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.     

Fluid migration and vein formation during deformation and greenschist facies metamorphism at Ormiston Gorge, central Australia

During the Alice Springs Orogeny, deformation at Ormiston Gorge, central Australia, occurred under lower- to middle-greenschist facies conditions. Dolomites of the Bitter Springs Formation and quartzites. metagreywackes, and metapelites of the Heavitree Quartzite contain abundant early-, syn-, and post-tectonic veins. However, though vein densities locally approach 15%, the distribution of veins and the oxygen isotope geochemistry of wallrocks and veins suggest that fluid movement was on a local scale. The Heavitree Quartzite contains quartz veins that, even along the main thrust plane, have similar δ¹⁸O values (13.5–16.9%o) to those of their wallrocks (13.6–16.9%o), with Δ¹⁸O(vein-wallrock) values of -0.6 to 0.4%o. In contrast, the Bitter Springs Formation contains predominantly dolomite veins that have δ¹⁸O values of 23.4 to 27.7%o. These differences are observed even at the boundary between the Heavitree and Bitter Springs rocks, implying that significant fluid exchange between these rocks has not occurred, or that fluid flow was channelled through areas outside those sampled for this study. By contrast with the Heavitree Quartzite, δ¹⁸O values of wallrocks in individual samples of the Bitter Springs Formation are significantly higher (23.3–29.1%o) than those of the veins, with δ¹⁸O(vein-wallrock) values up to -4%o (average of -2.1%o). These systematic differences in δ¹⁸O values most likely result from oxygen isotope fractionation caused by fluid immiscibility or disequilibrium dissolution. Smaller differences in δ¹³C values between some dolomite veins and wallrocks [δ¹³C(vein-wallrock) up to -1.9%o, average of -0.5%o] are also explained by these processes. This study indicates that large volumes of veins may be produced by repeated fracturing and fluid migration within particular rock units, without involving large volumes of externally derived fluids.     

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.     

Oxygen and Carbon Isotope Study of Calcite and Dolomite in the Disseminated Au-Ag Telluride Bulawan Deposit, Negros Island, Philippines

Abstract: The disseminated Au‐Ag telluride Bulawan deposit, Negros island, Philippines, is hosted by dacite porphyry breccia pipes which formed in a Middle Miocene dacite porphyry stock. Electrum and Au‐Ag tellurides occur mostly as grains intergrown with or filling voids between sphalerite, pyrite, chalcopyrite, galena and tennantite. Calcite, quartz and rare dolomite are the principal gangue minerals. Four types of alteration were recognized in the deposit, namely; propylitic, K‐feldspar‐sericitic, sericitic and carbonate alteration. Carbonate alteration is correlatable to the gold deposition stage and occurs mostly along fault zones. The δ¹⁸O and δ¹³C compositions of calcite and dolomite in propylite zone and ore‐stage dacite porphyry breccia were determined. The δ¹⁸O values of calcite in propylitized andesite range from +12.2 to +14.7%, and their δ¹³C values range from ‐6.1 to ‐1.0%. The δ¹⁸O values of calcite and dolomite in sericite‐ and carbonate‐altered, mineralized dacite porphyry breccia and dacite porphyry rocks range from +15.1 to +23.1%, and the δ¹³C values of calcite and dolomite range from ‐3.9 to +0.9%. The δ¹⁸O and δ¹³C values of the hydrothermal fluids were estimated from inferred temperatures of formation on the basis of fluid inclusion microthermometry. The δ¹⁸O values of hydrothermal fluid for the propylitic alteration were calculated to be +8.5 ‐ +9.5%, assuming 375°C. On the other hand, the δ¹⁸O values of ore solutions for base metal and Au mineralization were computed to be +13.6 ‐ +14.6%, assuming 270°C. The hydrothermal fluids that formed the Bulawan deposit are dilute and ¹⁸O‐enriched fluids which reacted with ¹⁸O‐ and ¹³C‐rich wallrocks such as limestone.     

Geology and Geochemistry of the Dashuigou Tellurium Deposit,Western Sichuan,China

The Dashuigou tellurium deposit, located on the western margin of the Yangtze platform, is unique. The deposit is hosted by Triassic metabasalt 50 to 80 meters thick. The orebodies occur as a group of NNE-striking parallel veins. Mineralization developed in three stages: Stage I— pyrrhotite-pyrite, Stage II—tetradymite, and Stage III—chalcopyrite-pyrite. Stage II is the principal tellurium mineralization stage and the tellurium-bearing minerals are mainly tetradymite, tsumoite, tellurbismuth, joseite, calaverite, stuetzite, and native tellurium. The general ore grade of the tellurium in Stage II ranges from 0.2 to 5 wt%, and it reaches 15 to 25 wt% for the massive ores. The dominant gangue minerals are calcite and dolomite, with minor biotite, muscovite, albite, quartz, and chlorite.

Fluid-inclusion studies of calcite, dolomite, and quartz from Stages I, II, and III yield homogenization temperatures of 356° to 260° C (mean = 320° C), 295° to 198° C (mean = 240°), and 235° to 152° C (mean = 170° C), respectively. Salinities of primary fluid inclusions in all three stages are 1.5 to 5.8 wt% NaCl equivalent, 9 to 15.2 wt% NaCl equivalent, and 2.8 to 3.0 wt% NaCl equivalent, respectively.

Isotopic studies show that δ34 values of sulfides range from -2.2 to +2.8 per mil. δ¹³C values of calcites and dolomites in the ore veins range from -5.3 to -7.42 per mil, and δ¹⁸O values range from +10.9 to +13.1 per mil, which are quite different from the δ¹³C values of+1.0 to +2.8 per mil and δ¹⁸O values of +16.8 to +28.5 per mil for the calcites from the Triassic carbonates in the deposit. The δD and δ¹⁸O values of muscovite and quartz were measured to be -61 to -54 per mil and +9.9 to +13.0 per mil, respectively. Values of δ¹⁸O_water computed from fluid-inclusion trapping temperatures are +3.9 and +7 per mil.

A date of 93 Ma was obtained through measurement of muscovite from the No. 12 ore vein. Sulfur-, oxygen-, carbon-, and hydrogenisotope data indicate that the ore-forming substances of the Dashuigou tellurium deposit were derived from deep-seated sources, and the mineralizations probably are associated with Late Mesozoic alkaline or alkaline granitic magmatism. The estimated sulfur fugacities (fs₂) are 10^?16.7 for Stage I and 10^?14 to 10^15.5 for Stage II, whereas the tellurium fugacities (f_Te2) are 10^?15 to 10^?14 and 10^?11.2 to 10^?10.5, respectively.     

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

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

Characteristic Features of REE and Pb–Zn–Ag Mineralizations in the Na Son Deposit,Northeastern Vietnam

The Na Son deposit is a small‐scale Pb–ZnPb–Zn–Ag deposit in northeast Vietnam and consists of biotite–chlorite schist, reddish altered rocks, quartz veins and syenite. The biotite–chlorite schist is intruded by syenite. Reddish altered rocks occur as an alteration halo between the biotite–allanite‐bearing quartz veins and the biotite–chlorite schist. Allanite occurs in the biotite–allanite‐bearing quartz veins and in the proximal reddish altered rocks. Rare earth element (REE) fluorocarbonate minerals occur along fractures or at rim of allanite crystals. The later horizontal aggregates of sulfide veins and veinlets cut the earlier reddish altered rocks. The earlier Pb–Zn veins consist of a large amount of galena and lesser amounts of sphalerite, pyrite and molybdenite. The later Cu veins cutting the Pb–Zn veins include chalcopyrite and lesser amounts of tetrahedrite and pyrite. The occurrences of two‐phase H₂O–CO₂ fluid inclusions in quartz from biotite–allanite‐bearing quartz veins and REE‐bearing fluorocarbonate minerals in allanite suggest the presence of CO₂ and F in the hydrothermal fluid. The oxygen isotopic ratios of the reddish altered rocks, biotite–chlorite schist, and syenite range from +13.9 to +14.9 ‰, +11.5 to +13.3 ‰, and +10.1 to +11.6 ‰, respectively. Assuming an isotopic equilibrium between quartz (+14.6 to +15.8 ‰) and biotite (+8.6 ‰) in the biotite–allanite‐bearing quartz vein, formation temperature was estimated to be 400°C. At 400°C, δ¹⁸O values of the hydrothermal fluid in equilibrium with quartz and biotite range from +10.5 to +11.7 ‰. These δ¹⁸O values are consistent with fluid that is derived from metamorphism. Assuming an isotopic equilibrium between galena (+1.5 to +1.7 ‰) and chalcopyrite (+3.4 ‰), the formation temperature was estimated to be approximately 300°C. The formation temperature of the Na Son deposit decreased with the progress of mineralization. Based on the geological data, occurrence of REE‐bearing minerals and oxygen isotopic ratios, the REE mineralization is thought to result from interaction between biotite–chlorite schist and REE‐, CO₂‐ and F‐bearing metamorphic fluid at 400°C under a rock‐dominant condition.     

Local distribution of oxygen isotopes and fluid exchange during genesis of the corundum-bearing rocks of Khitostrov Island

New data are presented on the distribution of oxygen isotopes and conditions of the local isotope equilibrium in high-Al rocks rocks of Khitostrov Island showing abnormally low δ¹⁸O values (below–25‰). The temperatures of isotope equilibrium are within 400–475°C. The minimum δ¹⁸O values have been registered in the in plagioclase, whereas the same phases in kyanite-bearing rocks lacking corundum demonstrate δ¹⁸O values usually 3–5‰ higher. The fluid δ¹⁸O value varies from–22 to–16‰ at 475 ± 15°C, from–18 to–23‰ at 425 ± 25°C, and from–17 to–22‰ at 380 ± 15°C. The results obtained do not require abnormal depletion of δ¹⁸O values owing to the infiltration of an external fluid under the Svecofennian transformations. The association of corundum-bearing rocks with the basic intrusions, the presence of zircon cores of older ages compared to these rocks, and the peculiarities of rock chemistry may be ascribed to the fact that lower crustal layers of ancient rocks depleted in δ¹⁸O before metamorphism were captured by basite melts.     

Dating and Fluid Geochemistry of the Sarkobu Gold Deposit in Altay, Xinjiang, China

The dating of fluid inclusions of quartz yields an Ar-Ar isochrone age of 320.4±6 Ma. Three types of fluid inclusions have been identified with the homogenization temperature ranging from 157℃ to 362℃. The homogenization temperature consists of two groups. The first group varies from 157℃ to 166℃, and the second from 232℃ to 362℃. Their chemical composition is dominated by Na+-Ca2+-Mg2+ and Cl-. The relative concentration of ions is characteristic by Na+>Ca2+>K+>Mg2+ and C1->SO42-> F-. The δD and δ18O values indicate that the ore-forming fluid originates from mixing of multi-source water. The Sarkobu gold deposit has experienced two mineralization stages: gold was enriched during the volcanic-exhalative-sedimentary process in the early stage, while the gold deposit was finally formed under compression-shearing during the orogenic period.     

Formation of the Dongmozhazhua Pb–Zn Deposit in the Thrust‐Fold Setting of the Tibetan Plateau,China: Evidence from Fluid Inclusion and Stable Isotope Data

The Dongmozhazhua deposit, the largest Pb–Zn deposit in south Qinghai, China, is stratabound, carbonate‐hosted and associated with epigenetic dolomitization and silicification of Lower–Middle Permian—Upper Triassic limestones in the hanging walls of a Cenozoic thrust fault system. The mineralization is localized in a Cenozoic thrust‐folded belt along the northeastern edge of the Tibetan plateau, which was formed due to the India–Asia plate collision during the early Tertiary. The deposit comprises 16 orebodies with variable thicknesses (1.5–26.3 m) and lengths (160–1820 m). The ores occur as dissemination, vein, and breccia cement. The main sulfide assemblage is sphalerite + galena + pyrite + marcasite ± chalcopyrite ± tetrahedrite, and gangue minerals consist mainly of calcite, dolomite, barite, and quartz. Samples of pre‐ to post‐ore stages calcite yielded δ¹³C and δ¹⁸O values that are, respectively, similar to and lower than those yielded by the host limestones, suggesting that the calcite formed from fluids derived from carbonate dissolution. Fluid inclusions in calcite and sphalerite in the polymetallic sulfidization stage mostly comprise liquid and gas phases at room temperature, with moderate homogenization temperatures (100–140°C) and high salinities (21–28 wt% NaCl eq.). Micro‐thermometric fluid inclusion data point to polysaline brines as ore‐forming fluids. The δD and δ¹⁸O values of ore fluids, cation compositions of fluid inclusions, and geological information suggest two main possible fluid sources, namely basinal brines and evaporated seawater. The fluid inclusion data and regional geology suggest that basinal brines derived from Tertiary basins located southeast of the Dongmozhazhua deposit migrated along deep detachment zones of the regional thrust system, leached substantial base metals from country rocks, and finally ascended along thrust faults at Dongmozhazhua. There, the base‐metal‐rich basinal brines mixed with bacterially‐reduced H₂S‐bearing fluids derived from evaporated seawater preserved in the Permo–Triassic carbonate strata. The mixing of the two fluids resulted in Pb–Zn mineralization. The Dongmozhazhua Pb–Zn deposit has many characteristics that are similar to MVT Pb–Zn deposits worldwide.     

Geochemical peculiarities of the formation of the Novoshirokinskii gold-polymetallic deposit,Eastern Transbaikalia,Russia

The fluid inclusions in minerals and isotope composition of sulfur in sulfides and carbon and oxygen in carbonates are studied for the Novoshirokinskii gold-polymetallic deposit. The ore-forming fluids are characterized by the following physico-chemical and isotope-geochemical parameters: temperature of 290–100°C, salinity of 13–2.5 wt % NaCl-equiv., δ¹⁸O from +8 to 0‰, δ¹³C of 2.5 ± 0.5‰, and δ³⁴S of 10.5 ± 1.0‰. It is concluded that the Late Proterozoic-Early Cambrian carbonaceous-terrigenous and carbonate rocks were involved in the Late Jurassic ore-magmatic system.     

Origin of the Okrouhlá Radouň episyenite-hosted uranium deposit,Bohemian Massif,Czech Republic: fluid inclusion and stable isotope constraints

The Okrouhlá Radouň shear zone hosted uranium deposit is developed along the contact of Variscan granites and high-grade metasedimentary rocks of the Moldanubian Zone of the Bohemian Massif. The pre-ore pervasive alteration of wall rocks is characterized by chloritization of mafic minerals, followed by albitization of feldspars and dissolution of quartz giving rise to episyenites. The subsequent fluid circulation led to precipitation of disseminated uraninite and coffinite, and later on, post-ore quartz and carbonate mineralization containing base metal sulfides. The fluid inclusion and stable isotope data suggest low homogenization temperatures (～50–140 °C during pre-ore albitization and post-ore carbonatization, up to 230 °C during pre-ore chloritization), variable fluid salinities (0–25 wt.% NaCl eq.), low fluid δ¹⁸O values (?10 to +2 ‰ V-SMOW), low fluid δ¹³C values (?9 to ?15 ‰ V-PDB), and highly variable ionic composition of the aqueous fluids (especially Na/Ca, Br/Cl, I/Cl, SO₄/Cl, NO₃/Cl ratios). The available data suggest participation of three fluid endmembers of primarily surficial origin during alteration and mineralization at the deposit: (1) local meteoric water, (2) Na–Ca–Cl basinal brines or shield brines, (3) SO₄–NO₃–Cl–(H)CO₃ playa-like fluids. Pre-ore albitization was caused by circulation of alkaline, oxidized, and Na-rich playa fluids, whereas basinal/shield brines and meteoric water were more important during the post-ore stage of alteration.     

Fluid Inclusions and Hydrogen,Oxygen, and Lead Isotopes of the Antuoling Molybdenum Deposit,Northern Taihang Mountains,China

The Antuoling Mo deposit is a major porphyry‐type deposit in the polymetallic metallogenic belt of the northern Taihang Mountains, China. The processes of mineralization in this deposit can be divided into three stages: an early quartz–pyrite stage, a middle quartz–polymetallic sulfide stage, and a late quartz–carbonate stage. Four types of primary fluid inclusions are found in the deposit: two‐phase aqueous inclusions, daughter‐mineral‐bearing multiphase inclusions, CO₂–H₂O inclusions, and pure CO₂ inclusions. From the early to the late ore‐forming stages, the homogenization temperatures of the fluid inclusions are 300 to >500°C, 270–425°C, and 195–330°C, respectively, with salinities of up to 50.2 wt%, 5.3–47.3 wt%, and 2.2–10.4 wt% NaCl equivalent, revealing that the ore‐forming fluids changed from high temperature and high salinity to lower temperature and lower salinity. Moreover, based on the laser Raman spectra, the compositions of the fluid inclusions evolved from the NaCl–CO₂–H₂O to the NaCl–H₂O system. The δ¹⁸O_H2O and δD values of quartz in the deposit range from +3.9‰ to +7.0‰ and ?117.5‰ to ?134.2‰, respectively, reflecting the δD of local meteoric water after oxygen isotopic exchange with host rocks. The Pb isotope values of the sulfides (²⁰⁸Pb/²⁰⁴Pb, 36.320–37.428; ²⁰⁷Pb/²⁰⁴Pb, 15.210–15.495; ²⁰⁶Pb/²⁰⁴Pb, 16.366–17.822) indicate that the ore‐forming materials originated from a mixed upper mantle–lower crust source.     

Geochemical characteristics of gold mineralization of the Huai Kham On deposit,Sukhothai Fold Belt,Northern Thailand

The Huai Kham On gold deposit is located in the central part of the Sukhothai Fold Belt, northern Thailand. The Sukhothai Fold Belt represents an accretionary complex formed by subduction and collision between the Indochina and Sibumasu Terranes. There are many small gold deposits in the Sukhothai Fold Belt; however, the styles and formation environments of those gold deposits are not clear. The geology of the Huai Kham On deposit consists of volcanic and volcanosedimentary rocks, limestone, and low‐grade metamorphic rocks of Carboniferous to Triassic age. Gold‐bearing quartz veins are hosted by volcanic and volcanosedimentary rocks. The quartz veins can be divided into four stages. The mineral assemblage of the gold‐bearing quartz veins of Stages I and II comprises quartz, calcite, illite, pyrite, native gold, galena, chalcopyrite, and sphalerite. Quartz veins of Stage III consist of microcrystalline quartz, dolomite, calcite, pyrite, native gold, and chalcopyrite. Veins of Stage IV consist of calcite, dolomite, chlorite, and quartz. Fluid inclusions in quartz veins are classified into liquid‐rich two‐phase (Types I_A and I_B), carbonic‐aqueous (Type II), and carbonic (Type III) fluid inclusions. The homogenization temperatures of Types I_A and II fluid inclusions that are related to the gold‐bearing quartz veins from Stages I to III ranged from 240° to 280°C. The δ¹⁸O values of quartz veins of Stages I to III range from +12.9 to +13.4‰, suggesting the presence of a homogeneous hydrothermal solution without temperature variation such as a decrease of temperature during the formation of gold‐bearing quartz veins from Stages I to III in the Huai Kham On gold deposit. Based on the calculated formation temperature of 280°C, the δ¹⁸O values of the hydrothermal solution that formed the gold‐bearing quartz veins range from +3.2 to +3.7‰, which falls into the range of metamorphic waters. The gold‐bearing quartz veins of the Huai Kham On deposit are interpreted to be the products of metamorphic water.     

Fluid inclusions and C-H-O-S isotope systematics of early Permian porphyry Mo mineralization of the West Junggar region,NW China: the Suyunhe example

ABSTRACT

The Suyunhe porphyry Mo deposit, located in the West Junggar terrane, is the largest molybdenum deposit found in Xinjiang to date, with a proven reserve of 0.57 Mt. The Suyunhe deposit is associated with Early Permian granitic rocks, which emplaced into the volcano-sedimentary sequences of the Middle Devonian Barluk Formation. Four metallogenic stages are identified in this study. Stage I is marked by the quartz-magnetite-K-feldspar±biotite±pyrite±molybdenite veins, which mainly occurred in the intensively potassic alternation zone and were formed at high temperature (>481°C), high salinity (58.6?65.18 wt.%), and relatively high oxygen fugacity conditions with a fluid system of NaCl-H₂O-CO₂. Stage II is the main metallogenic stage and develops numerous quartz-molybdenite±pyrite veins associated with muscovite–chlorite alteration, which were formed by immiscible fluids at medium-high temperature (210?427°C), medium-high salinity (43.36?49.90 wt.%), and relatively low oxygen fugacity conditions with the fluid system of NaCl-H₂O-CO₂-CH₄-C₂H₆. After the main Mo-mineralization, quartz-polymetallic sulphides veins associated with quartz–sericite alteration were formed by fluids at medium-low temperature, low-salinity conditions with the fluid system of NaCl-H₂O-CO₂ in stage III. The following quartz-polymetallic sulphide veins are quartz-calcite±pyrite veins associated with calcite alteration, which were formed by fluids at low temperature and low-salinity conditions with a fluid system of NaCl-H₂O in stage IV.

The δ¹⁸O‰ values indicate that the ore fluids of stages I and II are dominated by magmatic water, whereas stages III and IV are dominated by meteoric water. A wide range of δ³⁴S‰ values (?7.1 to 3.4‰) of sulphides between stages I and II indicates that increasing the reducibility plays an important role in molybdenum mineralization. The δ¹³C_CH4 values suggest that CH₄ of the ore fluids mainly results from the assimilation–contamination of carbonaceous country rocks, and partly derives from magma. However, the δ¹³C_CO2 values suggest that CO₂ of the ore fluids mainly originates from magma, and minor derives from wall-rocks as well as meteoric water.     

Fluid Inclusions and Hydrogen,Oxygen, Sulfur Isotopes of Nuri Cu‐W‐Mo Deposit in the Southern Gangdese,Tibet

The Nuri Cu‐W‐Mo deposit is located in the southern subzone of the Cenozoic Gangdese Cu‐Mo metallogenic belt. The intrusive rocks exposed in the Nuri ore district consist of quartz diorite, granodiorite, monzogranite, granite porphyry, quartz diorite porphyrite and granodiorite porphyry, all of which intrude in the Cretaceous strata of the Bima Group. Owing to the intense metasomatism and hydrothermal alteration, carbonate rocks of the Bima Group form stratiform skarn and hornfels. The mineralization at the Nuri deposit is dominated by skarn, quartz vein and porphyry type. Ore minerals are chalcopyrite, pyrite, molybdenite, scheelite, bornite and tetrahedrite, etc. The oxidized orebodies contain malachite and covellite on the surface. The mineralization of the Nuri deposit is divided into skarn stage, retrograde stage, oxide stage, quartz‐polymetallic sulfide stage and quartz‐carbonate stage. Detailed petrographic observation on the fluid inclusions in garnet, scheelite and quartz from the different stages shows that there are four types of primary fluid inclusions: two‐phase aqueous inclusions, daughter mineral‐bearing multiphase inclusions, CO₂‐rich inclusions and single‐phase inclusions. The homogenization temperature of the fluid inclusions are 280°C–386°C (skarn stage), 200°C–340°C (oxide stage), 140°C–375°C (quartz‐polymetallic sulfide stage) and 160°C–280°C (quartz‐carbonate stage), showing a temperature decreasing trend from the skarn stage to the quartz‐carbonate stage. The salinity of the corresponding stages are 2.9%–49.7 wt% (NaCl) equiv., 2.1%–7.2 wt% (NaCl) equiv._, 2.6%–55.8 wt% (NaCl) equiv. and 1.2%–15.3 wt% (NaCl) equiv., respectively. The analyses of CO₂‐rich inclusions suggest that the ore‐forming pressures are 22.1 M Pa–50.4 M Pa, corresponding to the depth of 0.9 km–2.2 km. The Laser Raman spectrum of the inclusions shows the fluid compositions are dominated in H₂O, with some CO₂ and very little CH₄, N₂, etc. δD values of garnet are between ?114.4‰ and ?108.7‰ and δ¹⁸O_H2O between 5.9‰ and 6.7‰; δD of scheelite range from ?103.2‰ to ?101.29‰ and δ¹⁸O_H2O values between 2.17‰ and 4.09‰; δD of quartz between ?110.2‰ and ?92.5‰ and δ¹⁸O_H2O between ?3.5‰ and 4.3‰. The results indicate that the fluid came from a deep magmatic hydrothermal system, and the proportion of meteoric water increased during the migration of original fluid. The δ³⁴S values of sulfides, concentrated in a rage between ?0.32‰ to 2.5‰, show that the sulfur has a homogeneous source with characteristics of magmatic sulfur. The characters of fluid inclusions, combined with hydrogen‐oxygen and sulfur isotopes data, show that the ore‐forming fluids of the Nuri deposit formed by a relatively high temperature, high salinity fluid originated from magma, which mixed with low temperature, low salinity meteoric water during the evolution. The fluid flow through wall carbonate rocks resulted in the formation of layered skarn and generated CO₂ or other gases. During the reaction, the ore‐forming fluid boiled and produced fractures when the pressure exceeded the overburden pressure. Themeteoric water mixed with the ore‐forming fluid along the fractures. The boiling changed the pressure and temperature, oxygen fugacity, physical and chemical conditions of the whole mineralization system. The escape of CO₂ from the fluid by boiling resulted in scheelite precipitation. The fluid mixing and boiling reduced the solubility of metal sulfides and led the precipitation of chalcopyrite, molybdenite, pyrite and other sulfide.     

Geology,Fluid Inclusion Characteristics and H–O–C Isotopes of Large Lijiagou Pegmatite Spodumene Deposit in Songpan–Garze Fold Belt,Eastern Tibet: Implications for ore Genesis

The large, newly discovered Lijiagou pegmatite spodumene deposit, is located southeast of the Ke'eryin pegmatite ore field, in the central Songpan–Garze Fold Belt (SGFB), Eastern Tibet. The Lijiagou albite spodumene pegmatites are unzoned, granite‐pegmatites of the subtype LCT (Lithium, Cesium, and Tantalum) and consist of medium‐ to coarse‐grained spodumene, lepidolite, microcline, albite, quartz, muscovite, and accessory amounts of beryl, cassiterite, columbite–tantalite and zircon. Secondary fluid inclusions in quartz and spodumene include two‐phase aqueous inclusions (V + L), mono‐phase vapor inclusions (V); three‐phase CO₂‐rich CO₂–H₂O inclusions (CO₂ + V + L) and less abundant liquid inclusions (L). The homogenization temperature of the fluid inclusions are low (257.3 to 204.3°C in early stage, 250.3 to 199.6°C in middle stage, 218.7 to 200.6°C in late stage). Fluid inclusions were formed during the long cooling period from the temperature of the pegmatite emplacement. Liquid–vapor–gas boiling was extensive during the middle and late stages. The salinity of the corresponding stages are 15.4 to 13.0 wt.% NaCl equiv., 12.5 to 9.1 wt.% NaCl equiv. and 9.8 to 7.8 wt.% NaCl equiv., respectively. δ¹⁸O values of fluid are 7.2 to 5.2‰, 5.6 to 3.9‰ and 2.7 to −0.2‰ from early to late stages; and δD range from −75.1 to −76.8‰, −59.0 to −73.5‰ and −61.6 to −85.5‰ respectively. The δ¹³C of CO₂ values are −5.6 to −6.6‰, −8.5 to −19.9‰, −11.8 to −18.7‰ from early to late stages, suggesting that CO₂ in the fluids were probably sourced from a magmatic system, possibly with some mixing of CO₂ dissolved in groundwater. δD and δ¹⁸O values of fluid indicate that the fluids were originally magmatic water and mixed with some meteoric water in late stage. The magma evolution sequence in the Ke'eryin orefield, from the central two‐mica granite through the Lijiagou deposit out to the distal pegmatites, with the ages gradually decreasing, indicates that the Ke'eryin complex rocks are the product of multistage magmatic activity. The large Lijiagou spodumene deposit is a typical magmatic, fractional crystallization related pegmatite deposit.     

The mangazeya Ag–Pb–Zn vein deposit hosted in sedimentary rocks,Sakha-Yakutia,Russia: Mineral assemblages,fluid inclusions,stable isotopes (C,O, S), and origin

The succession of mineral assemblages, chemistry of gangue and ore minerals, fluid inclusions, and stable isotopes (C, O, S) in minerals have been studied in the Mangazeya silver–base-metal deposit hosted in terrigenous rocks of the Verkhoyansk Fold–Thrust Belt. The deposit is localized in the junction zone of the Kuranakh Anticlinorium and the Sartanga Synclinorium at the steep eastern limb of the Endybal Anticline. The deposit is situated at the intersection of the regional Nyuektame and North Tirekhtyakh faults. Igneous rocks are represented by the Endybal massif of granodiorite porphyry 97.8 ± 0.9 Ma in age and dikes varying in composition. One preore and three types of ore mineralization separated in space are distinguished: quartz–pyrite–arsenopyrite (I), quartz–carbonate–sulfide (II), and silver–base-metal (III). Quartz and carbonate (siderite) are predominant in ore veins. Ore minerals are represented by arsenopyrite, pyrite, sphalerite, galena, fahlore, and less frequent sulfosalts. Three types of fluid inclusions in quartz differ in phase compositions: two- or three-phase aqueous–carbon dioxide (FI I), carbon dioxide gas (FI II), and two-phase (FI III) containing liquid and a gas bubble. The homogenization temperature and salinity fall within the ranges of 367–217°C and 13.8–2.6 wt % NaCl equiv in FI I; 336–126°C and 15.4–0.8 wt % NaCl equiv in FI III. Carbon dioxide in FI II was homogenized in gas at +30.2 to +15.3°C and at +27.2 to 29.0°C in liquid. The δ³⁴S values for minerals of type I range from–1.8 to +4.7‰ (V-CDT); of type II, from–7.4 to +6.6‰; and of type III, from–5.6 to +7.1‰. δ¹³C and δ¹⁸O vary from–7.0 to–6.7‰ (V-PDB) and from +16.6 to +17.1 (V-SMOW) in siderite-I; from–9.1 to–6.9‰ (V-PDB) and from +14.6 to +18.9 (V-SMOW) in siderite-II; from–5.4 to–3.1‰ (V-PDB) and from +14.6 to +19.5 (V-SMOW) in ankerite; and from–4.2 to–2.9‰ (V-PDB) and from +13.5 to +16.8 (V-SMOW) in calcite. The data on mineral assemblages, fluid inclusions, and ratios of stable isotopes allow us to speak about the formation of the Mangazeya deposit in relation to the activity of the hydrothermal–magmatic system. The latter combines emplacement of subvolcanic granitic stocks and involvement of fluids variable in salinity and temperature in ore deposition zone. The fluids released from crystallizing felsic magma and were formed in a convective cell by heating of meteoric and marine waters. The mechanism of ore deposition is related to phase separation (boiling) and mixing of fluids.     

Mineral and stable isotope compositions,phase equilibria and 40Ar–39Ar geochronology from the iron skarn deposit in Sangan,northeastern Iran

The Sangan iron skarn deposit is located on the eastern edge of the Sabzevar-Doruneh Magmatic Belt, northeastern Iran. Mineralization occurs at the contact between Eocene igneous rocks and Cretaceous carbonates. The silicate-dominant prograde skarn stage consists of garnet and clinopyroxene, whereas the retrograde stage is dominated by magnetite associated with minor hematite, phlogopite, pyrite, and chalcopyrite. Phase equilibria and mineral chemistry studies reveal that the skarn formed within a temperature range of ∼375° to 580 °C and that the mineralizing fluid evolved from a hot, low oxygen fugacity, alkaline fluid during the silicate-dominant stage to a fluid of relatively lower temperature and higher oxygen fugacity at the magnetite-dominant stage. The δ¹⁸O values of magnetite and garnet vary from +3.1 to +7.5‰ and +7.7 to +11.6‰, respectively. The calculated δ¹⁸O_H2O values of fluid in equilibrium with magnetite and garnet range from +9.8 to +11.1‰ and +10.1 to +14.8‰, respectively. These elevated δ¹⁸O_H2O values suggest interaction of magmatic water with ¹⁸O-enriched carbonates. The high δ³⁴S values (+10.6 to +17.0‰) of pyrite separates from the Sangan iron ore indicate that evaporites had an important role in the evolution of the hydrothermal fluid. Phlogopite separates from the massive ores yield ⁴⁰Ar/³⁹Ar plateau ages of 41.97 ± 0.2 and 42.47 ± 0.2 Ma, indicating that the skarn formation and associated iron mineralization was related to the oldest episode of magmatism in Sangan at ∼42 Ma. Eocene time marked a peak of magmatic activity and associated skarn in the post-collisional setting in northeastern Iran, whereas Oligo-Miocene magmatic activity and associated skarn in the Urumieh-Dokhtar Magmatic Belt are related to subduction. In addition, skarn mineralization in northeastern and eastern Iran is iron type, but skarn mineralization in the Urumieh-Dokhtar magmatic belt is copper – iron and copper type.     

China’s First Independent Cobalt Deposit and its Metallogenic Mechanism: Evidence from Fluid Inclusions and Isotopic Geochemistry

The Tuolugou cobalt deposit is the first independent large-scale Co- and Au-bearing deposit discovered in northwestern China. It is located in the eastern Kunlun orogenic belt in Qinghai Province, and occurs conformably in low-grade metamorphic volcano-sedimentary rock series with well-developed Na-rich hydrothermal sedimentary rocks and typical hydrothermal sedimentary ore fabrics. Fluid inclusions and isotopic geochemistry studies suggest that cobalt mineralizing fluid is dominated by NaCl-H2O system, accompanied by NaCl-CO2-H2O-N2 system responsible for gold mineralization. Massive, banded and disseminated pyrite ores have similar compositions of He and Ar isotopes from the mineralizing fluid, with 3He/4He range between 0.10 to 0.31Ra (averaging 0.21Ra), and 40Ar/36Ar between 302 and 569 (averaging 373), which reflects that Co mineralizing fluids derived dominantly from meteoric water deeply circulating. δ34S values of pyrite approaches to zero (δ34S ranging from ?4.5‰ to +1.5‰, centering around ?1.8‰ to ?0.2‰), reflecting its deep source. Ore lead is characterized by distinctly high radiogenesis, with 206Pb/204Pb>19.279, 207Pb/204Pb>15.691 and 208Pb/204Pb>39.627, and its values show an increase trend from country rocks, regional Paleozoic volcanic rocks to ores. This may have suggested that high radiogentic ore Pb derived mainly from country rocks by leaching meteoric water-dominated hydrothermal fluid during its circulation at depth. Cobalt occurs mainly in sulfide phase (such as pyrite), but cobalt enrichment, and presence and increasing contents of Co-bearing minerals have a positive correlation with metamorphic degree. The Tuolugou deposit and other typical strata-bound Co-Cu-Au deposits have striking similarities in the geological features and metallogenic pattern of primary cobalt. All of them are syngenetic hydrothermal exhalative sedimentation in origin.