn values ranging from 0.10 to 0.30‰ in all stages of the mineralization, but sphalerite samples from the limestone breccia-hosted ore show variable δ⁶⁶Zn values between − 0.03 and 0.20‰. Our data on sphalerite precipitated during the earlier stages of mineralization has a constant δ⁶⁶Zn value and cogenetic pyrite displays a very light sulfur isotope signature, which we believe to reflect a sulfur source that formed during bacterial sulfate reduction (BSR). The Stage 3 sphalerite and pyrite precipitated from a late influx of metal-rich basinal brine, which had a relatively constant variable δ⁶⁶Zn isotopic composition due to open system isotope fractionation, and a near zero δ³³S composition due to the influence of abiotic thermochemical sulfate reduction from observed sulfates in the host rock.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

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% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O 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 (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 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 δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). 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.     

Characterisation and isotopic evolution of saline waters of the Outokumpu Deep Drill Hole,Finland – Implications for water origin and deep terrestrial biosphere

The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L⁻¹) containing significant amounts of gas, mainly CH₄ (up to 32 mmol L⁻¹), N₂ (up to 10 mmol L⁻¹), H₂ (up to 3.1 mmol L⁻¹) and He (up to 1.1 mmol L⁻¹) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ²H varies from −90‰ to −56‰ (VSMOW) and δ¹⁸O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ²H vs. δ¹⁸O diagram. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between ²H and ¹⁸O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ²H and δ¹⁸O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Determination of germanium isotopic compositions of sulfides by hydride generation MC-ICP-MS and its application to the Pb–Zn deposits in SW China

Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ⁷⁴Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ⁷⁴Ge. Spex and Merck standard solutions yield mean δ⁷⁴Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ⁷⁴Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ⁷⁴Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ⁷⁴Ge_pyrite < δ⁷⁴Ge_sphalerite < δ⁷⁴Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.