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 multimetal 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 δ34S 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°C) 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.     

Genesis of the Changba–Lijiagou Giant Pb-Zn Deposit, West Qinling, Central China: Constraints from S-Pb-C-O isotopes

The extensive Changba-Lijiagou Pb-Zn deposit is located in the north of the Xihe–Chengxian ore cluster in West Qinling. The ore bodies are mainly hosted in the marble, dolomitic marble and biotite-calcite-quartz schist of the Middle Devonian Anjiacha Formation, and are structurally controlled by the fault and anticline. The ore-forming process can be divided into three main stages, based on field geological features and mineral assemblages. The mineral assemblages of hydrothermal stage I are pale-yellow coarse grain, low Fe sphalerite, pyrite with pits, barite and biotite. The mineral assemblages of hydrothermal stage II are black-brown cryptocrystalline, high Fe shalerite, pyrite without pits, marcasite or arsenopyrite replace the pyrite with pits, K-feldspar. The features of hydrothermal stage III are calcite-quartz-sulfide vein cutting the laminated, banded ore body. Forty-two sulfur isotope analyses, twenty-five lead isotope analyses and nineteen carbon and oxygen isotope analyses were determined on sphalerite, pyrite, galena and calcite. The δ34 S values of stage I(20.3 to 29.0‰) are consistent with the δ34 S of sulfate(barite) in the stratum. Combined with geological feature, inclusion characteristics and EPMA data, we propose that TSR has played a key role in the formation of the sulfides in stage I. The δ34 S values of stage II sphalerite and pyrite(15.1 to 23.0‰) are between sulfides in the host rock, magmatic sulfur and the sulfate(barite) in the stratum. This result suggests that multiple S reservoirs were the sources for S2-in stage II. The δ34 S values of stage III(13.1 to 22‰) combined with the structure of the geological and mineral features suggest a magmatic hydrothermal origin of the mineralization. The lead isotope compositions of the sulfides have 206 Pb/204 Pb ranging from 17.9480 to 17.9782, 207 Pb/204 Pb ranging from 15.611 to 15.622, and 208 Pb/204 Pb ranging from 38.1368 to 38.1691 in the three ore-forming stages. The narrow and symmetric distributions of the lead isotope values reflect homogenization of granite and mantle sources before the Pb-Zn mineralization. The δ13 CPDB and δ18 OSMOW values of stage I range from-0.1 to 2.4‰ and from 18.8 to 21.7‰. The values and inclusion data indicate that the source of fluids in stage I was the dissolution of marine carbonate. The δ13 CPDB and δ18 OSMOW values of stage II range from-4 to 1‰ and from 12.3 to 20.3‰, suggesting multiple C-O reservoirs in the Changba deposit and the addition of mantle-source fluid to the system. The values in stage III are-3.1‰ and 19.7‰, respectively. We infer that the process of mineralization involved evaporitic salt and sedimentary organic-bearing units interacting through thermochemical sulfate reduction through the isotopic, mineralogy and inclusion evidences. Subsequently, the geology feature, mineral assemblages, EPMA data and isotopic values support the conclusion that the ore-forming hydrothermal fluids were mixed with magmatic hydrothermal fluids and forming the massive dark sphalerite, then yielding the calcite-quartz-sulfide vein ore type at the last stage. The genesis of this ore deposit was epigenetic rather than the previously-proposed sedimentary-exhalative(SEDEX) type.     

Stable Isotopes and Halogen Geochemistry of the Huayuan Carbonate-hosted Pb-Zn Ore District, South China: Implications for the Salt Source of Ore-forming Fluids

The Huayuan Pb-Zn ore district in China, located in western Hunan Province, is a giant carbonate-hosted Pb-Zn ore district. The source of ore-forming brines in this ore district remains poorly constrained. Whether the highly saline brines are derived from evaporated seawater or dissolved evaporates continues to be intensely debated. Carbonate minerals associated with Pb-Zn mineralization have δ13CV-PDB and δ18OV-SMOW values ranging from ?5.55‰ to +1.35‰ (mean value of ?0.69‰; n = 14) and +16.28‰ to +25.05‰ (mean value of +20.22‰; n = 14), respectively. This indicates that carbonate minerals are dominantly formed from dissolved ore-hosted carbonate rocks. The δ34S values of sulfides range from +20.2‰ to +36.8‰, with an average value of +30.0‰ (n = 27). These results suggest that sulfur is predominantly derived from the thermochemical sulfate reduction of marine sulfate. The crush-leach analyzed solute data of fluid inclusions in sphalerite show the ore-forming fluids have Cl/Br molar ratios range from 118 to 384, and Na/Br molar ratios from 39 to 160 (n = 8). These Cl/Br ratios of hydrothermal fluid are much lower than those of seawater (657 to 564), but are consistent with bittern brines through early halite precipitation. We propose that ore-forming fluids are mainly derived from evaporitic basin brines, which leached base metals from the basement and/or country rocks. The brine then migrated to the basin margins through clastic rocks of basement and then precipitated sul?des by thermochemical sulfate reduction.     

The Bulong Gold Deposit-a Quartz-Barite Vein Type Gold Deposit in Xinjiang:Geological Characteristics and S, He and Ar Isotopic Compositions

The Bulong gold deposit, located in the southwest Tianshan in China, occurs in the Upper Devonian finegrained clastic rocks. The gold orebodies are controlled by an gently inclined interlayer fractured zone. They are hosted only in quartz-barite veins though there are barite veins and quartz veins in the ore district. The δ34S values of pyrite in the ores range from 14.6‰ to 19.2‰ and those of barite from 35.0‰ to 39.6‰, indicating that the sulfur was derived from the strata. 3He/4He ratios of fluid inclusions in pyrite are 0.24-0.82 R/Ra, approximating to that of the crust. The 40Ar/39Ar ratios range from 338 to 471, slightly higher than that of the atmosphere. 40Ar /4He ratios of ore fluids range from 0.015 to 0.412 with a mean of 0.153. Helium and argon isotope compositions of fluid inclusions show that the ore fluids of the Bulong gold deposit were mainly derived from the crust.     

Geology and C-O isotope geochemistry of carbonate-hosted Pb-Zn deposits, NW Guizhou Province, SW China

The Pb-Zn metallogenic district in NW Guizhou Province is an important part of the Yun-nan-Sichuan-Guizhou Pb-Zn metallogenic province, and also is one of the most important Pb-Zn producers in China. The hosting rocks of the Pb-Zn deposits are Devonian to Permian carbonate rocks, and the basement rocks are meta-sedimentary and igneous rocks of the Proterozoic Kunyang and Huili groups. The ore minerals are composed of sphalerite, galena and pyrite, and the gangue minerals are include calcite and dolomite. Geology and C-O isotope of these deposits were studied in this paper. The results show that δ13C and δ18O values of hydrothermal calcite, altered wall rocks-dolostone, sedimentary calcite and hosting carbonate rocks range from -5.3‰ to -0.6 ‰ (mean -3.4‰) and +11.3‰ to +20.9 ‰ (mean +17.2‰), -3.0‰ to +0.9 ‰ (mean -1.3‰) and +17.0‰ to +20.8‰ (mean +19.7‰), +0.6‰ to +2.5 ‰ (mean +1.4‰) and +23.4‰ to +26.5 ‰ (mean +24.6‰), and -1.8‰ to +3.9‰ (mean +0.7‰) and +21.0‰ to +26.8‰ (mean +22.9‰), respectively, implying that CO2 in the ore-forming fluids was mainly a result of dissolution of Devonian and Carboniferous carbonate rocks. However, it is difficult to evaluate the contribution of sediment de-hydroxylation. Based on the integrated analysis of geology, C and O isotopes, it is believed that the ore-forming fluids of these carbonate-hosted Pb-Zn deposits in this area were derived from multiple sources, including hosting carbonate rocks, Devonian to Permian sedimentary rocks and basement rocks (the Kun-yang and Huili groups). Therefore, the fluids mixing is the main precipitation mechanism of the Pb-Zn deposit in this province.     

Geological Characteristics and Genesis of the Jiamoshan MVT Pb–Zn Deposit in the Sanjiang belt, Tibetan Plateau

The carbonate-hosted Pb–Zn deposits in the Sanjiang metallogenic belt on the Tibetan Plateau are typical of MVT Pb–Zn deposits that form in thrust-fold belts. The Jiamoshan Pb–Zn deposit is located in the Changdu area in the middle part of the Sanjiang belt, and it represents a new style of MVT deposit that was controlled by karst structures in a thrust–fold system. Such a karst-controlled MVT Pb–Zn deposit in thrust settings has not previously been described in detail, and we therefore mapped the geology of the deposit and undertook a detailed study of its genesis. The karst structures that host the Jiamoshan deposit were formed in Triassic limestones along secondary reverse faults, and the orebodies have irregular tubular shapes. The main sulfide minerals are galena, sphalerite, and pyrite that occur in massive and lamellar form. The ore-forming fluids belonged to a Mg2+–Na+–K+–SO2-4–Cl-–F-–NO-3–H2 O system at low temperatures(120–130°C) but with high salinities(19–22% NaCl eq.). We have recognized basinal brine as the source of the ore-forming fluids on the basis of their H–O isotopic compositions(-145‰ to-93‰ for δDV-SMOW and-2.22‰ to 13.00‰ for δ18 Ofluid), the ratios of Cl/Br(14–1196) and Na/Br(16–586) in the hydrothermal fluids, and the C–O isotopic compositions of calcite(-5.0‰ to 3.7‰ for δ13 CV-PDB and 15.1‰ to 22.3‰ for δ18 OV-SMOW). These fluids may have been derived from evaporated seawater trapped in marine strata at depth or from Paleogene–Neogene basins on the surface. The δ34 S values are low in the galena(-3.2‰ to 0.6‰) but high in the barite(27.1‰), indicating that the reduced sulfur came from gypsum in the regional Cenozoic basins and from sulfates in trapped paleo-seawater by bacterial sulfate reduction. The Pb isotopic compositions of the galena samples(18.3270–18.3482 for 206 Pb/204 Pb, 15.6345–15.6390 for 207 Pb/204 Pb, and 38.5503–38.5582 for 208 Pb/204 Pb) are similar to those of the regional Triassic volcanic-arc rocks that formed during the closure of the Paleo-Tethys, indicating these arc rocks were the source of the metals in the deposit. Taking into account our new observations and data, as well as regional Pb–Zn metallogenic processes, we present here a new model for MVT deposits controlled by karst structures in thrust–fold systems.     

H-O-S-Pb Isotopic Compositions of the Chagele Pb-Zn-Cu-Mo Deposit,Tibet: Implications for the Ore-forming Processes and Comparison with Pb-Zn (Cu-Mo) Deposits in Middle-east Segment of the Nyainqentanglha Metallogenic BeltEI北大核心CSCD

The Chagele is a typical Pb-Zn-Cu-Mo deposit located in the western Nyainqentanglha Pb-Zn-Ag-Fe-Cu metallogenic belt (NPMB) that immediately north of the Gangdese porphyry copper belt, Tibet. The deposit contains three ore types: the porphyry (Cu) Mo ores occur as thin veins hosted in the granite porphyry; the skarn (Cu) Pb-Zn type ores are of vein-type or lenticular-type mainly occurring in the external contact zone and interstratified crack zone; and the hydrothermal vein Pb-Zn type ores are controlled by the NNE-striking faults and situated in the structural fractured zones and the up walls of fault zones. The (Cu) Pb-Zn ores consist mainly of galena, sphalerite, chalcopyrite, pyrite, malachite, showing automorphic granular, hypautomorphic to allotriomorphic granular and metasomatic-relict textures, and exhibiting mainly veined, banded, disseminated and massive structures. Hydrothermal alteration includes skarnization, silicification and limonitization. The (Cu) Mo ores consists mainly of chalcopyrite and molybdenite, and minor pyrite. The (Cu) Mo ores are characterized by scaly texture, veinlet and massive structures. It has reserves of 0.38 Mt Pb, 0.6 Mt Zn and 110.1 t Ag, with average grade of 2.08%, 3.29% and 6.07 g/t, respectively, and is considered as a deposit with huge ore-prospecting potential in western of NPMB. However, the ore-forming material and genesis of the Chagele deposit are still not clear. This paper systematically investigated the H, O, S and Pb isotopes of the Chagele deposit and compared it with the other Pb-Zn (Cu-Mo) deposits in the middle-east segment of NPMB. Isotopic geochemical analyses showed that the fluids have δ18O values of -2.2‰ to 2.9‰ and δD values of -189‰ to -157‰, respectively, indicative of mixing between magmatic and meteoric waters. The bimodal distribution of δ34 S values for sulfides (-5.6‰ to -0.8‰, the average: -3.7‰ and 1.1‰ to 2.6‰, the average: 1.8‰) indicated that sulfur of the ores were derived from both wall rocks and magma, while the Cu-Mo orebodies was mainly derived from the granite porphyry. The sulfides have 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values in ranges of 18.614 to 18.688, 15.657 to 15.747 and 38.988 to 39.269; similarly the granite porphyries have 206Pb/204Pb, 207Pb/204Pb and 208Pb/204Pb values of 18.663 to 19.058, 15.643 to 15.664, and 39.002 to 39.559, respectively, implying that both of them were originated from the upper crust. The H-O-S-Pb isotopic characteristics of the Chagele deposit are similar to those of the Pb-Zn polymetallic deposits in the mid-east NPMB, suggesting that these deposits have similar ore-forming fluid and material sources. It can be concluded that the Chagele deposit is a typical porphyry type Mo deposit + skarn type-hydrothermal vein type of Cu-Pb-Zn deposit. Moreover, we argue that the mineralization is not only confined to the mid-east NPMB, the western segment of the belt with similar tectonic-magmatism also has high potential of ore mineralization. © 2018, Science Press. All right reserved.     

The genesis of the slab window-related Arzular low-sulfidation epithermal gold mineralization （eastern Pontides, NE Turkey）

The Arzular mineralization is one of the best examples of epithermal gold deposits in the eastern Pontides orogenic belt.The mineralization is hosted by the subduction-related basaltic andesites and is mainly controlled by E-W and NE-SW trending fracture zones.The main ore minerals are galena, sphalerite,pyrite.chalcopyrite.tetrahedrite and gold.Homogenization temperatures of fluid inclusions are between 130 and 295℃ for quartz and between 90 and 133℃ for sphalerite.Sulphur isotope values obtained from pyrite,galena and sphalerite vary between 1.2‰ and 3‰.indicating that sulphur belongs to magmatic origin and was derived from the Lutetian non-adakitic granitic intrusions in the region.Oxygen isotope values are between 15.0‰ and 16.7‰ and hydrogen isotope values are between -87‰ and -91‰ The sulphur isotope thermometer yielded temperatures in the range of 244-291℃ for the ore formation.Our results support the hypothesis that the Arzular mineralization is a low-sulfidation epithermal gold deposit associated with non-adakitic subduction- related granitic magmas that were generated by slab window-related processes in a south-dipping subduction zone during the Lutetian.     

Sources and Evolution of the Ore-forming Materials in the Anqing Cu-Fe Deposit in Anhui Province-Geological and S,C, O Isotopic ConstraintsEI北大核心CSCD

The Anqing Cu-Fe deposit is one of the representative large Cu-Fe deposits along the Yangtze River in Anhui province, with controversial metallogenic mechanism. Based on the ore-forming geological characteristics, this paper focus on the sulfur, carbon and oxygen isotopic compositions of the ores and surrounding rocks, and discuss the sources and evolution processes of the ore-forming materials. The Cu-Fe deposit occurs in the contact zone between the early Yanshanian Yueshan diorite and Triassic marble, with clear horizontal zonings in the skarns and ore bodies. The garnet skarn and thick massive magnetite ore body commonly occur within the external contact zone, which have clear boundaries with the surrounding rocks; whereas the diopside skarns with disseminated copper sulfide commonly occur within the internal contact zone and show gradual and transitional relations with the diorite. The δ34S values of the ores range from -6.5‰ to 10.6‰, and show a V-shaped trend from the diorite to the outer marble. This compositional variation indicates that most of the sulfur may come from magma, with involvement of some pre-Triassic clastic strata sulfur and Triassic marine sulfates in the later stage. The δ13C values of the gangue minerals range from -5.5‰ to 2.0‰, which decrease from the external contact zone to internal contact zone, indicating that the carbons of the ore-forming fluids may be mainly derived from magma, with some Triassic carbonate stratigraphic carbon involved. The marbles nearby the orebody show δ18O values lower than those of the Triassic strata, indicating that they have been remolded by the low δ18O magmatic hydrothermal fluids. The magnetite have some magma filling geological features and extremely low δ18O value, may be the result from the filling of the high temperature iron-rich fluids along the contact zone and fault. This study shows that the ore-magma filling type and hydrothermal-metasomatic type ore bodies coexist in the Anqing Fe-Cu deposit. The immiscibility between iron oxide and silicate melt occurred in magma chamber, which resulted in the formation of iron-rich fluid. The fluid migrated upward and eventually precipitated in a favorable tectonic area or contact zone, and the magnetite ore bodies were formed in the outer contact zone. By the later fluid mixing, filling metasomasis, and water-rock reaction between the differentiated hydrothermal solutions and diorite, the copper ore bodies and the copper-bearing altered diorite were formed in the internal contact zone. © 2018, Science Press. All right reserved.     

Geochemical Characteristics and Sources of Ore-forming Fluids of the Mayuan Pb-Zn Deposit, Nanzheng, Shaanxi, China

The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%(NaCl equiv.).The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_(fluid) values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰(SMOW),and the δ~(18)O_(fluid)values calculated from δ~(18)O_(quartz) and δ~(18)O_(calcite) values range from 4.5‰ to 16.7‰(SMOW).These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ~(13)C_(CH4) values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰(PDB),suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction(TSR) was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type(MVT) deposit.     

Sulfur isotope variations from orebody to hand-specimen scale at the Mežica lead–zinc deposit, Slovenia: a predominantly biogenic pattern

The Mississippi Valley-type (MVT) Pb–Zn ore district at Mežica is hosted by Middle to Upper Triassic platform carbonate rocks in the Northern Karavanke/Drau Range geotectonic units of the Eastern Alps, northeastern Slovenia. The mineralization at Mežica covers an area of 64 km² with more than 350 orebodies and numerous galena and sphalerite occurrences, which formed epigenetically, both conformable and discordant to bedding. While knowledge on the style of mineralization has grown considerably, the origin of discordant mineralization is still debated. Sulfur stable isotope analyses of 149 sulfide samples from the different types of orebodies provide new insights on the genesis of these mineralizations and their relationship. Over the whole mining district, sphalerite and galena have δ ³⁴ S values in the range of –24.7 to –1.5‰ VCDT (–13.5 ± 5.0‰) and –24.7 to –1.4‰ (–10.7 ± 5.9‰), respectively. These values are in the range of the main MVT deposits of the Drau Range. All sulfide δ ³⁴ S values are negative within a broad range, with δ ³⁴ S _pyrite <δ ³⁴ S _sphalerite <δ ³⁴ S _galena for both conformable and discordant orebodies, indicating isotopically heterogeneous H₂S in the ore-forming fluids and precipitation of the sulfides at thermodynamic disequilibrium. This clearly supports that the main sulfide sulfur originates from bacterially mediated reduction (BSR) of Middle to Upper Triassic seawater sulfate or evaporite sulfate. Thermochemical sulfate reduction (TSR) by organic compounds contributed a minor amount of ³⁴S-enriched H₂S to the ore fluid. The variations of δ ³⁴ S values of galena and coarse-grained sphalerite at orefield scale are generally larger than the differences observed in single hand specimens. The progressively more negative δ ³⁴ S values with time along the different sphalerite generations are consistent with mixing of different H₂S sources, with a decreasing contribution of H₂S from regional TSR, and an increase from a local H₂S reservoir produced by BSR (i.e., sedimentary biogenic pyrite, organo-sulfur compounds). Galena in discordant ore (–11.9 to –1.7‰; –7.0 ± 2.7‰, n = 12) tends to be depleted in ³⁴ S compared with conformable ore (–24.7 to –2.8‰, –11.7 ± 6.2‰, n = 39). A similar trend is observed from fine-crystalline sphalerite I to coarse open-space filling sphalerite II. Some variation of the sulfide δ ³⁴ S values is attributed to the inherent variability of bacterial sulfate reduction, including metabolic recycling in a locally partially closed system and contribution of H₂S from hydrolysis of biogenic pyrite and thermal cracking of organo-sulfur compounds. The results suggest that the conformable orebodies originated by mixing of hydrothermal saline metal-rich fluid with H₂S-rich pore waters during late burial diagenesis, while the discordant orebodies formed by mobilization of the earlier conformable mineralization.     

Algal-bacterial fabrics of ores and their genetic implications in the longtang lead-zinc deposit at Yanbian,Sichuan

The Longtang Pb-Zn deposit occurs in the Upper Sinian Guanyinyan Formation. The host rocks include sandy shale, cherty limestone and dolomitic limestone. The deposit is a typical one of thallogen origin. The mineral assemblage in the ore is made up of sphalerite, galena, pyrite, enargite, tennantite, seligmannite, asphalt, etc. The ore-forming process is possessed of multiepisode and multi-stage characters. Generally, sphalerites exhibit algal stromatolitic, bacterial and algal colloidal textures, providing evidence for the direct involvement of algae and bacteria in mineralization of ore-forming elements during sedimentary diagenesis. This is the first transmigration of ore-forming elements. However, pyrite embracing bacteria and galena replacing/filling trichomes are typical organic textures, which are related to organic carbon and bitumen that can adsorb or reduce ore-forming elements. This is an indirect process of organic mineralization, i.e., the second transmigration of ore-forming elements. δ³⁴S values are all greater than 5%., indicating the dominance of the heavy sulfur isotopes. The ore-forming temperature deduced from fluid inclusions ranges from 100°C to 150°C±. All this goes to show that the Longtang Pb-Zn deposit is of thallogen origin. This project was granted by the National Natural Science Foundation of China.     

Sulfur isotopic compositions of the Huize super-large Pb–Zn deposit, Yunnan Province, China: Implications for the source of sulfur in the ore-forming fluids

The Huize Pb–Zn deposit of Yunnan Province, China, is located in the center of the Sichuan–Yunnan–Guizhou Pb–Zn–Ag district. Four primary orebodies (orebody No. 1, No. 6, No. 8 and No. 10), with Pb + Zn reserves from 0.5 Mt to 1 Mt, have been found at depth in this deposit. This paper provides new data on the sulfur isotopic compositions of the four orebodies. The data show that the principal sulfide minerals (galena, sphalerite and pyrite) in the four orebodies are enriched in heavy sulfur, the δ³⁴S values between 10.9‰ and 17.7‰ and where δ³⁴S_pyrite > δ³⁴S_sphalerite > δ³⁴S_galena. The δ³⁴S values of sulfide are close to that of the sulfates from the carbonate strata within the region. The similarity in sulfur isotope composition between sulfides and sulfates indicates the sulfur in the ore-forming fluids was likely derived by thermochemical sulfate reduction of sulfates contained within carbonate units.     

Geochemical Characteristics of Jinwozi Gold Deposit,Xinjiang

The Jinwozi gold deposit consists of gold-bearing quartz veins in a biotite granodiorite of Hercynian age (zircon U-Pb age ≈ 335.7 Ma). Ore mineralogy is simple. In addition to native gold, there are only small amounts of sulfides, mainly pyrite and minor sphalerite, chalcopyrite and galena. δ³⁴S values average 6.69‰, and δ¹⁸O 13.99‰ Abundant CO₂ is contained in fluid inclusions from quartz. Homogenization temperatures of fluid inclusions are between 186 and 262 °C. REE distribution patterns indicate that the igneous mass may have been derived from a common initial material of calcareous-argillaceous sediments and alkali basalts as the country rocks. In other words, the Jinwozi granodiorite is of remelting origin from crustal material. Isotopic evidence of S, O and Pb shows that the ore-forming material is genetically related to magmatic hydrothermal activity.     

相山西部牛头山铅锌矿化体成矿物质来源:原位硫同位素的制约

近年来,在相山铀矿田的西部牛头山地区深部发现了铅锌矿化体,其成因机制不明.为探讨牛头山铅锌矿化体物质来源,开展了硫化物原位硫同位素分析研究.根据硫化物矿物之间的充填和包裹关系判断,铅锌矿化体金属硫化物形成的先后顺序是:黄铁矿形成最早,方铅矿和闪锌矿次之,细脉状黄铜矿形成最晚.利用LA-MC-ICP-MS技术对矿化体中几种金属硫化物分别进行了系统的原位硫同位素分析.结果显示:黄铁矿、闪锌矿、方铅矿、细脉状黄铜矿的δ34S值介于-4.8‰~+5.4‰之间,各硫化物矿物之间硫同位素未达到完全平衡分馏,利用黄铁矿δ34S值得到的矿化流体δ34S_ΣS值（总硫同位素组成）近似为+3.7‰,与共生矿物对（闪锌矿-方铅矿）图解法得到的闪锌矿和方铅矿沉淀时矿化流体的δ34S_ΣS值（+3.2‰）相近,表明形成牛头山铅锌矿化体的矿化流体δ34S_ΣS值大约为+3.7‰,为岩浆硫.结合前人的岩浆岩年龄数据,我们判断该铅锌矿化体金属硫化物的硫可能主要来自次火山岩相花岗斑岩岩浆热液.同一薄片中闪锌矿δ34S值高于共生的方铅矿,表明两者硫同位素基本平衡,利用共生矿物对（闪锌矿-方铅矿）硫同位素温度计计算得出平衡温度为197~476℃,与前人通过脉石矿物流体包裹体得到的铅锌矿化流体温度基本一致.相山火山盆地与相邻的北武夷黄岗山、梨子坑等产铅锌矿的火山盆地具有相似的成矿条件及成矿物质来源,使相山火山盆地具有良好的铅锌多金属找矿前景.      

Metallogenesis and ore-forming time of the Changtuxili Mn–Ag–Pb–Zn deposit in Inner Mongolia: Evidence from C–O–S isotopes and U–Pb geochronology

This paper reports new geochronological (U–Pb) and isotope (C, O, and S) data to investigate the timing of mineralization and mode of ore genesis for the recently discovered Changtuxili Mn–Ag–Pb–Zn deposit, located on the western slopes of the southern Great Hinggan Range in NE China. The mineralization is hosted by intermediate–acidic lavas and pyroclastic rocks of the Baiyingaolao Formation. Three stages of mineralization are identified: quartz–pyrite (Stage I), galena–sphalerite–tetrahedrite–rhodochrosite (Stage II), and quartz–pyrite (Stage III). δ¹³C and δ¹⁸O values for carbonate from the ore vary from −8.51‰ to −4.96‰ and 3.97‰ to 15.90‰, respectively, which are indicative of a low-temperature alteration environment. δ³⁴S_V-CDT values of sulfides range from −1.77‰ to 4.16‰ and show a trend of equilibrium fractionation (δ³⁴S_Py ​> ​δ³⁴S_Sp ​> ​δ³⁴S_Gn). These features indicate that pyrite, sphalerite, and galena precipitated during the period of mineralization. The alteration mineral assemblage and isotope data indicate that the weakly acidic to weakly alkaline ore-forming fluid was derived largely from meteoric water and the ore-forming elements C and S originated from magma. During the mineralization, a geochemical barrier was formed by changes in the pH of the ore-forming fluid, leading to the precipitation of rhodochrosite. On the basis of the mineralization characteristics, new isotope data, and comparison with adjacent deposits, we propose that the Changtuxili Mn–Ag–Pb–Zn deposit is an intermediate-to low-sulfidation epithermal deposit whose formation was controlled by fractures and variability in the pH of the ore-forming fluid. The surrounding volcanic rocks yield zircon U–Pb ages of 160−146 ​Ma (Late Jurassic), indicating that the mineralization is younger than 146 ​Ma.     

Geology and geochemistry of the Changba SEDEX Pb-Zn deposit,Qinling orogenic belt,China

The Changba Pb-Zn SEDEX deposit occurs in the Middle Devonian sequence of the Anjiaca Formation of the Western Qinling Hercynian Orogen in the Gansu Province, China. The Changba-II orebody is hosted in biotite quartz schist and is the largest of 143 stratiform orebodies that are hosted either in biotite quartz schist or marble. The Changba-II comprises two types of mineralization: a bedded facies and an underlying breccia lens. The bedded section exhibits three sulfide sub-facies zoned from bottom to top: 1) banded sphalerite intercalated with quartz albitite; 2) interbedded massive pyrite and sphalerite ore; and 3) banded sphalerite ore intercalated with banded baritite. Major metallic minerals are sphalerite, pyrite, galena, with minor arsenopyrite, pyrrhotite, boulangerite, and rare chalcopyrite. The bedded sulfides are underlain by a lens of brecciated and albitized biotite-quartz schists cemented by sulfides and tourmaline.Massive and bedded sulfide ³⁴S values range from 8.1 to 29.3, whereas barite ³⁴S values range from 20.8 to 31.5. Disseminated pyrite in footwall schists has ³⁴S values ranging from 8.1 to 10.6, and increase to values ranging from 11.1 to 14.7 in the hangingwall. The lower ³⁴S values for massive and bedded sulfides are interpreted to be derived from progressive bacterial sulfate reduction (BSR) of Devonian seawater in a sulfate-restricted sub-basin. The higher ³⁴S values for massive and bedded sulfides could be a product of quantitative BSR but this is incompatible with barite being more abundant above the bedded sulfides. Instead, it is more likely that thermochemical sulfate reduction of seawater sulfate or of evaporite was the source of heavy hydrothermal sulfur. Heavy hydrothermal sulfur was injected into a sulfate-restricted sub-basin where it mixed with low ³⁴S BSR sulfide to form the massive and bedded sulfides. The REE patterns of sulfide layers and associated quartz albitite and baritite are similar to those of the host biotite quartz schists, suggesting that the hydrothermal fluids leached REE from the underlying rocks. Pb isotope ratios in galena form an array between the Upper Crust and the Mantle reservoir curves, which indicates that the lead is derived from upper crustal rocks comprising mafic igneous units. The Sr⁸⁷/Sr⁸⁶ ratio of 0.7101 for carbonate within the sulfide layers also suggests that Sr is derived from the mixing of Sr leached from upper crustal rocks with Middle Devonian seawater Sr. A Rb-Sr isochron age of 389.4 ± 6.4 Ma for sulfide layers and the interbedded hydrothermal sediments is consistent with the age of host Mid-Devonian strata. Ar³⁹/Ar⁴⁰ plateau age at 352.8 ± 3.5 Ma and Ar³⁹-Ar⁴⁰ isochron age of 346.6 ± 6.4 Ma for albite in the quartz albitite intercalated with sulfide layers indicate either albite formation after the sulfides or thermal resetting of the Rb-Sr system at about 350 Ma, the age of collision between the North China and Yangtze cratons.Editorial handling: E. Frimmel     

Carbon and sulfur isotopic compositions of Early Cambrian black shales,NW Hunan,China: Implications for the Paleoceanographic sedimentary environment

In order to better understand the paleoceanographic sedimentary environment of the Lower Cambrian black shales extensively distributed in South China, outcropped along the present southern margin of the Yangtze Platform with a width of ca. 200-400 km and a length of more than 1500 km, we present new paired δ13C data on carbonates (δ13Ccarb) and associated organic carbon (δ13Corg) and δ34Spy data on sedimentary pyrite in black shales from three sections (Ganziping, Shancha and Xiaohekou) located in NW Hunan, China. In these sections, a total of 82 Lower Cambrian black shale samples have δ13Ccarb values ranging from -4.0‰ to 1.7‰ with an average value of -2.1‰, and δ13Corg values between -34.9‰ and -28.8‰, averaging -31.9‰. The ?34Spy values of 16 separated sedi-mentary pyrite samples from the black shales vary between +10.2‰ and +28.7‰ with an average value of +19.5‰, presenting a small isotope fractionation between seawater sulfate and sedimentary sulfide. The model calculation based on credible data from the paired analyses for δ13Ccarb and δ13Corg of 11 black shale samples shows a high CO2 concentration in the Early Cambrian atmosphere, about 20 times higher than pre-industrial revolution values, consis-tent with previous global predictions. The small sulfur isotope fractionation between seawater sulfate and sedimen-tary sulfide in black shales, only 15.5‰ on average, implies a low sulfate level in the Early Cambrian seawater around 1 mmol. In combination with a high degree of pyritization (DOP) in the black shales, it is suggested that sul-fidic deep-ocean water could have lingered up to the earliest Cambrian in this area. The black shale deposition is envisaged in a stratified marine basin, with a surface euphotic and oxygenated water layer and sulfidic deeper water, controlled by a continental margin rift.     

An ultraviolet laser microprobe for the in situ analysis of multisulfur isotopes and its use in measuring Archean sulfur isotope mass-independent anomalies

A laser fluorination microprobe system has been constructed for high-accuracy, high-precision multisulfur isotope analysis with improved spatial resolution. The system uses two lasers: (a) a KrF excimer laser for in situ spot analysis by ultraviolet (UV) photoablation with λ = 248 nm and (b) a CO₂ laser for whole-grain analysis of powdered samples by infrared heating at λ = 10.6 μm. A CO₂ laser is necessary for the analysis of interlaboratory isotope reference materials because they are supplied as powders. The δ³⁴S and δ³³S compositions of reference materials measured with a CO₂ laser fluorination system agree (±0.2‰, 1σ) with the recommended values by the Sulfur Isotope Working Group of the International Atomic Energy Agency [Ding et al 2001] and [Taylor]. The precision of replicate analyses of powdered sulfide minerals with the CO₂ laser is typically ±0.2‰ (1σ) for δ³⁴S.The in situ fluorination of sulfides with a KrF excimer laser (λ = 248 nm) was validated by comparison of measurements of side-by-side laser craters and powders excavated from drill holes. Powders from drill holes were analyzed with the CO₂ laser. In situ laser craters and drill hole powders give the same δ³⁴S_V-CDT and δ³³S_V-CDT values within 0.2‰. The δ³⁴S_V-CDT and δ³³S_V-CDT values of both powders and in situ analyses are independent of F₂ gas pressure over a range of 15 to 65 torr. No dependence of δ³⁴S_V-CDT and δ³³S_V-CDT values on UV laser energy fluence has been observed. Mineral-specific fractionation of sulfur isotopes in analyzing pyrite, sphalerite, galena, troilite, and chalcopyrite has not been observed with a KrF excimer laser (λ = 248 nm). Test analyses with an ArF excimer laser (λ = 193 nm), however, gave fractionated sulfur isotope ratios.A range of Δ³³S anomalies of from - 1.5 to +3.0‰ in Archean samples from the North Pole district, Pilbara Craton, Australia, and from black shale of the Lokamonna Formation, South Africa, were verified by in situ analysis of individual pyrite grains with a KrF excimer laser. These results show that a combination of high-accuracy, high-precision analyses with improved spatial resolution permits locating and analyzing host minerals of non-mass-dependent sulfur isotope anomalies.