Sulfur Isotope Variations of Metallic Ore Deposits in the Gyeongsang Basin,South Korea

Many metallic ore deposits of the Late Cretaceous to Early Tertiary periods are distributed in the Gyeongsang Basin. Previous and newly analyzed sulfur isotope data of 309 sulfide samples from 56 ore deposits were reviewed to discuss the genetic characteristics in relation to granitoid rocks. The metallogenic provinces of the Gyeongsang Basin are divided into the Au–Ag(–Cu–Pb–Zn) province in the western basin where the sedimentary rocks of the Shindong and Hayang groups are distributed, Pb–Zn(–Au–Ag–Cu), Cu–Pb–Zn(–Au–Ag), and Fe–W(–Mo) province in the central basin where the volcanic rocks of the Yucheon Group are dominant, and Cu(–Mo–W–Fe) province in the southeastern basin where both sedimentary rocks of the Hayang Group and Tertiary volcanic rocks are present. Average sulfur isotope compositions of the ore deposits show high tendencies ranging from 2.2 to 11.7‰ (average 5.4‰) in the Pb–Zn(–Au–Ag–Cu) province, ?0.7 to 11.5‰ (average 4.6‰) in the Cu–Pb–Zn(–Au–Ag) province, and 3.7 to 11.4‰ (average 7.5‰) in the Fe–W(–Mo) province in relation to magnetite‐series granitoids, whereas they are low in the Au–Ag(–Cu–Pb–Zn) province in relation to ilmenite‐series granitoids, ranging from ?2.9 to 5.7‰ (average 1.7‰). In the Cu(–Mo–W–Fe) province δ³⁴S values are intermediate ranging from 0.3 to 7.7‰ (average 3.6‰) and locally high δ³⁴S values are likely attributable to sulfur derived from the Tertiary volcanic rocks during hydrothermal alteration through faults commonly developed in this region. Magma originated by the partial melting of the ³⁴S‐enriched oceanic plate intruded into the volcanic rocks and formed magnetite‐series granitoids in the central basin, which contributed to high δ³⁴S values of the metallic deposits. Conversely, ilmenite‐series granitoids were formed by assimilation of sedimentary rocks rich in organic sulfur that influenced the low δ³⁴S values of the deposits in the western and southeastern provinces.     

Cadmium and sulfur isotopic compositions of the Tianbaoshan Zn–Pb–Cd deposit,Sichuan Province,China

Although Zn–Pb deposits are one of the most important Cd reservoirs in the earth, few studies have focused on the Cd isotopic fractionation in Zn–Pb hydrothermal systems. This study investigates the causes and consequences of cadmium and sulfur isotope fractionation in a large hydrothermal system at the Tianbaoshan Zn–Pb–Cd deposit from the Sichuan–Yunnan–Guizhou (SYG) metallogenic province, SW China. Moderate variations in Cd and S isotope compositions have been measured in sphalerite cover a distance of about 78 m. Sphalerite has δ^114/110Cd values ranging from 0.01 to 0.57‰, and sulfides (sphalerite, galena and chalcopyrite) have δ³⁴S_CDT values ranging from 0.2 to 5.0‰. Although δ³⁴S_CDT and δ^114/110Cd values in sphalerites have no regular spatial variations, the δ³⁴S_CDT values in galena and calculated ore-forming fluid temperatures decreased from 2.1 to 0.2‰ and from about 290 to 130 °C, respectively, from the bottom to the top of the deposit. Heavy Cd isotopes are enriched in early precipitated sphalerite in contrast to previous studies. We suggest that Cd isotopic compositions in ore-forming fluids are heterogeneous, which result in heavy Cd isotope enrichment in early precipitated sphalerite. In comparison with other Zn–Pb deposits in the SYG area, the Tianbaoshan deposit has moderate Cd contents and small isotope fractionation, suggesting differences in origin to other Zn–Pb deposits in the SYG province.In the Tianbaoshan deposit, the calculated δ³⁴S∑_S-fluids value is 4.2‰, which is not only higher than the mantle-derived magmatic sulfur (0 ± 3‰), but also quite lower than those of Ediacaran marine sulfates (about 30 to 35‰). Thus, we suggest that reduced sulfur of ore-forming fluids in the deposit was mainly derived from the leaching of the basement, which contains large amount of volcanic or intrusive rocks. Based upon a combination of Cd and S isotopic systems, the Tianbaoshan deposit has different geochemical characteristics from typical Zn–Pb deposits (e.g., the Huize deposit) in SYG area, indicating the unique origin of this deposit.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

Geology and Geochemistry of the Bianbianshan Au‐Ag‐Cu‐Pb‐Zn Deposit,Southern Da Hinggan Mountains,Northeastern China

The Bianbianshan deposit, the unique gold-polymetal (Au-Ag-Cu-Pb-Zn) veined deposit of the polymetal metallogenic belt of the southern segment of Da Hinggan Mountains mineral province, is located at the southern part of the Hercynian fold belt of the south segment of Da Hinggan Mountains mineral province, NE China. Ores at the Bianbianshan deposit occur within Cretaceous andesite and rhyolite in the form of gold-bearing quartz veins and veinlet groups containing native gold, electrum, pyrite, chalcopyrite, galena and sphalerite. The deposit is hosted by structurally controlled faults associated with intense hydrothermal alteration. The typical alteration assemblage is sericite + chlorite + calcite + quartz, with an inner pyrite - sericite - quartz zone and an outer seicite - chlorite - calcite - epidote zone between orebodies and wall rocks. δ34 S values of 17 sulfides from ores changing from –1.67 to +0.49‰ with average of –0.49‰, are similar to δ34 S values of magmatic or igneous sulfide sulfur. 206Pb/204Pb, 207Pb/204Pb and 208Pb/ 204Pb data of sulfide from ores range within 17.66–17.75, 15.50–15.60, and 37.64–38.00, respectively. These sulfur and lead isotope compositions imply that ore-forming materials might mainly originate from deep sources. H and O isotope study of quartz from ore-bearing veins indicate a mixed source of deep-seated magmatic water and shallower meteoric water. The ore formations resulted from a combination of hydrothermal fluid mixing and a structural setting favoring gold-polymetal deposition. Fluid mixing was possibly the key factor resulting in Au-Ag-Cu-Pb-Zn deposition in the deposit. The metallogenesis of the Bianbianshan deposit may have a relationship with the Cretaceous volcanic-subvolcanic magmatic activity, and formed during the late stage of the crust thinning of North China.     

S,Pb, C and O isotopic compositions and ore genesis of the strata-bound polymetallic sulfide deposits in central Inner Mongolia,China

The strata-bound Cu−Pb−Zn polymetallic sulfide deposits occur in metamorphic rocks of greenschist phase of the middle-upper Proterozoic Langshan Group in central Inner Mongolia. δ³⁴S values for sulfides range from −3.1‰ to +37.3‰, and an apparent difference is noticed between vein sulfides and those in bedded rocks. For example, δ³⁴S values for bedded pyrite range from +10.6‰ to +20.0‰, while those for vein pyrite vary from −3.1‰ to +14.1‰. δ³⁴S of bedded pyrrhotite is in the range +7.9‰–+23.5‰ in comparison with +6.5‰–+17.1‰ for vein pyrrhotite. The wide scatter of δ³⁴S and the enrichment of heavier sulfur indicate that sulfur may have been derived from H₂S as a result of bacterial reduction of sulfates in the sea water. Sulfur isotopic composition also differs from deposit to deposit in this area because of the difference in environment in which they were formed. The mobilization of bedded sulfides in response to regional metamorphism and magmatic intrusion led to the formation of vein sulfides. δ¹⁸O and δ¹³C of ore-bearing rocks and wall rocks are within the range typical of ordinary marine facies, with the exception of lower values for ore-bearing marble at Huogeqi probably due to diopsidization and tremalitization of carbonate rocks. Pb isotopic composition is relatively stable and characterized by lower radio-genetic lead. The age of basement rocks was calculated to be about 23.9 Ma and ore-forming age 7.8 Ma.²⁰⁷Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb and²⁰⁸Pb/²⁰⁴Pb−²⁰⁶Pb/²⁰⁴Pb plots indicate that Pb may probably be derived from the lower crust or upper mantle. It is believed that the deposits in this region are related to submarine volcanic exhalation superimposed by later regional metamorphism and magmatic intrusion.     

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.

     

Carbonization and geochemical characteristics of graphite-bearing rocks in the northern Khanka terrane,primorie, Russian Far East

Regional carbonization was examined in Riphean metamorphic complexes in the northern part of the Khanka terrane. The results obtained by various techniques of physicochemical analysis indicate that all petrographic rock varieties of this complex bear elevated concentrations (from 10⁻⁴ to 10⁻⁶ wt %) of Au and PGE. XRF data were used to describe a wide spectrum of trace elements: Ti, V, Ni, Cr, Pt, Pd, Re, Rh, Os, Ir, Cu, Hg, Au, Ag, Ta, Nb, Sr, Rb, Zr, La, W, Sn, Pb, and Zn. The Rb/Sr-Ba diagram shows the fields of anatectic granite-gneisses, biotite granites, lamprophyres, graphitized crystalline schists, black shales, skarns, and quartz-graphite metasomatic rocks. The C isotopic composition in graphite from the metaigneous rocks (lamprophyres and crystalline schists of the amphibolite facies) corresponds to δ¹³C from −8.5 to −8.7‰, which suggests that the carbon could be of endogenic provenance. The carbon isotopic composition of the greenschist-facies black shales corresponds to δ¹³C from −19.9 to −26.6‰, as is typical of organogenic carbon. The concentrations of precious metals in the rocks are, on average, one order of magnitude lower than in the graphitized crystalline schists. The origin of the precious-metal ore mineralization was likely genetically related to the regional carbonization process.     

Fluctuations in a magmatic sulphur isotope signature from the Pinnacles Mine,New South Wales,Australia

Sulphur isotopic compositions of 29 sulphide samples from the Broken Hill-type Pinnacles Deposit, NSW, are found to cluster at 0%. (mean −0.8‰). The restricted range of the (δ³⁴S) values between −3.5 and + 3.7‰ with a mean of −0.8‰, is interpreted as reflecting partial oxidation of a dominantly magmatic sulphur source. δ³⁴S data for galena samples fall into two groups: (1) isotopically heavier galenas (range −0.7 to 0.0‰; mean −0.4‰) which come mainly from the footwall Zn lode and (2) isotopically lighter galenas (range −3.5 to −0.8‰; mean −2.2‰) which are from the main Pb lode. Sphalerite, pyrrhotite and chalcopyrite have slightly heavier isotopic compositions (range −1.6 to +3.7‰ mean +0.3‰) but exhibit the same stratigraphic differentiation. These data are interpreted as representing fluctuating conditions at the site of ore deposition, in which upwelling hydrothermal fluids were subject to increasing fO₂ and decreasing temperature with time.     

The Niujiaotang Cd-rich zinc deposit,Duyun, Guizhou province,southwest China: ore genesis and mechanisms of cadmium concentration

The Niujiaotang zinc deposit in southeastern Guizhou, China, is a Mississippi Valley-type Zn deposit within Early Cambrian carbonate rocks. Sphalerite is enriched in cadmium (average 1.4 wt.% Cd), which occurs mostly as isomorphous impurities in the sphalerite lattice. Discrete cadmium minerals (greenockite and otavite) are rare and are found almost exclusively in the oxidation zone of the deposit, probably formed as secondary minerals during weathering–leaching processes. Geochemical data show that the sulfides are enriched in heavy sulfur, with δ³⁴S ranging from +10.0‰ to +32.8‰ (mean +22.5‰). The consistent Pb isotopic compositions in different sulfide minerals are similar to that of Cambrian strata. The ore lead probably came from U- and Th-rich upper crustal rocks, such as the Lower Cambrian Wuxun Formation. The ore fluid is of low-temperature (101°C to 142°C) type, with a Na–Ca–Mg–Cl-dominant composition, and is interpreted as oil-field brine. The data indicate that the metals were mainly derived from the Early Cambrian strata (Qingxudong and Wuxun Formations), whereas sulfur is sourced from sulfate in Cambrian strata or oil-field brines of the Majiang petroleum paleoreservoir. The genetic model for the deposit invokes an Early Cambrian shallow-sea environment on the Yangtze Platform. Zinc and Cd in seawater were concentrated in abundant algae via unknown biological mechanisms, resulting in large amounts of Zn- and Cd-rich algal ooliths. During the Ordovician, concurrent with destruction of the Majiang petroleum paleoreservoir, oil-field brines migrated from the center of the basin to the margin leaching metals from the Cambrian strata. In the Niujiaotang area, preexisting Zn and Cd, particularly in the Qingxudong and Wuxun Formation, were further mobilized by hot brines rising along the Zaolou fault system, forming stratiform and generally conformable Zn–Cd orebodies in reactive carbonate lithologies.     

Sulfur isotopic composition of the Bainiuchang super-large Ag polymetallic deposit, Yunnan Province, China： Implications for the source of sulfur in ore-forming fluids

The Bainiuchang deposit in Yunnan Province, China, is located geographically between the Gejiu ore field and the Dulong ore field. In addition to >7000 t Ag reserves, the deposit possesses large-scale Pb, Zn, Sn reserves and a mass of dispersed elements (i.e., In, Cd, Ge, Ga, etc.). Based on systematic studies of sulfur isotopic composition, the authors conclude: The Bainiuchang deposit experienced two epochs of metallogenesis, i.e., the Middle-Cambrian sea-floor exhalative sedimentary metallogenic epoch and the Yanshanian magmatic hydrothermal superimposition metallogenic epoch. In the two metallogenic epochs, the δ³⁴S values of sulfides were all near 0, showing a tendency of being enriched slightly in heavy sulfur. The δ³⁴S values of sulfides in the early metallogenic epoch are within the range of 2‰–5‰ with a peak value range of 2‰–3‰ and an average of 3.0‰, and those of sulfides in the late metallogenic epoch are within the range of 2‰–6‰ with a peak value of 3‰–4‰ and an average of 3.9‰. For the single metallogenic epoch, sulfur in the ore-forming fluids in the early epoch already reached isotopic equilibrium and was derived mainly from underneath the magma chamber or basement metamorphic igneous rocks. Sulfur in the sulfides in the late epoch was derived mainly from magmatic hydrothermal fluids formed in the process of remelting of the basement metamorphic igneous rocks.     

Sulfur Isotopic Composition of Sulfides in Skarn and Vein Mineralization of the Dal’negorsk Ore Region (Primorye)

The S isotopic composition in the ore-forming minerals galena and sphalerite was studied in different Ag–Pb–Zn deposits of the region. It was pointed out that the δ³⁴S modal values range from–1.2 to +6.7‰ in the minerals with a positive value for the skarn mineralization. In the flyschoid formation, the vein-type mineralization is characterized by negative and positive values. The narrow range of δ³⁴S values indicates the marginal-continental type of the mineralization and the multiple origins of its sources.     

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.     

西藏甲玛铜多金属矿硫同位素地球化学研究

西藏墨竹工卡县甲玛铜多金属矿床位于冈底斯成矿带东段,Cu、Mo、Pb+Zn、Au、Ag均达大型规模,并伴生Co、Bi、W、Ni等多金属矿化。黄铜矿、斑铜矿、辉钼矿、方铅矿、闪锌矿、黝铜矿、辉铜矿等硫化物为主要的矿石矿物,硫酸盐矿物以硬石膏为主,含矿岩浆岩以花岗斑岩、二长花岗斑岩和花岗闪长斑岩为主。通过对甲玛矿区主要硫化物和硬石膏的硫同位素分析,并结合前人研究,甲玛矿区硫化物的硫同位素δ34S值变化于13.6‰～+12.5‰,平均值1.33‰(样品数86)、硬石膏δ34S值+0.5‰～+1.8‰,平均值+1.13‰(样品数3)、岩浆岩δ34S值0.7‰～0.2‰,平均值0.5‰(样品数3),与岩浆硫δ34S值0±3‰一致。闪锌矿-方铅矿-黄铜矿矿物对的硫同位素地质温度计,显示成矿温度为408～433℃,说明其形成时硫同位素处于平衡状态。冈底斯成矿带上的驱龙等斑岩型矿床中硫化物和岩浆岩硫同位素,均具有δ34S值变化范围小,平均值接近0值,与岩浆硫特征一致的特点,反映了甲玛铜多金属矿床具有矽卡岩-斑岩型矿床硫同位素地球化学特征,硫以岩浆来源为主。     

Geochemistry and genesis of the Lengenbach Pb-Zn-As-Tl-Ba-mineralisation,Binn Valley,Switzerland

 The Lengenbach Pb-Zn-As-Tl-Ba mineralisation is located in Triassic dolostones of the Penninic zone in the Swiss Alps where Alpine metamorphism reached upper greenschist to lower amphibolite grade. Geochemical data are used to constrain the origin of this unique occurrence. Two metamorphic redox environments are present: the As(III)-rich zone is controlled by barite-pyrite while the reduced zone contains graphite or pyrrhotite-pyrite and formally zerovalent As. The As(III)-rich zone is characterised by a mineral assemblage consistent with fO₂ in the stability field of barite+pyrite. An As-(Pb, Tl)-rich sulphide melt coexisted with a hydrothermal fluid at >kk300 °C in this zone. Mineralised dolostones are anomalous in As, Pb, Ag, Tl, Hg, Zn, Ba, Cd, Fe, Cu, Mo, U, V, B, Ga, Cr and possibly Sn and Au (in order of decreasing enrichment). As, Pb and Zn are present in the 0.1 to 1% range, Tl and Ag reach several hundred ppm. Uraninite is concentrated in silicate-rich bands and yields a late Alpine U-Pb age of 18.5±0.5 Ma. Pb- and S isotopic variations are interpreted by metamorphic overprinting and re-equilibration within an isochemically metamorphosed mineralisation. Hydrothermal sulphides are more strongly affected by uranogenic Pb than massive Pb-As-sulphides representing a former sulphide melt. The least overprinted mineralisation is characterised by ²⁰⁶Pb/²⁰⁴Pb U003U=18.44−18.56, ²⁰⁷Pb/²⁰⁴Pb=15.60−15.75, ²⁰⁸Pb/²⁰⁴Pb =38.44−38.84 and δ³⁴S (sulphide)=−25±2‰. S isotopic variations are largely a result of sulphide-sulphate re-equilibration yielding temperatures of 450± 30 °C. ⁸⁷Sr/⁸⁶Sr ratios of mineralised samples are lower than or equal to host dolostones, precluding major infiltration of basement-derived fluids during Alpine metamorphism. The Sr source (⁸⁷Sr/⁸⁶Sr close to 0.708) probably was seawater with a radiogenic, detrital mineral component. The genesis of the unique Lengenbach mineralisation is interpreted as the result of isochemical metamorphic overprinting of a carbonate hosted stratiform sulphide mineralisation. Well-crystallised sulphide minerals in fissures and druses formed during retrograde cooling of a sulphide melt in equilibrium with a hydrothermal fluid. The primary mineralisation was probably formed at or close below the sea floor and fed by sulphide-poor hydrothermal fluids. Sulphide was largely derived from seawater by open system bacterial sulphate reduction. U, V and Mo may be seawater-derived. Received: 1 February 1995/Accepted: 10 January 1996     

Sulfur, lead and helium isotopic compositions of sulfide minerals from the Dachang Sn-polymetallic ore district in South China: implication for ore genesis

Summary The Dachang Sn-polymetallic ore district is one of the largest tin producing districts in China. Its origin has long been in dispute between magmatic-hydrothermal replacement and submarine exhalative-hydrothermal origin. The Dachang ore district comprises several types of ore deposits, including the Lamo magmatogenic skarn deposit near a granite intrusion, the Changpo-Tongkeng bedded and vein-type sulfide deposit, and the Gaofeng massive sulfide deposit. Sulfide minerals from the Lamo skarn ores show δ³⁴S values in the range between −3 and +4‰ with a mean close to zero, suggesting a major magmatic sulfur source that likely was the intrusive Longxianggai granite. Sulfide minerals from the Gaofeng massive ores show higher δ³⁴S values between +5 and +12‰, whereas sulfide minerals from the Changpo-Tongkeng bedded ores display lighter δ³⁴S values between −7 and −0.2‰. The difference in the sulfur isotope ranges in the two deposits can be interpreted by different degrees of inorganic thermochemcial reduction of marine sulfate using a one-step batch separation fractionation model. Sulfur isotopic compositions from the vein-type ores at Changpo-Tongkeng vary widely from −8 to +4‰, but most of the data cluster around −2.9‰, which is close to that of bedded ores (−3.6‰). The sulfur in vein-type ores might be derived from bedded ores or it represents a mixture of magmatic- and sedimentary-derived sulfur. Pb isotopic compositions of sulfide minerals in the Dachang ore district reveal a difference between massive and bedded ores, with the massive ores displaying more radiogenic Pb isotope ratios. Correlations of ²⁰⁶Pb/²⁰⁴Pb and ²⁰⁷Pb/²⁰⁴Pb or ²⁰⁸Pb/²⁰⁴Pb for the massive and bedded ores are interpreted as two-component mixing of Pb leached from sedimentary host rocks and from deep-seated Precambrian basement rocks composed of metamorphosed volcano-sedimentary rocks. Pb isotopic compositions of sulfide minerals from vein-type ores overlap with those of bedded sulfides. Similar to the sulfur, the lead in vein-type ores might be derived from bedded ores. Skarn ores at Lamo show very limited variations in Pb isotopic compositions, which may reflect a major magmatic-hydrothermal lead source. Helium isotope data of fluid inclusions trapped in sulfides indicate that He in the massive and bedded ores has a different origin than He in fluorite of granite-related veins. The ³He/⁴He ratios of 1.2–2.9 Ra of fluid inclusions from sulfides at Gaofeng and Changpo-Tongkeng imply a contribution of mantle-derived fluids. Overall our data support a submarine exhalative-hydrothermal origin for the massive and bedded ore types at Dachang. Supplementary material to this paper is available in electronic form at Appendix available as electronic supplementary material     

Ore-forming material sources of the Jurassic Cu–Pb–Zn mineralization in the Qin–Hang ore belt,South China: Constraints from S–Pb isotopes

The Qin–Hang ore belt in South China, which serves as the boundary between the Yangtze and Cathaysia blocks, is marked by extensive Jurassic porphyry-skarn-metasomatic Cu–Pb–Zn polymetallic mineralization. In this contribution, S and Pb isotopic compositions of the Baoshan Cu–Pb–Zn deposit in the western portion of the Qin–Hang ore belt were analyzed to determine the ore-forming material sources in the area. This is coupled by the first systematic collection, compilation and interpretation of previously published S and Pb isotopic data of multiple sulfide minerals to reveal the metal origin and accumulation mechanism of the Cu–Pb–Zn mineralization from the significant deposits in the region (i.e., Dexing, Qibaoshan, Shuikoushan, Baoshan, Huangshaping, Tongshanling and Dabaoshan). The results show that Cu mineralization is characterized by low and narrow δ³⁴S (‰) range of values (–5 to 6) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.0, ²⁰⁷Pb/²⁰⁴Pb = 15.4–15.8, and ²⁰⁶Pb/²⁰⁴Pb = 17.7–18.7), which are consistent with those of local porphyries. In contrast, the Pb–Zn mineralization reveals higher and more variable δ³⁴S (‰) values (–4 to 18) and Pb isotopic ratios (²⁰⁸Pb/²⁰⁴Pb = 38.0–39.5, ²⁰⁷Pb/²⁰⁴Pb = 15.3–16.0, and ²⁰⁶Pb/²⁰⁴Pb = 18.0–19.0) that correspond to wall-rock and basement rock compositions in the region. This indicates that the sulfur and lead that formed the Cu mineralization in the Qin–Hang ore belt was mainly sourced from regional magmatism with mantle contributions, whereas the sulfur and lead for the Pb–Zn mineralization was likely derived from the host sedimentary rocks and Proterozoic metamorphic basement rocks, respectively. The S and Pb isotopic data, combined with the geochemical signatures of mineralization-related porphyries, suggest that the Cu was sourced from the deeper levels along with mantle-derived magmas. In contrast, the Pb–Zn probably originated from the crust, with partial melting of the crystalline basement in the Cathaysia Block. Consequently, a three-stage genetic model is proposed to explain the ore-forming processes of the Qin–Hang Cu-polymetallic belt in South China.     

Trace element and sulfur isotopic evidence for redox changes during formation of the Wallaby Gold Deposit,Western Australia

Wallaby is a major gold deposit of the St Ives Gold field of Western Australia, with an estimated resource of 8 million ounces of gold. It has a well-established paragenesis across five vein sets that displays macroscopic evidence of changing redox through time; from hematite to magnetite. Micro-analysis of pyrite from each vein generation shows a progressive and gradual change in redox conditions. The sulfur isotope composition has a δ³⁴S range of −7.7 to +9.8‰ using 3 μm spots on the Sensitive High Resolution Iron Micro Probe-Stable Isotope (SHRIMP-SI). Negative values indicative of an oxidized sulfur signature are found in the earliest generation of pyrite (which coexists with hematite) that also contains high concentrations of As, Ni, Zn, Ag, Sb, Cu and Pb. Conversely, positive values representative of reduced sulfur are found in later generations of pyrite, with lower concentrations of As, Ni, Sb, Cu, Zn and Pb. These later pyrite crystals display higher As/Ni, As/Sb, and As/Bi, and lower Cu/Te. These geochemical trends are the result of redox controlled transport and partitioning into pyrite of minor and trace elements now within the pyrite structure. Previous studies suggested a single orogenic event formed the Wallaby Deposit. This is not supported by the present study. Trace element ratios such as As/Ni clearly delineate the high Au generations and could be used as an exploration tool. It is suggested that pyrite from the Wallaby Gold Deposit formed via desulfidation and a gradual change in redox conditions within an evolving fluid and did not result from mixing of two separate fluids as previously advocated. Utilizing pyrite to link the entire fluid history of Wallaby demonstrates the general use of pyrite as a valuable mineral tracer in gold-bearing fluid systems.     

四川乌斯河大型锗铅锌矿床锗超常富集特征及其地质意义

锗(Ge)是我国的一种优势战略性关键矿产,闪锌矿是其主要载体和重要工业来源之一。尽管前人对闪锌矿富锗有了较为深刻的认识,但是对其中锗的替代方式和超常富集机制仍缺乏深入理解。位于扬子地块西南缘的川滇黔铅锌矿集区是我国最重要的锗和铅锌资源基地之一,区内的乌斯河大型铅锌矿床(5.4Mt@8.6%Zn,2.0%Pb)显著超常富锗(铅锌矿石中Ge平均品位为72.3×10~(-6),闪锌矿中Ge含量高达1934×10~(-6))。何种因素制约该矿床中锗的超常富集亟待解密。乌斯河矿床发育两期闪锌矿,早期闪锌矿(Sp1)单偏光下呈白色-棕黑色,发育半自形细粒结构,浸染状构造;晚期闪锌矿(Sp2)单偏光下呈白色-红色或灰色-棕黑色,发育自形-半自形细-粗粒结构,块状或脉状构造。激光剥蚀耦合等离子体质谱(LA-ICPMS)闪锌矿原位微量元素含量分析结果显示,闪锌矿中Ge含量为3.17×10~(-6)～1934×10~(-6),平均563×10~(-6),相对Ge的地壳丰度(1.5×10~(-6))具有显著超常富集特征(高达1000倍)。闪锌矿中Ge与Fe、Cu、Ag、Pb具有正相关关系,而与Cd呈负相关性。元素面扫描(Mapping)结果显示,闪锌矿中Ge主要以类质同象形式存在,且Ge与Fe、Cu、Ag、Pb、Cd等元素相关关系与含量分析结果一致。结构相似度计算结果进一步显示,Sp1中Ge与Ag相关程度最高,而Sp2中Ge与Cu相关系数最大,暗示结构相似度计算在比较元素相关关系中有较大的应用潜力。然而,乌斯河矿床闪锌矿中Cu、Ag含量常低于Ge含量,且(Ge/Cu) mol和(Ge/Ag) mol比值变化范围大,所以单一的元素相关程度分析并不能完全解决Ge替代方式问题。综合研究认为,该矿床闪锌矿中Ge替代方式与Cu、Ag等元素关系不大,而是直接替代Zn(Ge(4+)■2Zn~(2+)或Ge~(2+)■Zn~(2+))。另外,乌斯河矿床同一闪锌矿颗粒不同部位(如扇形分区和振荡环带) Ge含量变化显著,暗示Ge的超常富集很可能受闪锌矿的沉淀速率和结晶过程控制,而Sp1与Sp2中Ge含量的明显差异,则很可能与成矿流体演化过程流体成分和成矿物理化学条件改变有关。因此,乌斯河大型锗铅锌矿床锗的超常富集是流体成分、物化条件、沉淀速率和结晶过程等多要素耦合作用特殊地球化学过程的结果,并受到矿物和矿床等不同尺度苛刻成矿条件的影响。     

Trace metal nanoparticles in pyrite

Hydrothermal pyrite contains significant amounts of minor and trace elements including As, Pb, Sb, Bi, Cu, Co, Ni, Zn, Au, Ag, Se and Te, which can be incorporated into nanoparticles (NPs). NP-bearing pyrite is most common in hydrothermal ore deposits that contain a wide range of trace elements, especially deposits that formed at low temperatures. In this study, we have characterized the chemical composition and structure of these NPs and their host pyrite with high-resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED), high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM), analytical electron microscopy (AEM), and electron microprobe analysis (EMPA). Pyrite containing the NPs comes from two types of common low-temperature deposits, Carlin-type (Lone Tree, Screamer, Deep Star (Nevada, USA)), and epithermal (Pueblo Viejo (Dominican Republic) and Porgera (Papua New-Guinea)).EMPA analyses of the pyrite show maximum concentrations of As (11.2), Ni (3.04), Cu (2.99), Sb (2.24), Pb (0.99), Co (0.58), Se (0.2), Au (0.19), Hg (0.19), Ag (0.16), Zn (0.04), and Te (0.04) (in wt.%). Three types of pyrite have been investigated: “pure” or “barren” pyrite, Cu-rich pyrite and As-rich pyrite. Arsenic in pyrite from Carlin-type deposits and the Porgera epithermal deposit is negatively correlated with S, whereas some (colloform) pyrite from Pueblo Viejo shows a negative correlation between As + Cu and Fe. HRTEM observations and SAED patterns confirm that almost all NPs are crystalline and that their size varies from 5 to 100 nm (except for NPs of galena, which have diameters of up to 500 nm). NPs can be divided into three groups on the basis of their chemical composition: (i) native metals: Au, Ag, Ag–Au (electrum); (ii) sulfides and sulfosalts: PbS (galena), HgS (cinnabar), Pb–Sb–S, Ag–Pb–S, Pb–Ag–Sb–S, Pb–Sb–Bi–Ag–Te–S, Pb–Te–Sb–Au–Ag–Bi–S, Cu–Fe–S NPs, and Au–Ag–As–Ni–S; and (iii) Fe-bearing NPs: Fe–As–Ag–Ni–S, Fe–As–Sb–Pb–Ni–Au–S, all of which are in a matrix of distorted and polycrystalline pyrite. TEM-EDX spectra collected from the NPs and pyrite matrix document preferential partitioning of trace metals including Pb, Bi, Sb, Au, Ag, Ni, Te, and As into the NPs. The NPs formed due to exsolution from the pyrite matrix, most commonly for NPs less than 10 nm in size, and direct precipitation from the hydrothermal fluid and deposition into the growing pyrite, most commonly for those > 20 nm in size. NPs containing numerous heavy metals are likely to be found in pyrite and/or other sulfides in various hydrothermal, diagenetic and groundwater systems dominated by reducing conditions.     

Phosphorite-hosted zinc and lead mineralization in the Sekarna deposit (Central Tunisia)

The Sekarna Zn–Pb deposit is located in Central Tunisia at the northeastern edge of the Cenozoic Rohia graben. Mineralization comprises two major ore types: (1) disseminated Zn–Pb sulfides that occur as lenses in sedimentary phosphorite layers and (2) cavity-filling zinc oxides (calamine-type ores) that crosscut Late Cretaceous and Early Eocene limestone. We studied Zn sulfide mineralization in the Saint Pierre ore body, which is hosted in a 5-m-thick sedimentary phosphorite unit of Early Eocene age. The sulfide mineralization occurs as replacements of carbonate cement in phosphorite. The ores comprise stratiform lenses rich in sphalerite with minor galena, Fe sulfides, and earlier diagenetic barite. Laser ablation–inductively coupled plasma mass spectrometry analyses of sphalerite and galena show a wide range of minor element contents with significant enrichment of cadmium in both sphalerite (6,000–20,000 ppm) and galena (12–189 ppm). The minor element enrichments likely reflect the influence of the immediate organic-rich host rocks. Fluid inclusions in sphalerite give homogenization temperatures of 80–130°C. The final ice melting temperatures range from −22°C to −11°C, which correspond to salinities of 15–24 wt.% NaCl eq. and suggest a basinal brine origin for the fluids. Sulfur isotope analyses show uniformly negative values for sphalerite (−11.2‰ to −9.3‰) and galena (−16‰ to −12.3‰). The δ³⁴S of barite, which averages 25.1‰, is 4‰ higher than the value for Eocene seawater sulfate. The sulfur isotopic compositions are inferred to reflect sulfur derivation through bacterial reduction of contemporaneous seawater sulfate, possibly in restricted basins where organic matter was abundant. The Pb isotopes suggest an upper crustal lead source.