Unique Origin of Skarn at the Ohori Base Metal Deposit,Yamagata Prefecture,NE Japan: C,O and S Isotopic Study

The Ohori ore deposit is one of the Cu–Pb–Zn deposits in the Green Tuff region, NE Japan, and consists of skarn‐type (Kaninomata) and vein‐type (Nakanomata) orebodies. The former has a unique origin because its original calcareous rocks were made by hydrothermal precipitation during Miocene submarine volcanism. Carbon and oxygen isotope ratios of skarn calcite and sulfur isotope ratios of sulfides were measured in and around the deposit. Carbon and oxygen isotope ratios of the skarn calcite are δ¹³C = ?15.51 to ?5.1‰, δ¹⁸O = +3.6 to +22.5‰. δ¹³C values are slightly lower than those of the Cretaceous skarn deposits in Japan. These isotope ratios of the Kaninomata skarn show that the original calcareous rocks resemble the present submarine hydrothermal carbonates at the CLAM Site, Okinawa Trough, than Cenozoic limestones, even though some isotopic shifts had occurred during later skarnization. δ³⁴S ratios of the sulfide minerals from the Kaninomata and Nakanomata orebodies are mostly in a narrow range of +4.0 to +7.0‰ and they resemble each other, suggesting the same sulfur origin for the both deposits. The magnetite‐series Tertiary Kaninomatasawa granite is distributed just beneath the skarn layer and has δ³⁴S ratios of +7.5 to 8.1‰. The heavy sulfur isotope ratio of the skarn sulfides may have been affected by the Kaninomatasawa granite.     

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.     

Source Diversity of Ore Sulfur from Mesozoic-Cenozoic Mineral Deposits in the Korean Peninsula Region

Abstract: Sulfides from the Daebo Jurassic granitoids and some ore deposits from Korean Peninsula and Sikhote Alin occurring in different basement settings were analyzed for δ³⁴S values. Highly positive values were obtained from Jurassic Mo skarn deposit at Geumseong of the Ogcheon belt (average +13. 0%), Au‐quartz vein deposits at Unsan, North Korea (+6. 7%), and late Paleozoic Sn‐F deposit at Votnesenka (+8. 2%), Khanka massif, Russia. Together with published data of that region, regional variation of δ³⁴S values is shown across Korean Peninsula. Sulfur isotopic data published are compiled on 88 ore deposits, whose mineralization epochs belong to Cretaceous (58 deposits), Jurassic (25 deposits) and Precambrian (4 deposits) in South Korea. Average sulfur isotopic values vary across South Korea as follows: Cretaceous deposits in the Gyeongsang basin, +4. 8% ranging +1.2 ? +12.7‰ (n=28); Jurassic and Cretaceous deposits in the Sobaegsan massif, +3. 5% ranging 0.0 ? +7.8‰ (n=20); those of the Ogcheon belt, +6. 4% ranging ‐0.5 ? +15.4‰(n=19); those of the Gyeonggi massif, +5. 5% ranging +2.1 ? +9.0‰(n = 21). The δ³⁴S values of South Korea tend to be concentrated around +5. 5 permil, exhibiting little, if any, a systematic variation across the geotectonic belts. This tendency is seen also in North Korea and Northeast China within the Cino‐Korean Block, and may be called as Cino‐Korean type. Sulfur of this type is derived mostly from the crystalline basement. Khanka massif of Russia seems to have features of the Cino‐Korean type. In contrast, paired positive/negative belts corresponding to magnetite‐series/ilmenite‐series granitic belts are overwhelming in the Japanese Islands, especially in Southwest Japan. The similar trend is also seen in southern Sikhote Alin and northern Okhotsk Rim, which may be called as Japanese type. Source of the sulfur in this type is likely in the subducting oceanic slab for positive value and accreted sedimentary complex for the negative value, respectively. The Daebo granitoids have an average rock δ³⁴S value of +5. 3 permil, which should have reflected that of the source rocks in the continental crust. The ore sulfur heavier than this value may have been originated in other granitoids having even higher δ³⁴S values, or the ore fluids interacted directly with sulfate sulfur of the host evaporites or carbonate rocks. Rock isotopic values of granitoids and basement rocks need to be examined in future from the above point of view in mind.     

Fluid properties and sources of Sixiangchang carbonate-associated mercury deposit,southwest China

Mercury mines in Guizhou province are the main base of mercury production and the most important resource base in China. The San-Dan mercury belt in Guizhou province contains a series of important mercury deposits. However, the source of metallogenic materials and the properties of metallogenic fluid of these mercury deposits have long been a controversial issue. In this study, we used cathode luminescence techniques to distinguish different stages of dolomite and calcite, laser ablation inductively coupled plasma mass spectrometry to analyze the trace elements, and stable isotope mass spectrometry techniques to analyze C–O isotopes compositions of dolomite and calcite in the Sixiangchang mercury deposit in San-Dan mercury belt. We also measured the sulfur isotope composition of cinnabar. Our study showed that dolomite can be divided into two stages, the lumpy dolomite associated with cinnabar in Dol 1 stage and dolomite vein in Dol 2 stage, which is associated with Cal 2 stage calcite vein. With the progress of mineralization, Al, As, Mo, Sb, and Sr elements were gradually enriched in the ore-forming fluid. The rare earth element (REE) partition curve of Dol 1 stage dolomite showed a trend of light REE enrichment. Cal 2 stage calcite and Dol 2 stage dolomite exhibited a flat-type REE partition curve, and Dol 2 stage dolomite showed a strong negative anomaly for Eu. δ¹³C of carbonate mineral variation ranges from − 6.89 to − 2.16 ‰, while δ¹⁸O variation ranges from 13.80 to 23.09 ‰, and the δ³⁴S variation range of cinnabar is 16.51–24.28 ‰. Carbonate mineral trace elements and C–O isotopes compositions suggested that early ore-forming fluid was reduced, and late ore-forming fluid was oxidized. The ore-forming fluid of the Sixiangchang mercury deposit is a mixture of deep crustal fluid and meteoric water in deep thermal circulation, and involved in the oxidation of organic matter. The cinnabar δ³⁴S results showed that sulfur mainly came from seawater sulfate with the participation of microbial reduction. Sulfur is sedimentary in origin and was derived mainly from the host-rock strata.

     

Variation of Cl and SO3 Contents of Microphenocrystic Apatite in Intermediate to Silicic Igneous Rocks of Cenozoic Japanese Island Arcs: Implications for Porphyry Cu Metallogenesis in the Western Pacific Island Arcs

Abstract. Determinations of SO₃ and Cl contents of igneous accessory apatite were carried out on Late Cenozoic intermediate to silicic intrusive and volcanic rocks in the Japanese island arcs of the western Pacific rim including the southwestern Kuril arc (eastern Hokkaido), Northeast Japan arc (southwestern Hokkaido through northeastern Honshu to central Honshu), Izu‐Bonin arc, Kyushu‐Palau ridge, Southwest Japan arc (northern Kyushu) and northern Ryukyu arc (southern Kyushu). These were compared to those from the Western Luzon arc, Philippines, to better understand the metallogenesis of porphyry Cu deposits in the western Pacific island arcs. In addition, SO₃ and Cl contents of accessory apatite in the Cretaceous magnetite‐series granitic rocks in the Kitakami belt (northeastern Honshu) and the Miocene ilmenite‐series granitic rocks in the Outer Zone of Southwest Japan (southern Kyushu) were also examined. Microphenocrystic apatites in shallow intrusions associated with porphyry Cu deposits in the Western Luzon arc contain >0.1 wt% S as SO₃. Such high SO₃ contents of microphenocrystic apatite are a common characteristic of hydrous mag‐matism in the Western Luzon arc, from 15 Ma old tonalitic plutonic rocks of the Luzon Central Cordillera to present‐day volcanism at Mount Pinatubo. The accessory apatite in intrusive rocks associated with porphyry Cu deposits, especially those at the Santo Tomas II deposit, show significantly high Cl contents (>2 wt%). The SO₃ contents of microphenocrystic apatite in most of the hydrous silicic rocks along the volcanic front, in andesites related to native sulfur deposits, and in Miocene and younger shallow granitic intrusions in northeastern Honshu, are generally <0.1 wt%. On the other hand, the SO₃ contents of apatite in such rocks from eastern Hokkaido, southwestern Hokkaido, Izu, northern Kyushu and southern Kyushu are similar to those from the Western Luzon arc. The SO₃ contents of accessory apatite in the Cretaceous magnetite‐series granitic rocks in the Kitakami belt are variable, whereas those of the Miocene ilmenite‐series granitic rocks in southern Kyushu are extremely low. The Cl contents of accessory apatite in some rocks of the Northeast Japan arc, Izu‐Bonin arc and Southwest Japan arc are significantly high. In terms of the Cl and SO₃ contents of microphenocrystic apatite, Cenozoic Japanese arc magmatism show similarities with arc magmatism associated elsewhere with porphyry Cu mineralization, except for the most of northeastern Honshu of the Northeast Japan arc. Apatite commonly occurs as inclusions in other phenocrystic phases. Thus the variation in SO₃ contents of apatite is a feature of early stage magmatic differentiation. The SO₃ contents of microphenocrystic apatite are considered to reflect the redox state of the magma source region or fluids encountered during magma generation.     

Microstructure and geochemistry studies on Messinian gypsum deposits from the Northern Coast of Egypt

Messinian gypsum deposits from Dir El-Baraqan area, Northern Coast of Egypt, were investigated by stable sulfur isotope method, X-ray diffraction, infrared spectroscopy, optical microscopy, and scanning electron microscopy to differentiate features formed under substantial microbial influences as indicator of paleoenvironments. Petrographically, gypsum deposits were classified into three types: biolaminated gypsum, disordered selenite, and swallow-tail selenitic crystals. Biolaminated gypsum is characterized by regular alternating dark and light laminae, which were formed due to the seasonal environmental changes in Dir El-Baraqan area. Stable sulfur isotope data show that the gypsum deposits are characterized by δ³⁴S values ranging from +18.1 to +28.1 ‰. In swallow-tail gypsum, the δ³⁴S values are characterized by a narrow range (from +20.0 to +20.2 ‰) which is considered as the primary phase. In biolaminated gypsum, the δ³⁴S values ranged from +22.8 to +28.1 ‰ which is considered as the secondary phase. However, the white laminae are characterized by δ³⁴S values ranging from +22.8 to +24.1 ‰, while dark laminae are characterized by δ³⁴S values ranging from +27.2 to +28.1 ‰. The high δ³⁴S values of dark laminae revealed the increasing activity of sulfate-reducing bacteria.     

Stable isotope,petrological, and fluid inclusion studies of minor mineral deposits from the McArthur Basin: Implications for the genesis of some sediment‐hosted base metal mineralization from the Northern Territory

The geology, stable isotopes and fluid inclusions from mineralized and unmineralized Middle Proterozoic sequences of the McArthur Basin, Northern Territory, have been studied at Eastern Creek, Bulman Mines, Beetle Springs, and other localities in the McArthur Basin where disseminated sulphides in unmineralized black shales were available from drill core. At Eastern Creek, galena and minor chalcopyrite (δ³⁴S+3.6 to +11.2%o) occur in an evaporitic sedimentary sequence. Barite (δ³⁴S+18.4 to +24.7%o) also occurs, and saline brines are trapped along healed fractures in the barite. Pressure‐corrected trapping temperatures in the barite (95–138°C), and in vein dolomite (158–168°C) agree with temperature estimates from the degree of maturation of the sedimentary organic matter. The δ¹⁸O and δ¹³C_Co2 values of the mineralizing fluid were calculated to be +3.5 to +4.5%o and ‐2.7%o, respectively. Sedimentary dolomite has restricted δ¹³C and δ¹⁸O ranges, within the reported ranges for non‐mineralized Middle Proterozoic dolomite. An ore formation model developed for Eastern Creek, in which a basinal fluid at about 200°C carrying base metals and sulphide was released from underlying sediments during local fault movement, may be applicable to a number of other deposits. The mineralization deposited from these fluids occurs only below the pre‐Roper Group unconformity, implying that it may be older than the basal Roper Group. The δ³⁴S values of iron sulphides in fine grained black dolostones (not associated with mineral deposits) from the McArthur Basin were assessed in the light of the values found for sulphides in modern organic‐rich sedimentary environments. The data so obtained suggest that the considerable concentration of iron sulphide in the mineral deposits formed, at least in part, from heated basinal waters and that disseminated iron sulphides remote from mineralization also formed from a similar source.     

Sulfur Isotopic Variation of Yanshanian Magmatic-hydrothermal Deposits in Southern China

Abstract: Sulfur isotope data (δ³⁴S) of sulfides of more than 6700 samples from 157 ore deposits associated with Early and Late Yanshanian granitic and volcanic activities in South China are reviewed and summarized. Averaged δ³⁴S values of individual deposits vary from ‐9. 3 to +20. 6%, and show a normal distribution pattern with the average of +2%. About 88 % of the ore deposits have values within the range, ?2.5 ? +13.6‰, of associated Yanshanian granitoids. There is a temporal‐spatial variation of δ³⁴S values of the ore deposits. However, no clear zonal distribution parallel to geotectonic NNE lineaments was observed. Spatial distribution of ore sulfide δ³⁴S values in most of the NE part of the whole studied area coincides with that of Yanshanian granitoids and volcanic rocks. A downward tendency of the average values in time is: +3. 0% (n=7, J₁) → +1. 6% (n=29, J₂) → +1. 7% (n=68, J₃) → +1. 8% (n=37, K₁) → ?1. 5% (n=16, K₂). There is an “island” of high and variable δ³⁴S values (0? +16.5‰) occurring within a generally low trough zone (?8 ? 0%) of N‐S about 800 km and E‐W 100 to 300 km, bounded by 110°E ? 116°E longitudes and 22°N ? 31°N latitudes. The island occurs at the junction of three tectonic units and a NE‐trending crustal matching line implying a variety of magmatism occurred at the junction. The low trough zone coincides with a low ferric/ferrous ratio zone of Early Yanshanian granitoids, indicating their genetic relationship. Different genetic types of ore deposits show different histogram patterns suggesting different relationships to magmatic rocks and host strata. Granite/greisen/pegmatite type deposits are most closely associated with granitoids, with average ore sul‐fide δ³⁴S values for individual ore deposits ranging between ‐2. 0 and +4. 1%, and an average of +0. 5% (n = 15) close to type meteoric value of 0%. Porphyry‐type deposits have also narrow range of ?2.2 ? + 4.9‰, with an average value of +1. 1% (n = 18). Skarn‐type dominated ore deposits have a nearly normal distribution pattern with an average of +1. 6% (n = 62), ranging from ‐5. 3 to +11. 5%. Volcano‐subvolcanic ore deposits range between ‐3. 1 and +5. 9% with an average of +2. 3% (n = 19). Other types of hydrothermal ore deposits have averaged δ³⁴S values of individual ones from ‐9. 3 to +20. 6%, with average value of +1. 3% (n=43). Vertical and horizontal zonations of δ³⁴S values of ore deposits around their associated granitoid plutons are observed in several localities. Such zonations may be caused by interaction between magma and/or magmatic fluids and host sedimentary rocks, as well as the evolution of physico‐chemical conditions of ore‐forming fluids. Spatial distribution of ore sulfur isotope compositions is also clearly controlled by tectonics and deep faults. Ore sulfur isotope composition is sometimes strongly affected by host sedimentary rocks, especially by evaporite sulfur with much higher δ³⁴S value and partly by biogenic sulfur with low δ³⁴S value. The δ³⁴S values of Yanshanian granitoids are from ‐2. 5 to +13. 6% for both rock samples and pyrite/pyrrhotite separates from granitic rocks, with similar spatial distribution pattern to those of associated ore deposits. The ore deposits associated with ilmenite‐series granitoids have δ³⁴S values ranging between ‐7. 5 and +10. 4% with an average of +1. 0%, while the ore deposits associated with magnetite‐series granitoids ranging between ?8.0 ? +11.5‰ with an average of +1. 1%. δ³⁴S values of ore deposits tend to converge to +3% as the Fe₂O₃/FeO ratio of associated granitoids increases from 0. 45 to 8. 7.     

Hydrothermal uranium deposits and sulfur isotopes

Research on sulfur isotopes in hydrothermal uranium deposits with acid alterations shed much light on the genetic aspects of hydrothermal uranium deposits. Based on the studies of uranium deposits of different genesis, it is concluded that σ³⁴S of Sulfides in hydrothermal uranium deposits derived from residual magma is within the range of +2‰ ?2.6‰, approximately the same as meteorite sulfur. δ³⁴S of Sulfides in polygenetic hydrothermal uranium deposits is slightly lighter than meteorite sulfur and varies over a restricted range (6.7‰), averaging ?10.15‰. Two intervals can be recognized with respect to sulfur isotopic compositions in palingenetic hydrothermal uranium deposits. δ³⁴S of sulfides formed in diagenesis, autometamorphism and hypothermal stages is similar to meteorite sulfur. On the other hand, at the stage starting from the alteration of uranium mineralization to the formation o uranium deposits and postmineralization the average δ³⁴S is -7.89‰, with a wider range of δ³⁴S variation (13.7‰), which can be attributed to the enrichment of δ³⁴S in palingenetic hydrothermal solutions.     

The Geochemical Characteristics and Minerogenic Model for the Amo Hypothermal Tin Deposit in Ximeng County, Yunnan Province

Through studies on the element geochemistry, alteration of country rocks, ore-forming fluids and isotopegeochemistry of the Arno tin deposit in the metamorphic rocks of the Upper Proterozoic Ximeng Group, theauthors consider that the concentration of the B-F-Li-Rb-Cs-Sn association is related to acidic magmatism inthe study area. The Fe-Mg-Li tourmaline in the ore is the replaced product of the country rocks byhypothermal fluid. The δ~(18)O values of mineral separates are +2.01- +13.16‰ and their δ~(34)S values, +2.6-+7.2‰. The ore-forming materials were derived from hydrothermal fluid of granitic magma. For themineralization, the temperature is 450°-350℃, the pressure, 450-1000×10~5 Pa, and the age, Himalayan(21.5 Ma). According to the geochemical characteristics, a minerogenic model is established: the deposit is ahypothermal cassiterite-quartz vein type tin deposit controlled by the hidden Himalayan granites.     

中国主要类型锑矿床硫同位素组成及地球化学特征

中国主要类型锑矿床的硫同位素组成范围变化很大,锑矿床中各种矿物（辉锑矿、黄铁矿、闪锌矿、雄黄、方铅矿、重晶石、毒砂、辰砂、脆硫锑铅矿）的δ３４Ｓ值从－３２．７‰变化到＋３４．８‰,极差值高达６７．５‰。各类锑矿床中矿物的硫同位素组成变化各异,说明锑矿床成因较复杂,硫的来源不仅有海水中沉淀的硫酸盐硫,而且还有生物、细菌形式的还原硫和深源硫（岩浆作用、喷流作用等）,从而形成不同类型或成因复杂的锑矿床     

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.     

Sulfur Isotope Geochemistry of the Supergiant Xikuangshan Sb Deposit, Central Hunan, China: Constraints on Sources of Ore Constituents

Abstract. The supergiant Xikuangshan Sb deposit is located in the Middle to Upper Devonian limestone of central Hunan, China. Primary ores are composed of early-stage stibnite and calcite with rare pyrite, early main-stage stibnite and quartz, and late main-stage stibnite and calcite. New sulfur isotope data reveal the clustering of δ³⁴S values (+5 ∼ +8 %) for both early and late main-stage stibnite; a single early-stage stibnite exhibits δ³⁴S value (+7.5 %) identical to its main ore-stage counterparts and the coexisting calcite has almost unmodified carbon isotope composition (-4.4 %). The data suggest a probable common source of sulfur for stibnite that was deposited at different paragenetic stages. A much wider variation in δ³⁴S values for early main-stage stibnite (+3.5 to +16.3 %, av. +7.5 %) compared to that for late main-stage stibnite (+5.3 to +8.1 %, av. +6.2 %) can be interpreted to be due to local interaction of earlier ore fluid with Devonian host rocks. The previous studies show that the Precambrian basement contains elevated Sb concentrations, and two distinctive sulfur reservoirs with δ³⁴S_pyrite values at ca. +11 ∼ +24 % and -7.0 ∼-11 %. The homogenizing effect for sulfur hydrothermally leached from the two reservoirs might have provided ore constituents for the Xikuangshan fluids.     

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.     

城门山及武山铜矿床的硫同位素研究

地质概况江西城门山矿床和武山矿床是长江中下游铁铜成矿带大冶-九江成矿亚带东南部位的两个与斑岩有成因关系的铜矿床。在地质构造上,前者处于九江-瑞昌东西向拗陷带中的长山-城门湖背斜倾伏端的北翼,后者处在横立山-黄桥向斜东端的北翼。两矿区的地层分布相似,主要是志留系至三叠系地层。其中,泥盆系上统五通组砂岩及石炭系中统黄龙组灰岩与矿床关系密切。     

Sulfur-Isotope Characteristics of the Volcanogenic Cu-Zn-Pb Deposits of the Eastern Pontide Region,Northeastern Turkey

In the Eastern Pontide Region of northeastern Turkey, volcanogenic Cu-Zn-Pb deposits of the Kuroko type are widespread within the dacitic series of the Liassic-Eocene volcano-sedimentary succession. Sulfide mineralization within the studied deposits shows four different depositional styles: disseminated ore; polymetallic stockwork ores; polymetallic massive ores; and disseminated pyrite in the hanging-wall tuff units. Only the stockwork and massive ores are economically important, and usually one or the other dominates in each ore body.

The δ³⁴S of sulfide minerals belonging to the various styles of mineralization are in the range from ?2.6 to +5.2% (VCDT): pyrite has the highest values and the galena lowest values in agreement with the usual isotopic-fractionation trends. Massive ores have heavier sulfur-isotope composition among the mineralization styles and the heaviest values are recorded in barite- and gypsum-rich deposits. The close similarity of the δ³⁴S among the various mineralization episodes in some deposits indicates a single sulfur source having a stable and homogenous composition.

The δ³⁴S of sulfates fall into three groups: barites and primary gypsum (15.4 to 20.4%), close to coeval seawater sulfate; one value of barite (25.4%) heavier than coeval sea water; and values of secondary gypsum (2.2 to 8.0%) either very light compared to coeval seawater sulfate, or within the range recorded from sulfide minerals. The δ³⁴S values of pyrite disseminated in the brecciated dacite tuff units are very close to zero and similar to the ones reported for magmatic rocks, suggesting a magmatic source for the sulfur of the earliest sulfide mineralization episode. These δ³⁴S data are not sufficient to calculate the fraction of the reduced sulfur derived from seawater sulfate, as the associated fractionation factor cannot be constrained.     

The sulfur isotopic composition of sulfides from ores and host rocks of the Upper Kolyma region,Magadan Oblast

More than 200 analyses of the sulfur isotopic composition of sulfides from various terrigenous and intrusive host rocks, metasomatically altered wall rocks, and gold lodes of the Upper Kolyma region are presented. In accessory pyrite of the metaterrigenous rocks, δ³⁴S varies from ?23.1 to +5.7‰ δ³⁴S of pyrite and arsenopyrite from gold-quartz mineralization is within the range ?10.6 to ?0.4‰ and is close to the average δ³⁴S of pyrite from the metaterrigenous rocks (?4.4‰). In the intrusive rocks, δ³⁴S of pyrite varies from ?3.8 to +2.6‰ (+0.7‰, on average) and drastically differs from δ³⁴S of arsenopyrite from postmagmatic gold-rare-metal mineralization (?7.9 to ?2.7‰; ?5.2‰, on average). The comparison of the δ³⁴S of accessory sulfides from the host rocks with δ³⁴S of sulfides from the gold deposits suggests that sulfur mobilized from the terrigenous sequences participated in the hydrothermal process. The results obtained are consistent with the metamorphic model of the formation of gold-quartz deposits in the Upper Kolyma region.     

Origin of sulfur species in acid sulfate-chloride thermal waters,northeastern Japan

Acid sulfate-chloride thermal water samples collected together with fumarolic gases from various volcanic areas in northeastern Japan were studied chemically and isotogdically. δ³⁴S (COT) values of sulfate and hydrogen sulfide from these volcanic hot springs range from +4.0 to +31 and from ?15.0 to ?2.0% respectively, with δ³⁴S_ys value of +2.5 to +31. The δ³⁴S of the sulfate in the more saline waters tends to become smaller with increasing ratio of SO₄ to Cl, although the chemical and isotopic composition of acid thermal water within some areas may be altered by secondary processes during the discharge of the thermal waters. This trend can be explained by the reaction of the volcanic gases, having S/Cl of 4 ~ 7 and total sulfur of ~0% in δ³⁴S, with ground water at 200°C, and/or the removal of sulfide phase depleted in ³⁴S from the acid thermal water formed by the disproportionation of volcanic sulfur. The sulfur species in acid sulfate-chloride thermal water are shown to be volcanic exhalations.     

Late Hercynian polymetallic vein-type base-metal mineralization in the Iberian Pyrite Belt: fluid-inclusion and stable-isotope geochemistry (S–O–H–Cl)

Late Variscan vein-type mineralization in the Iberian Pyrite Belt, related to the rejuvenation of pre-existing fractures during late Variscan extensional tectonism, comprises pyrite–chalcopyrite, quartz–galena–sphalerite, quartz–stibnite–arsenopyrite, quartz–pyrite, quartz–cassiterite–scheelite, fluorite–galena–sphalerite–chalcopyrite, and quartz–manganese oxide mineral assemblages. Studies of fluid inclusions in quartz, stibnite, and barite as well as the sulfur isotopic compositions of stibnite, galena, and barite from three occurrences in the central part of the Iberian Pyrite Belt reveal compelling evidence for there having been different sources of sulfur and depositional conditions. Quartz–stibnite mineralization formed at temperatures of about 200 °C from fluids which had undergone two-phase separation during ascent. Antimony and sulfide are most probably derived by alteration of a deeper lying, volcanic-hosted massive sulfide mineralization, as indicated by δ³⁴S signatures from ?1.45 to ?2.74‰. Sub-critical phase separation of the fluid caused extreme fractionation of chlorine isotopes (δ³⁷Cl between ?1.8 and 3.2‰), which correlates with a fractionation of the Cl/Br ratios. The source of another high-salinity fluid trapped in inclusions in late-stage quartz from quartz–stibnite veins remains unclear. By contrast, quartz–galena veins derived sulfide (and metals?) by alteration of a sedimentary source, most likely shale-hosted massive sulfides. The δ³⁴S values in galena from the two study sites vary between ?15.42 and ?19.04‰. Barite which is associated with galena has significantly different δ³⁴S values (?0.2 to 6.44‰) and is assumed to have formed by mixing of the ascending fluids with meteoric water.     

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.