Carbon and Oxygen Isotopic Characteristics of REE—Fluorocarbonate Minerals and Their Genetic Implications,Bayan Obo Deposit,Inner Mongloia,China

REE－fluorocarbonates as major REE minerals in the Bayan Obo deposit,the largest REE deposit in the world,were analyzed for their stable isotopic compositions,The δ^13 C and δ^18 O values of huanghoite,cebaite and bastnaesite from late-stage veins vary in the ranges of 7.8--4.0‰ and 6.7-9.4‰,respectively,These data are relatively similar to those of bastnaesites from banded ores:δ^13C-5.6--5.2‰ andδ^18O3.6-5.5‰.The REE fluorocarbonates from both late-staege veins and banded ores are characterized by lower δ^13 C and δ^18O values,especially the δ^18O values of bastnaesites from banded ores.Compared with them,the disseminated bastnaesits the dolomite-type ores possess rather highδ^13 C and δ^18O values,i.e.,-2.1-0.4‰ and 8.6-12.9‰ respectively.The high values are typical of the sedimentary host dolomite rocks as well as of the dolomite-type-ores.The carbon and oxygen isotopic characteristics of REE fluorocarbonate minerals provide new evidence for the hypothesis on the origin of Bayan Obo deposit-epigenetic hydrothermal metasomatism.     

Geology and Isotope Geochemistry of the Dongzhongla Pb–Zn Deposit in Tibet: Implications for the Origin of the Ore‐Forming Fluids and Storage Condition of Certain Metals

As a newly discovered medium‐sized deposit (proven Pb + Zn resources of 0.23 Mt, 9.43% Pb and 8.73% Zn), the Dongzhongla skarn Pb–Zn deposit is located in the northern margin of the eastern Gangdese, central Lhasa block. Based on the geological conditions in this deposit of ore‐forming fluids, H, O, C, S, Pb, Sr, and noble gas isotopic compositions were analyzed. Results show that δ¹⁸O_SMOW of quartz and calcite ranged from −9.85 to 4.17‰, and δD_SMOW ranged from −124.7 to −99.6‰ (where SMOW is the standard mean ocean water), indicating magma fluids mixed with meteoric water in ore‐forming fluids. The δ¹³C_PDB and δ¹⁸O_SMOW values of calcite range from −1.4 to −1.1‰ and from 5.3 to 15.90‰, respectively, show compositions consistent with the carbonate limestone in the surrounding rocks, implying that the carbon was primarily sourced from the dissolution of carbonate strata in the Luobadui Formation. The ore δ³⁴S composition varied in a narrow range of 2.8 to 5.7‰, mostly between 4‰ and 5‰. The total sulfur isotopic value δ³⁴S was 4.7‰ with characteristics of magmatic sulfur. The ³He/⁴He values of pyrite and galena ranged from 0.101 to 5.7 Ra, lower than those of mantle‐derived fluids (6 ± 1 Ra), but higher than those of the crust (0.01–0.05 Ra), and therefore classified as a crust–mantle mixed source. The Pb isotopic composition for ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of the ores were in the ranges of 18.628–18.746, 15.698–15.802, and 39.077–39.430, respectively, consistent with the Pb isotopic composition of magmatic rocks in the deposit, classified as upper‐crust lead. The ore lead was likely sourced partially from the crustal basement of the Lhasa Terrane. The initial (⁸⁷Sr/⁸⁶Sr)_i value from five sulfide samples ranged from 0.71732 to 0.72767, and associated ore‐forming fluids were mainly sourced from the partial melting of the upper‐crust materials. Pb isotopic compositions of ore sulfides from the Dongzhongla deposit are similar to that of the Yuiguila and Mengya'a deposit, indicating that they have similar sources of metal‐rich ore‐forming solution. According to basic skarn mineralogy, the economic metals, and the origin of the ore‐forming fluids, the Dongzhongla deposit was classified as a skarn‐type Pb–Zn deposit.     

Sulfur Isotope Study on Hg and Sb Deposits in Japan

Abstract. Sulfur isotope ratios of cinnabar from Hg deposits and stibnite, jamesonite and berthierite from Sb deposits in Japan are examined in order to understand metallogeneses of Hg and Sb deposits in Japanese island arcs. The studied Hg and Sb deposits include the Hg deposit at Yamato‐suigin (Honshu) and the Sb deposit at Ichinokawa (Shikoku) in the Southwest Japan arc. In addition, Hg deposits including Itomuka and Ryushoden in central Hokkaido and Hg and Sb mineralizations in Northeast Japan arc are examined. The δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, including the Itomuka and Ryushoden deposits range widely, from ‐10 to +16 %o, the highest values encountered at the Samani deposit. The δ³⁴S values of cinnabar from other areas in Japan range from ‐12 to +5 %o, having δ³⁴S values higher than +2 %o from southwestern Hokkaido (Meiji deposit), Shikoku (Suii deposit) and Kyushu (Hasami and Yamagano deposits). On the other hand, the δ³⁴S values of stibnite from all areas in Japan range from ‐14 to +5 %o, having positive δ³⁴S values higher than +2 %o up to +5 %o from southwestern Hokkaido (Yakumo, Toyotomi and Teine deposits) and eastern‐central Honshu (Hachiman and Daikoku deposits). The variation in δ³⁴S values of Hg and Sb deposits may reflect the variation in δ³⁴S values of country rocks or variation in mixing ratio of sulfur extracted from the country rocks, sulfur derived from seawater sulfate, and sulfur derived from magmatic emanations. The relatively high δ³⁴S values of cinnabar and stibnite higher than +2 %o from southwestern Hokkaido, eastern‐central Honshu and Kyushu are probably caused by contribution of volcanic emanation from arc magmas having positive σδ³⁴S values, whereas the positive δ³⁴S values of cinnabar higher than +2 %o from Suii deposit in Shikoku may be attributed to structurally substituted sulfate in limestone country rocks and/or sulfur derived from seawater sulfate. However, the wide range of the δ³⁴S values of cinnabar from the Hidaka‐Kitami district, central Hokkaido, is difficult to explain at this moment. Other relatively low, negative δ³⁴S values of cinnabar and stibnite, berthierite from other areas in Japan may be attributed to 1) incorporation of isotopically light sedimentary sulfur or sulfur derived from ilmenite‐series silicic magma, or 2) less contribution of volcanic emanation from arc magmas having positive σδ³⁴S values.     

Genesis and Metallogenic Process of the Lujing Uranium Deposit,Southwest Jiangxi Province,China: Constraints of Micropetrography and S–C–O Isotopes

The Lujing uranium deposit, located in the southeastern part of the Nanling metallogenic province, is one of the representative granite‐related hydrothermal uranium deposits in South China. Basic geology, geochemistry, and geochronology of the deposit have been extensively studied. However, there is still a chronic lack of systematic research on the genesis and metallogenic process of the deposit. Thus, we recently carried out an electron microprobe and stable isotopic analysis. The main research results and progresses are as follows: Uranium minerals in this deposit include coffinite, pitchblende, and uranothorite, and small amounts of uranium exist in accessory minerals in the form of isomorphism. Coffinite, which occurs predominantly as the pseudomorphs after pitchblende, also occurs as a primary mineral and is locally formed from the remobilization of uranium from adjacent uranium‐bearing minerals. The mineralizing fluid was originally composed of a magmatic fluid generated by late Yanshanian magmatism. The high As content of pyrite in ores may reflect the addition of meteoric water, or the formation water (or both), to the magmatic hydrothermal system. The δ³⁴S values vary from −14.4‰ to 13.9‰ (mean δ³⁴S = −3.9‰), showing a range that is similar to nearby Cambrian metamorphic strata and Indosinian granites, indicating that these host rocks represent the source of sulfur; however, the possibility of a mantle source cannot be completely ruled out. According to our new isotopic data and recent Pb isotopic data, we conclude that the uranium in ores was derived by leaching dominantly from the uranium‐rich host rocks, especially the Cambrian metamorphic strata. The δ¹³C_PDB values (−8.75‰ to 1.40‰; mean δ¹³C_PDB = −5.41‰) and δ¹⁸O_SMOW values (5.45–18.62‰; mean δ¹⁸O = 13.02‰) of reddish calcite from the ore‐forming stage suggest that the CO₂ in the mineralizing fluids was derived predominantly from the mantle, with a small component contributed by marine carbonates. Based on these new data and previous research results, this paper proposes that uranium metallogenesis in the Lujing deposit is closely associated with mafic magmatism resulting from crustal extension during the Cretaceous to Paleogene in South China.     

The mixing of multi-source fluids in the Wusihe Zn–Pb ore deposit in Sichuan Province,Southwestern China

The Sichuan–Yunnan–Guizhou (SYG) metallogenic province of southwest China is one of the most important Zn–Pb ore zones in China, with ~ 200 Mt Zn–Pb ores at mean grades of 10 wt.% Zn and 5 wt.% Pb. The source and mechanism of the regional Zn–Pb mineralization remain controversial despite many investigations that have been conducted. The Wusihe Zn–Pb deposit is a representative large-scale Zn–Pb deposit in the northern SYG, which mainly occurs in the Dengying Formation and yields Zn–Pb resources of ~ 3.7 Mt. In this paper, Zn and S isotopes, and Fe and Cd contents of sphalerite from the Wusihe deposit were investigated in an attempt to constrain the controls on Zn and S isotopic variations, the potential sources of ore-forming components, and the possible mineralization mechanisms. Both the δ⁶⁶Zn and δ³⁴S values in sphalerite from the Wusihe deposit increase systematically from the bottom to the top of the strata-bound orebodies. Such spatial evolution in δ⁶⁶Zn and δ³⁴S values of sphalerite can be attributed to isotopic Rayleigh fractionation during sphalerite precipitation with temperature variations. The strong correlations between the Zn–S isotopic compositions and Fe–Cd concentrations in sphalerite suggest that their variations were dominated by a similar mechanism. However, the Rayleigh fractionation mechanism cannot explain the spatial variations of Fe and Cd concentrations of sphalerite in this deposit. It is noted that the bottom and top sphalerites from the strata-bound orebodies document contrasting Zn and S isotopic compositions which correspond to the Zn and S isotopic characteristics of basement rocks and host rocks, respectively. Therefore, the mixing of two-source fluids with distinct Zn–S isotopic signatures was responsible for the spatial variations of Zn–S isotopic compositions of sphalerite from the Wusihe deposit. The fluids from basement rocks are characterized by relatively lighter Zn (~ 0.2 ‰) and S (~ 5 ‰) isotopic compositions while the fluids from host rocks are marked by relatively heavier Zn (~ 0.6 ‰) and S (~ 15 ‰) isotopic compositions.

     

Petrology and stable isotope (S,C, O) studies of selected sedimenthosted basemetal ore deposits in the proterozoic Aravalli-Delhi Fold Belt,Rajasthan

An integrated mineralogical-geochemical and stable isotopic study of Pb-Zn deposits located at Kayar-Ghugra (Zn-Pb ± Ag), Rampura-Agucha (Zn-Pb, Ag), Dariba-Bethumni (Zn-Pb) and Zawar (Pb-Zn ± Cd, Ag) in Rajasthan is presented in this paper. The Kayar Zn-Pb deposit hosted by (i) phlogopite-tremolite bearing dolomitic carbonates and (ii) scapolite bearing calc-silicates, both belonging to Mesoproterozoic Delhi Supergroup exhibit distinctly different δ¹³C signatures being close to zero permil for the former reflecting deposition in pristine marine environment and much depleted isotopic values for the latter possibly related to post-depositional alterations. The Zn-Pb sulphides of Agucha, hosted in amphibolite facies to lower granulite facies metasedimentary units belonging to the Bhilwara Supergroup have δ³⁴S values that indicate (i) H₂S dominated regime characterized by low fO₂, low pH, wherein the δ³⁴S_(fluid) responsible for mineralisation approximates the δ³⁴S_(sulphide); (ii) the role of seawater in the generation of Agucha ores; (iii) the process of a low temperature oxidation of sulphides in the hydrothermal fluids resulting in the formation of sulphate, by the interaction of ground water; (iv) isotopic disequilibrium in sulphatesulphide pairs that explain oxidation of H₂S by acid groundwater (low pH) and deposition of sulphides at higher temperatures and (v) equilibrium isotopic fractionation of the coexisting sulphides reflecting in a higher concentration of H₂S (>10^?5m) in relation to the total metal content in the hydrothermal fluid $\left( {m_{H_2 S} \geqslant mS_{_{metals} } } \right)$ . Accordingly the concentration of sulphide-sulphate in the hydrothermal solution responsible for the mineralization in Agucha exceeds that of total metals. The sulphides of Bethumni-Rajpura-Dariba belt hosted in low to medium grade siliceous carbonates has a marginally positive (mean of +1.5‰) δ¹³C values. At Sindeswar, broad and widely scattered δ³⁴S values indicate a polymodal sedimentary source of sulphur that recrystallised at rather low temperature of < 50°C possibly during the processes of low temperature bacterial reduction. The C and O-isotopic studies on mineralized and non-mineralized carbonates reveal (i) normal marine depositional signatures for non-mineralized carbonates with possible minor influence of biogenic carbon during deposition and (ii) ore zone carbonates exhibit depleted δ¹³C values presumably due either to the deeper mantle-like source of carbonates or due to post-depositional equilibration with isotopically light meteoric waters. In Zawar belt, sulphides hosted in dolomitic carbonate indicated (i) near identical δ³⁴S values of disseminated galena and pyrite veinlets and depleted values of ?4.6 ‰ for late veins of massive galena of Zawar Mala (ii) pyritepyrrhotite veinlet having enhanced δ³⁴S values when compared to the PbS-ZnS veinlet in Morchia-Magra, Balaria and Baroi mines. The carbon isotopic values for carbonates of Zawar Mala mine area are mostly depleted and those from Balaria and Baroi mines exhibit values of ¹³C close to zero. The generally depleted δ ¹⁸O clustering around ?15 ‰ tally well with the reported Paleoproterozoic carbonates and is attributed to the post-depositional equilibration reactions with isotopically light meteoric waters. It is summarized that the host carbonates for Zn-Pb deposits occurring in different tectono-stratigraphic units in Rajasthan have largely similar but bimodal distribution of δ ¹⁸O and δ¹³C isotopic ratios that suggest normal marine values and much depleted values. Whereas the former seems to be in general agreement with the nature of distribution in the Palaeoproterozoic carbonates the latter is attributed to (i) depositional conditions of the basins that includes absence or presence of biogenic activity (ii) isotopic re-equilibration under different metamorphic recrystallization events and/or (iii) interaction with isotopically lighter meteoric waters. In contrast to the uniformity in the C and O distribution pattern, the S-isotopic distribution in the deposits of Rampura-Agucha, Bethumni-Rajpura-Darbia and Zawar mine areas show marked variations reflecting complex deposit-specific ore-forming processes in the said deposits.     

Sulfur isotopic studies of continental flood basalts in the Noril’sk region: implications for the association between lavas and ore-bearing intrusions

Previous studies of both ore and non-ore-bearing intrusives in the Permo-Triassic flood basalts of the Siberian platform in the Noril’sk area have shown that high-grade Ni-Cu-platinum group elements (PGE) mineralization is associated with anomalously high δ³⁴S values of ∼8 to 12‰. In addition, several researchers have proposed that observed depletions in the Cu, Ni, and PGE content of basaltic lavas of the Nadezhdinsky (Nd) Formation are related to diffusional exchange with, and upgrading in metal tenor of, sulfides in the volcanic conduit system. Sulfur isotopic studies of the lavas at Noril’sk were initiated to determine if interaction with crustally derived sulfur in the conduit system was evident, and if the Nd lavas in particular were characterized by an anomalous isotopic signature. δ³⁴S values of the lavas range from −4.5 to 8.7‰ Vienna Cañon Diablo Troilite (VCDT), with S concentrations from <40 to 1373 ppm. The majority of δ³⁴S values range from 0 to 4‰, and are similar to those from S-poor intrusions in the Noril’sk area. Although textural data are not supportive of early sulfide saturation and the presence of immiscible sulfide droplets in the lavas, recrystallization may have erased expected mineralogical and textural evidence. Mineralogical data indicate that hydrothermal alteration of the lavas has occurred, but S redistribution has been restricted to localized areas and δ³⁴S values have not been affected. The relatively low S concentrations of the lavas are thought to be due in large part to degassing of the lavas in the shallow conduit system and during eruption. Our calculations are consistent with the premise that degassing of basaltic magmas at temperatures in excess of ∼900°C at QFM leads to only minor ³⁴S-depletion of sulfur remaining in the melt, and decreases in δ³⁴S values of less than 2‰ at 90% degassing. For this reason all lavas with δ³⁴S values in excess of ∼ 2‰ require a contribution of ³⁴S-enriched country rock sulfur. Because of the high S content and δ³⁴S value (∼ 16-20‰) of evaporites in the country rocks at Noril’sk, contamination of less than 0.5% is required to explain the most ³⁴S-enriched lavas. The Nd lavas have an average δ³⁴S of 2.9‰, but show no difference in S isotopic composition relative to the other lavas, suggesting that metal depletion involved only limited S transfer, or that exchange between mantle-derived S and S of crustal origin buffered δ³⁴S values to less than ∼5‰. Anomalously positive δ³⁴S values, similar to those of the ore-bearing intrusives in the Noril’sk region, are not consistently found in low-S rocks, either lavas or intrusives. Although the mechanism for the derivation of sulfide in the ore-bearing intrusions remain speculative, it is clear that the formation of sulfide ores characterized by high metal tenors proceeded only in the presence of sulfur of crustal origin.     

Mineralogy and Formation Conditions of Novoshirokinsky Base Metal–Gold Deposit,Eastern Transbaikal Region,Russia

This article presents the new mineralogical, fluid inclusion, and isotopic data for ores of the Novoshirokinsky base metal–gold deposit. Mineralogical sequence is supplemented and specified. The mineral assemblages containing native gold are studied. Morphology, grain size and chemical composition of native gold are described. Major parameters and composition of mineralizing fluids of the main ore stages at the deposit are estimated: main base metal (mid-temperature conditions, fluid salinity 3.1–13.1 wt % equiv NaCl) and carbonate–base metal (low-temperature conditions, fluid salinity 1.0–12.9 wt % equiv. NaCl). Sulfur isotopic composition of sulfides from commercial mineral assemblages has been studied. The δ³⁴S value (+10.5 ± 1‰) of mineralizing fluid has been calculated. The Novoshirokinsky deposit is similar to epithermal deposits and is spatially related to the Late Jurassic porphyry system. Evidence is provided on carbonate rocks of basement involved in the ore-forming process.     

H-O-S-Cu-Pb Isotopic Constraints on the Origin of the Nage Cu-Pb Deposit, Southeast Guizhou Province, SW China

The Nage Cu-Pb deposit,a new found ore deposit in the southeast Guizhou province,southwest China,is located on the southwestern margin of the Jiangnan Orogenic Belt.Ore bodies are hosted in slate and phyllite of Neoproterozoic Jialu and Wuye Formations,and are structurally controlled by EW-trending fault.It contains Cu and Pb metals about 0.12 million tonnes with grades of 0.2 wt% to 3.4 wt% Cu and 1.1 wt% to 9.27 wt% Pb.Massive and disseminated Cu-Pb ores from the Nage deposit occur as either veinlets or disseminations in silicified rocks.The ore minerals include chalcopyrite,galena and pyrite,and gangue minerals are quartz,sericite and chlorite.The H-O isotopic compositions of quartz,S-Cu-Pb isotopic compositions of sulfide minerals,Pb isotopic compositions of whole rocks and ores have been analyzed to trace the sources of ore-forming fluids and metals for the Nage Cu-Pb deposit.The δ65CuNBS values of chalcopyrite range from-0.09% to +0.33‰,similar to basic igneous rocks and chalcopyrite from magmatic deposits.δ65CuNBS values of chalcopyrite from the early,middle and final mineralization stages show an increasing trend due to63Cu prior migrated in gas phase when fluids exsolution from magma.δ34SCDT values of sulfide minerals range from 2.7‰ to +2.8‰,similar to mantle-derived sulfur(0±3‰).The positive correlation between δ65CuNBS and δ34SCDT values of chalcopyrite indicates that a common source of copper metal and sulfur from magma.δDH2OSMOW and δ18OH2O-SMOW values of water in fluid inclusions of quartz range from 60.7‰ to 44.4‰ and +7.9‰ to +9.0‰(T=260°C),respectively and fall in the field for magmatic and metamorphic waters,implicating that mixed sources for H2O in hydrothermal fluids.Ores and sulfide minerals have a small range of Pb isotopic compositions(208Pb/204Pb=38.152 to 38.384,207Pb/204Pb=15.656 to 17.708 and 206Pb/204Pb=17.991 to 18.049) that are close to orogenic belt and upper crust Pb evolution curve,and similar to Neoproterozoic host rocks(208Pb/204Pb=38.201 to 38.6373,207Pb/204Pb=15.648 to 15.673 and 206Pb/204Pb=17.820 to 18.258),but higher than diabase(208Pb/204Pb=37.830 to 38.012,207Pb/204Pb=15.620 to 15.635 and206Pb/204Pb=17.808 to 17.902).These results imply that the Pb metal originated mainly from host rocks.The H-O-S-Cu-Pb isotopes tegather with geology,indicating that the ore genesis of the Nage Cu-Pb deposit is post-magmatic hydrothermal type.     

Ore‐forming Ages and Sulfur Isotope Study of Hydrothermal Deposits in Kamchatka,Russia

In Kamchatka, Central Koryak, Central Kamchatka and East Kamchatka metallogenic belts are distributed from northwest to southeast. K–Ar age, sulfur isotopic composition of sulfide minerals, and bulk chemical compositions of ores were analyzed for 13 ore deposits including hydrothermal gold‐silver and base metal, in order to elucidate the geological time periods of ore formation, relationship to regional volcanic belts, type of mineralization, and origin of sulfur in sulfides. The dating yielded ore‐forming ages of 41 Ma for the Ametistovoe deposit in the Central Koryak, 17.1 Ma for the Zolotoe deposit and 6.9 Ma for the Aginskoe deposit in the Central Kamchatka, and 7.4 Ma for the Porozhistoe deposit and 5.1 Ma for the Vilyuchinskoe deposit in the East Kamchatka metallogenic belt. The data combined with previous data of ore‐forming ages indicate that the time periods of ore formation in these metallogenic belts become young towards the southeast. The averaged δ³⁴S_CDT of sulfides are ?2.8‰ for the Ametistovoe deposit in Central Koryak, ?1.8‰ to +2.0‰ (av. ?0.1‰) for the Zolotoe, Aginskoe, Baranievskoe and Ozernovskoe deposits in Central Kamchatka, and ?0.7 to +3.8‰ (av. +1.7‰) for Bolshe‐Bannoe, Kumroch, Vilyuchinskoe, Bystrinskoe, Asachinskoe, Rodnikovoe, and Mutnovskoe deposits in East Kamchatka. The negative δ³⁴S_CDT value from the Ametistovoe deposit in Central Koryak is ascribed to the contamination of ³²S‐enriched sedimentary sulfur in the Ukelayat‐Lesnaya River trough of basement rock. Comparison of the sulfur isotope compositions of the mineral deposits shows similarity between the Central Koryak and Magadan metallogenic belts, and East Kamchatka and Kuril Islands belts. The Central Kamchatka belt is intermediate between these two groups in term of sulfur isotopic composition.     

Discovery of an abnormally high-δ34S barite deposit and a new understanding of global sulfur isotope variation during geological history

The evolution of the global sulfur isotope curve was plotted based on the δ34S values of evaporates resultant from oceanic evaporation. In the long period of geological history the δ34S values showed obvious peaks for three times during the process of ancient oceans’ sulfur isotope evolution, namely the Early Cambrian (+30‰), the Late Devonian (+25‰) and the Permian-Triassic transition interval (+17‰), but the causes of the abnormal rise of sulfur isotopic values during the geological period are still in question. In this paper, 18 samples collected from a large Devonian barite deposit from Zhenning County were analyzed to determine their δ34S values, revealing that the 18 samples have very high δ34S values (δ34S=41.88‰-+68.39‰), with an average close to 56.30‰, which are higher than the isotopic values of contemporary sulfates (+17‰- +25‰). A comparative analysis was conducted of the emerging of high δ34S barite deposits (from Cambrian and Devonian) and the δ34S variation curves of the ancient oceans. The results indicate that the time when the obvious peaks of δ34S values appeared and the time of massive sedimentation of high δ34S barite deposits are very close to each other, which, in our opinion, is not a coincidence. There may exist some correlations between the sulfur isotope evolution of ancient oceans during the diverse periods of geological history and the massive sedimentation of high δ34S barite deposits. Therefore, it is inferred that perhaps it was the massive sedimentation of high δ34S barites that caused the sharp rise of δ34S values in a short period of time.     

Sources of Matter and Ore-Producing Fluid of the Tamunyer Gold–Sulfide Deposit (Northern Urals): Isotope Results

The Tamunyer deposit is a typical example of gold–sulfide mineralization located in the lower lithologic–stratigraphic unit (S₂–D₁) of the Auerbach volcanic–plutonic belt. The latter comprises island–arc andesitic volcano–sediments, volcanics, and comagmatic intrusive formations. Carbonates have demonstrated intermediate values of δ¹³C between marine limestone and mantle. The quartz δ¹⁸O is in the range of 15.3–17.2‰. The δ³⁴S of sulfides from the beresitized volcano-sedimentary rocks and ores varies widely from –7.5 to 12‰. The calculated isotope compositions of H₂O, CO₂, and H₂S of the ore-bearing fluid imply two major sources of matter contributing to ore genesis: local rocks and foreign fluid. The ore-bearing fluid was formed by interaction and isotope equilibration between a deep magmatic fluid and marine carbonates (W/R ~ 1), with the contribution of sulfur from the volcano-sedimentary rocks.     

Origin of the Dachang gold deposit,NW China: constraints from H,O, S,and Pb isotope data

The Dachang gold deposit is located in the Late Triassic Songpan-Ganzi Fold Belt, NE Tibetan Plateau. Gold ore is concentrated as veins along secondary faults and fracture zones in the Bayan Har Group metaturbidites. No exposed felsic plutons are present in the vicinity of the deposit. The auriferous veins contain <15% sulphide minerals, mainly arsenopyrite, pyrite, and stibnite. Gold is commonly enclosed within arsenopyrite and pyrite. Typical alteration around the ore bodies includes silicification, sericitization, and weak carbonatization.

Gold-bearing quartz samples have δ¹⁸O values of 16.9–21.2‰ (V-SMOW) from which δ¹⁸O_H2O values of 6.2–9.6‰ can be calculated from the fluid inclusion temperatures (or 10.0 to 12.7‰ if we used the average arsenopyrite geothermometer temperature of 301°C). The δD values of fluid inclusions in quartz range from –90‰ to –72‰. δ³⁴S values of gold-bearing sulphides mainly range from –5.9‰ to –2.8‰ (V-CDT). Pyrite and arsenopyrite in ores have ²⁰⁶Pb/²⁰⁴Pb ratios of 18.2888 to 18.4702, ²⁰⁷Pb/²⁰⁴Pb ratios of 15.5763 to 15.6712, and ²⁰⁸Pb/²⁰⁴Pb ratios of 38.2298 to 38.8212. These isotopic compositions indicate that the ore-forming fluids were of metamorphic origin, and the S and Pb may have been derived from the host metaturbidites of the Bayan Har Group. The Dachang Au deposit has geological and geochemical features similar to orogenic gold deposits. We propose that the ores formed when the Songpan-Ganzi Fold Belt was intensely deformed by Late Triassic folding and thrusting. Large-scale thrusting resulted in regional allochthons of different scales, followed by secondary faults or fracture zones that controlled the ore bodies.     

A sulphur isotopic study of the Navia gold belt (Spain)

The Navia gold belt is located in the West Asturian-Leonese Zone of the Iberian Variscan Orogen. The host rocks of the mineralization are quartzites, sandstones and black shales of Cambro-Ordovician age. The gold belt extends along 35 km and has five major veins: Penedela, Encarnita, Fornaza, Carmina and S. Jose. The ores belong to at least four associations having contrasting mineralogies and textures. The δ³⁴S values for individual mineral phases reflect the polyphase metallogenic history. The older association (Stage 1) is Fe-Mn-rich and is made up of spessartine, grunerite-dannemorite and quartz, with magnetite, pyrrhotite and chalcopyrite as metallic phases. The mineralization of Stage 1 is followed by the As-rich Stage 2 with quartz, arsenopyrite and pyrite. The δ³⁴S values for pyrite range from 14.9 to 19.9 per mil (n = 16), and for arsenopyrite from 13.2 to 17.3 per mil (n = 7). The observed isotopic homogeneity likely implies isotopic equilibrium at the scale of the gold vein. Stage 3 contains a coarse-grained base metal sulphide-rich association. The δ⁴S values for sphalerite range from 16.4 to 20.6 per mil (n= 16), and for galena from 17.0 to 18.7 per mil (n = 11). δ³⁴S_sp > δ³⁴S_gl suggests that the sulphur isotopic fractionation of the ore-forming system had reached equilibrium. The youngest crosscutting mineral association (Stage 4) consists of Pb-Sb sulphosalts, bornite, electrum and quartz. The δ³⁴S values for sulphosalts range from 9.7 to 15.8 per mil, showing the lightest results of the Navia sulphides.The relatively tight clustering of δ³⁴S values of the Au-related sulphides, and the results of fluid inclusions and paragenetic studies, can be interpreted to indicate that the hydrothermal fluids of the last three stages were dominated by H₂S. In the H₂S predominant field, sulphide minerals precipitating from solutions would exhibit δ³⁴S values similar to the δ³⁴S_ΣS value of the ore fluid. The heavy δ³⁴S_ΣS of the Navia fluids is consistent with leaching of sulphur from the host rocks. The main sulphur source could be diagenetic pyrite from the siliciclastic rocks of the Cabos and Luarca Formations, which exhibit δ³⁴S values from 8.3 to 21.2 per mil. An additional sulphur-source in Stage 3 would be the leaching of disseminated sphalerite and galena present in Cambrian carbonates.     

Stable sulfur isotope partitioning during simulated petroleum formation as determined by hydrous pyrolysis of Ghareb Limestone, Israel

Hydrous pyrolysis experiments at 200 to 365°C were carried out on a thermally immature organic-rich limestone containing Type-IIS kerogen from the Ghareb Limestone in North Negev, Israel. This work focuses on the thermal behavior of both organic and inorganic sulfur species and the partitioning of their stable sulfur isotopes among organic and inorganic phases generated during hydrous pyrolyses. Most of the sulfur in the rock (85%) is organic sulfur. The most dominant sulfur transformation is cleavage of organic-bound sulfur to form H₂S_(gas). Up to 70% of this organic sulfur is released as H₂S_(gas) that is isotopically lighter than the sulfur in the kerogen. Organic sulfur is enriched by up to 2‰ in ³⁴S during thermal maturation compared with the initial δ³⁴S values. The δ³⁴S values of the three main organic fractions (kerogen, bitumen and expelled oil) are within 1‰ of one another. No thermochemical sulfate reduction or sulfate formation was observed during the experiments. The early released sulfur reacted with available iron to form secondary pyrite and is the most ³⁴S depleted phase, which is 21‰ lighter than the bulk organic sulfur. The large isotopic fractionation for the early formed H₂S is a result of the system not being in equilibrium. As partial pressure of H₂S_(gas) increases, retro reactions with the organic sulfur in the closed system may cause isotope exchange and isotopic homogenization. Part of the δ³⁴S-enriched secondary pyrite decomposes above 300°C resulting in a corresponding decrease in the δ³⁴S of the remaining pyrite. These results are relevant to interpreting thermal maturation processes and their effect on kerogen-oil-H₂S-pyrite correlations. In particular, the use of pyrite-kerogen δ³⁴S relations in reconstructing diagenetic conditions of thermally mature rocks is questionable because formation of secondary pyrite during thermal maturation can mask the isotopic signature and quantity of the original diagenetic pyrite. The main transformations of kerogen to bitumen and bitumen to oil can be recorded by using both sulfur content and δ³⁴S of each phase including the H₂S_(gas). H₂S generated in association with oil should be isotopically lighter or similar to oil. It is concluded that small isotopic differentiation obtained between organic and inorganic sulfur species suggests closed-system conditions. Conversely, open-system conditions may cause significant isotopic discrimination between the oil and its source kerogen. The magnitude of this discrimination is suggested to be highly dependent on the availability of iron in a source rock resulting in secondary formation of pyrite.     

Geology and Geochemistry of the Buerkesidai and Kuoerzhenkuola Gold Deposits in the Sawuershan Region, Xinjiang Uigur Autonomous Region, Northwest China

The Sawuershan region, one of the important gold metallogenic belts of Xinjiang, is located in the western part of the Kalatongke island arc zone of north Xinjiang, NW China. There are two gold deposits in mining, namely the Kuoerzhenkuola and the Buerkesidai deposits. Gold ores at the Kuoerzhenkuola deposit occur within Carboniferous andesite and volcanic breccias in the form of gold‐bearing quartz–pyrite veins and veinlet groups containing native gold, electrum, pyrite, pyrrhotite and chalcopyrite. Gold ores at the Buerkesidai deposit occur within Carboniferous tuffaceous siltstones in the form of gold‐bearing quartz veinlet groups and altered rocks, with electrum, pyrite and arsenopyrite as major metallic minerals. Both gold deposits are hosted by structurally controlled faults associated with intense hydrothermal alteration. The typical alteration assemblage is sericite + chlorite + calcite + quartz, with an inner pyrite–sericite zone and an outer chlorite–calcite–epidote zone between orebodies and wall rocks. δ³⁴S values (0.3–1.3‰) of pyrite of ores from Kuoerzhenkuola deposit are similar to those (0.4–2.9‰) of pyrite of ores from Buerkesidai deposit. δ³⁴S values (1.1–2.8‰) of pyrite from altered rocks are similar to δ³⁴S values of magmatic or igneous sulfide sulfur, but higher than those from ores. ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb data of sulfide from ores range within 17.72–18.56, 15.34–15.61, and 37.21–38.28, respectively. These sulfur and lead isotope compositions imply that ore‐forming materials might originate from multiple, mainly deep sources. He and Ar isotope study on fluid inclusions of pyrites from ores of Kuoerzhenkuola and Buerkesidai gold deposits produces ⁴⁰Ar/³⁶Ar and ³He/⁴He ratios in the range of 282–525 and 0.6–9.4 R/Ra, respectively, indicating a mixed source of deep‐seated magmatic water (mantle fluid) and shallower meteoric water. In terms of tectonic setting, the gold deposits in the Sawuershan region can be interpreted as epithermal. These formations resulted from a combination of protracted volcanic activity, hydrothermal fluid mixing, and a structural setting favoring gold deposition. Fluid mixing was possibly the key factor resulting in Au deposition in the gold deposits in Sawuershan region.     

A reconnaissance study of stable isotope ratios in archaean rocks from the yilgarn block,Western Australia

Isotopic compositions of sulphur, carbon, and oxygen have been determined for constituents from a total of 103 samples of sedimentary rocks, mafic and ultramafic igneous rocks, nickel ores, and gold ores from the Archaean Yilgarn Block.

Sulphides in the bulk of the sedimentary rocks have δ³⁴S values close to 0‰ and appear to have precipitated from solutions which incorporated magmatic sulphur (either juvenile or derived from older rocks). There is no evidence for widespread sulphate reduction.

δ³⁴S values of sulphides in the nickel deposits and associated mafic/ultramafic igneous rocks are within the magmatic range. The small, high‐grade deposits of the Kambalda‐Nepean‐Scotia type have small positive δ³⁴S values, and the large, low‐to‐medium grade dunite‐associated deposits of the Mount Keith‐Perseverance type have small negative δ³⁴S values.

Sulphides in the Kalgoorlie gold ores are enriched in ³²S relative to those in their host dolerite, supporting an epigenetic origin for the gold, under moderately high fO₂ conditions.

The δ¹³C values do not provide unequivocal evidence for the source(s) of the reduced carbon (kerogen) in the sedimentary rocks. Whilst they are compatible with biogenic derivation, it is not possible to rule out contributions from pre‐biotic organic ‘soup’ or from hydrothermal solutions of deep‐seated origin.

Carbonate in the sedimentary rocks are predominantly in epigenetic, sulphide‐bearing veinlets. In many cases, their δ¹³C values suggest precipitation from hydro‐thermal solutions containing magmatically derived CO₂. In only two samples are the petrographic features and δ¹³C values compatible with marine carbonates. Talc‐carbonate altered ultramafic igneous rocks have δ¹³C values consistent with their incorporation of magmatically derived CO₂.

The ?δ¹³C (carbonate‐kerogen) values for most of the sedimentary rock studied fall in a narrow range around +10‰, suggesting isotopic exchange between oxidized and reduced carbon species at moderately high temperatures (>250°C).

δ¹⁸O values of carbonate from both sedimentary rocks and igneous rocks are mainly within the range +7.2‰ to +18.0‰. If the values are primary they are consistent with the formation of carbonate from hydrothermal solutions of magmatic and/or metamorphic origin. However, it is also possible the δ¹⁸O values are the result of post‐depositional equilibration with meteoric waters.     

Geology,mineralogy, geochemistry and δ34S of sedimentary rock-hosted Au deposits in Song Hien structure,NE Vietnam

The Song Hien rift basin is considered to be one of the most important regions of gold mineralisation in North East Vietnam. A number of gold deposits in the Song Hien rift basin are hosted in Triassic and Devonian sedimentary formations of the basin. The largest among them are the Bo Va, Tham Riem and Khung Khoang deposits. The Bo Va deposit is hosted in carbonaceous sedimentary rocks of Triassic age, whereas the Tham Riem and Khung Khoang deposits are hosted in carbonaceous sedimentary rocks of Devonian ages. Based on the mineral composition of the ores, the deposits can be divided into to two types: (i) pyrite dominated and (ii) pyrite-arsenopyrite dominated. The Khung Khoang is of the first type and the Bo Va and Tham Riem deposits belong to the second type. The isotopic composition of pyrite and arsenopyrite in the Tham Riem deposit however, is close to that for the ores of the Bo Va deposit. The δ³⁴S value for pyrite ranging from −3.7‰ to −7.4‰ and for arsenopyrite ranging from −3.2‰ to 7.4‰. The δ³⁴S of pyrite in the ore from the Khung Khoang deposit however, has a much heavier isotopic composition of +18.9 to +20.2‰. A narrow range of the variation of sulfur isotopic composition of pyrite and arsenopyrite, the presence of visible gold as inclusions, the presence of chalcopyrite, sphalerite and other inclusions in arsenopyrite and pyrite, the large size of the grains of major ore minerals allow us to assume that the primary gold ores of the Bo Va and Tham Riem deposits underwent metamorphic transformations. The absence of arsenic, antimony, mercury and other characteristic elements in the ores of the Khung Khoang deposit, and substantially heavier isotopic composition of sulfur similar to the sulfur isotopic composition of marine sulfates in the Devonian, allow us to assume another source of the ore components, not connected with the Triassic sedimentary rocks of the Song Hien rift.     

Rare-Earth-Element and Isotopic Evidence for the Genesis of the Bajiazi Stratabound Sulfide Ore Bodies of Northeast China

This study examines the rare-earth-elemenl and isotopic geochemistry of sulfide ores and associated rocks in the Bajiazi sulfide deposits of northeastern China. The distribution and concentration of rare earth elements (REE) in sulfide ores and associated rocks from the Bajiazi deposits have been determined by inductively coupled plasma spectroscopy (ICP) methods. Birdwing-shaped rare-earth-element profiles are only observed in granitic rocks at Bajiazi. Diverse rare-earth-element profiles of the ores and dolostones are different from those of granite and are interpreted to reflect an early sedimentary-diagenetic mineralization stage during which rare earth elements were added to the ores and host rocks. The characteristic features of the abundances of REE in the Bajiazi samples, including granite and sedimentary host rocks, are demonstrated by a variety of Eu anomalies in the chondrite-normalized REE pattern. Eu is the most mobile element, exhibiting increasingly negative anomalies in granite rock samples relative to the depletion of the sulfide ores and associated sedimentary host rocks, which are considered to be caused by preferential scavenging of Eu from sea water to sediments.

The δ³⁴S values of sulfide minerals at Bajiazi generally range from ?12.3 to 14.2%, suggesting reduction both of marine sulfate and biogenic sources. The δ³⁴S values from different ore types, sulfide minerals, and mines indicate a sedimentary exhalative origin, although they were, to some extent, homogenized during late overprinting. The late-stage sulfides from Bajiazi are isotopieally remarkably homogeneous and are significantly, although slightly, enriched in δ³⁴S. These results imply multiple sources of sulfur derived from biogenic reduction, and/or sulfate in oceanic and/or connate waters, or from marine evaporites, and/or from magmatic hydrothermal sources. Isotopic temperatures from intersulfide fractionations (pyrite, sphalerite, and galena) range from 75° to 542°C, indicating the Bajiazi sulfide minerals have experienced different mineralizing stages.

Galena in the Bajiazi Proterozoic sediment-hosted Pb-Zn sulfide deposits has a very uniform Pb-isotope composition, with ²⁰⁶Pb/²⁰⁴Pb = 16.07 to 16.58, ²⁰⁷Pb/²⁰⁴Pb = 15.00 to 15.66, and ²⁰⁸Pb/²⁰⁴Pb = 36.13 to 36.92, suggesting that it all formed from a common mineralizing fluid. The variation of lead-isotopic values of ores is similar to that of their host sedimentary strata. The lead in the various ore types and host rocks within the Bajiazi district is virtually identical. Lead-isotope signatures, which generally plot very close to model crustal growth curves, characterized by a model age of ～1350 Ma, indicate a normal, nonradiogenic origin and an Early Proterozoic upper-crustal source for the lead in the ores. That lead was unrelated to the radiogenic lead in the Mesozoic granite.

The δ¹³C values range from +1 to ?5% PDB, and the δ¹⁸O values from ?6 to ?15% PDB. Later crystallization generations are enriched in the light isotopes of carbon and oxygen compared to early generations. The characteristics of carbon and oxygen isotopes of the Bajiazi deposits indicate that: (1) primary ores were precipitated in the Proterozoic marine environment; (2) both ores and host carbonates from the Bajiazi district are remarkably homogeneous in their carbon- and oxygen-isotope compositions during later tectonic, conlact-metamorphic stages; (3) although the variations in isotopic composition of carbon and oxygen are relatively small, a significant evolution toward a lighter isotopic composition with advancing diagenetic, tectonic, and contact metamorphic processes is observed; and (4) this evolution is independent of the presence or absence of ore minerals.     

REE, Mn, Fe, Mg and C, O Isotopic Geochemistry of Calcites from Furong Tin Deposit, South China: Evidence for the Genesis of the Hydrothermal Ore-forming Fluids

The Furong tin deposit in the central Nanling region, South China, consists of three main types of mineralization ores, i.e. skarn-, altered granite- and greisen-type ores, hosted in Carboniferous and Permian strata and Mesozoic granitic intrusions. Calcite is the dominant gangue mineral intergrown with ore bodies in the orefield. We have carried out REE, Mn, Fe, and Mg geochemical and C, and O isotopic studies on calcites to constrain the source and evolution of the ore-forming fluids. The calcites from the Furong deposit exhibit middle negative Eu anomaly (Eu/Eu*= 0.311–0.921), except for one which has an Eu/Eu* of 1.10, with the total REE content of 5.49–133 ppm. The results show that the calcites are characterized by two types of REE distribution patterns: a LREE-enriched pattern and a flat REE pattern. The LREE-enriched pattern of calcites accompanying greisen-type ore and skarn-type ore are similar to those of Qitianling granite. The REE, Mn, Fe, and Mg abundances of calcites exhibit a decreasing tendency from granite rock mass to wall rock, i.e. these abundances of calcites associated with altered granite-type and greisen-type ores are higher than those associated with skarn-type ores. The calcites from primary ores in the Furong deposit show large variation in carbon and oxygen isotopic compositions. The δ¹³C and δ¹⁸O of calcites are −0.4 to −12.7‰ and 2.8 to 16.4‰, respectively, and mainly fall within the range between mantle or magmatic carbon and marine carbonate. The calcites from greisen and altered granite ores in the Furong deposit display a negative correlation in the diagram of δ¹³C versus δ¹⁸O, probably owing to the CO₂-degassing of the ore-forming fluids. From the intrusion to wall-rock, the calcites display an increasing tendency with respect to δ¹³C values. This implies that the carbon isotopic compositions of the ore-bearing fluids have progressively changed from domination by magmatic carbon to sedimentary carbonate carbon. In combination with other geological and geochemical data, we suggest that the ore-forming fluids represent magmatic origin. We believe that the fluids exsolved from fractionation of the granitic magma, accompanying magmatism of the Qitianling granite complex, were involved in the mineralization of the Furong tin polymetallic deposit.