Characteristics of Triassic epithermal Au mineralization at the Q prospect,Chatree mining area,Central Thailand

The Chatree deposit is located in the Loei‐Phetchabun‐Nakhon Nayok volcanic belt that extends from Laos in the north through central and eastern Thailand into Cambodia. Gold‐bearing quartz veins at the Q prospect of the Chatree deposit are hosted within polymictic andesitic breccia and volcanic sedimentary breccia. The orebodies of the Chatree deposit consist of veins, veinlets and stockwork. Gold‐bearing quartz veins are composed mainly of quartz, calcite and illite with small amounts of adularia, chlorite and sulfide minerals. The gold‐bearing quartz veins were divided into five stages based on the cross‐cutting relationship and mineral assemblage. Intense gold mineralization occurred in Stages I and IV. The mineral assemblage of Stages I and IV is characterized by quartz–calcite–illite–laumontite–adularia–chlorite–sulfide minerals and electrum. Quartz textures of Stages I and IV are also characterized by microcrystalline and flamboyant textures, respectively. Coexistence of laumontite, illite and chlorite in the gold‐bearing quartz vein of Stage IV suggests that the gold‐bearing quartz veins were formed at approximately 200°C. The flamboyant and brecciated textures of the gold‐bearing quartz vein of Stage IV suggest that gold precipitated with silica minerals from a hydrothermal solution that was supersaturated by boiling. The δ¹⁸O values of quartz in Stages I to V range from +10.4 to +11.6‰ except for the δ¹⁸O value of quartz in Stage IV (+15.0‰). The increase in δ¹⁸O values of quartz at Stage IV is explained by boiling. P_H2O is estimated to be 16 bars at 200°C. The f_CO2 value is estimated to be 1 bar based on the presence of calcite in the mineral assemblage of Stage IV. The total pressure of the hydrothermal solution is approximately 20 bars at 200°C, suggesting that the gold‐bearing quartz veins of the Q prospect formed about 200 m below the paleosurface.     

Carbon and Oxygen Isotope Compositions of Calcite and Rhodochrosite from Geothermal Exploratory Drills TH‐4 and TH‐6 near the Toyoha Deposit,Hokkaido, Japan

We studied calcite and rhodochrosite from exploratory drill cores (TH‐4 and TH‐6) near the Toyoha deposit, southwestern Hokkaido, Japan, from the aspect of stable isotope geochemistry, together with measuring the homogenization temperatures of fluid inclusions. The alteration observed in the drill cores is classified into four zones: ore mineralized zone, mixed‐layer minerals zone, kaolin minerals zone, and propylitic zone. Calcite is widespread in all the zones except for the kaolin minerals zone. The occurrence of rhodochrosite is restricted in the ore mineralized zone associated with Fe, Mn‐rich chlorite and sulfides, the mineral assemblage of which is basically equivalent to that in the Toyoha veins. The measured δ¹⁸O_SMOW and δ¹³C_PDB values of calcite scatter in the relatively narrow ranges from ?2 to 5‰ and from ?9 to ?5‰, respectively; those of rhodochrosite from 3 to 9‰ and from ?9 to ?5‰, excluding some data with large deviations. The variation of the isotopic compositions with temperature and depth could be explained by a mixing process between a heated surface meteoric water (100°C δ¹⁸O =?12‰, δ¹³C =?10‰) and a deep high temperature water (300°C, δ¹⁸O =?5‰, δ¹³C =?4‰). Boiling was less effective in isotopic fractionation than that of mixing. The plots of δ¹⁸O and δ¹³C indicate that the carbonates precipitated from H₂CO₃‐dominated fluids under the conditions of pH = 6–7 and T = 200–300°C. The sequential precipitation from calcite to rhodochrosite in a vein brought about the disequilibrium isotopic fractionation between the two minerals. The hydrothermal fluids circulated during the precipitation of carbonates in TH‐4 and TH‐6 are similar in origin to the ore‐forming fluids pertaining to the formation of veins in the Toyoha deposit.     

Oxygen Isotopic Study on the Date‐Nagai Skarn‐Type Tungsten Deposit,Northeastern Japan

The skarn‐type tungsten deposit of the Date‐Nagai mine is genetically related to the granodiorite batholith of the Iidateyama body. Skarn is developed along the contact between pelitic hornfels and marble that remains as a small roof pendant body directly above the granodiorite batholith. Zonal arrangement of minerals is observed in skarn. The zonation consists of wollastonite, garnet, garnet‐epidote, and vesuvianite‐garnet zones, from marble to hornfels. Sheelite is included in garnet, garnet‐epidote, and vesuvianite‐garnet zones. The oxygen isotope values of skarn minerals were obtained as δ¹⁸O = 4.2–7.7‰ for garnet, 5.9–6.9‰ for vesuvianite, ?0.3–3.4‰ for scheelite, 6.0–10.9‰ for quartz, and 8.2‰ for muscovite. The temperature of skarn‐formation was calculated from oxygen isotopic values of scheelite‐quartz pairs to be 288°C. Calculated oxygen isotope values of fluid responsible for skarn minerals were 6.1–9.5‰ for garnet, 1.2–4.8‰ for scheelite, ?1.3‐3.6‰ for quartz, and 4.5‰ for muscovite. Garnet precipitated from the fluids of different δ¹⁸O values from scheelite, quartz, and muscovite. These δ¹⁸O values suggest that the origin of fluid responsible for garnet was magmatic water, while evidence for the presence of a meteoric component in the fluids responsible for middle to later stages minerals was confirmed.     

Mineral Paragenesis, Fluid Inclusions and Sulfur Isotope Systematics of the Lepanto Far Southeast Porphyry Cu-Au Deposit, Mankayan, Philippines

Abstract: The Lepanto Far Southeast porphyry Cu‐Au deposit is located beneath and to the southeast of the Lepanto enargite‐luzonite Cu–Au deposit in Mankayan, Benguet Province, Philippines. The principal orebody consists of potassic alteration subjected to partial retrograde chlorite alteration that rims stock‐work of quartz‐anhydrite veinlets. Fluid inclusions found in stockwork quartz and anhydrite in the biotitized orebody center are dominated by polyphase inclusions that homogenize at temperatures of >500C. Sulfur isotopic thermometry applied to the sulfides‐anhydrite pairs suggests around 500C. The principal ore minerals associated with quartz‐anhydrite stockworks are chalcopyrite and pyrite with minor bornite and Bi–Te–bearing tennantite, with trace of native gold. Rounded pyrite grains appear fractured and corroded and are interpreted as remnants of primary intermediate solid solution + pyrite assemblage. A breccia pipe truncates the deposit. Mineralization in the breccia pipe is brought by quartz‐anhydrite veinlets and infilling in the interstices between clasts. Chalcopyrite‐Au mineralization associated with molybdenite is recognized in the deeper zone in the breccia pipe. Fluid inclusion microthermometry on polyphase inclusions in veinlet quartz as well as sulfur isotope thermometry applied for the pair of anhydrite and sulfides suggests >450C. Fluid inclusions in veinlet quartz and anhydrite in the fringe advanced argillic alteration are chiefly composed of coexisting liquid‐rich inclusions and gas‐rich inclusions, in addition to coexisting polyphase inclusions and gas‐rich inclusions. These inclusions exhibit a wide range of homogenization temperatures, suggesting heterogeneous entrapping in the two‐fluid unmixing region. Sulfur isotopes of aqueous sulfide and sulfate exhibit a general trend from the smallest fractionation pairs (about 11%) in the biotitized orebody center to the largest fractionation (about 25%) pairs in the fringe advanced argillic alteration, suggesting a simple evolution of hydrothermal system. The slopes of arbitrary regression lines in δ³⁴S versus ³⁴S[SO₄ = –H₂S] diagram suggest that the abundance ratio of aqueous sulfate to sulfide in the hydrothermal fluid has been broadly constant at about 1:3 through temperature decrease. The intersection of these two regression lines at the δ³⁴S axis indicates that the bulk δ³⁴S is about +6%. Thus, the Lepanto FSE deposit is a further example which confirms enrichment in ³⁴S in the hydrous intermediate to silicic magmas and associated magmatic hydrothermal deposits in the western Luzon arc.     

Geological and Geophysical Studies of Sulfide Copper Mineralization in the Dochileh Area: An Example of Manto‐Type Deposit in the Sabzevar Zone,Iran

The Dochileh stratiform copper deposit in the Sabzevar Zone of northeastern Iran is hosted in the basaltic sequence of the Upper Eocene age. The host rock displays two hydrothermal events: zeolite–carbonate alteration that is a stratigraphic–lithologic feature and chlorite and chlorite/ferruginous alterations in the local mineralized structures. Ore formation is related to both hydrothermal events and occurs in both stratiform and vein mineralization types. Mineralization consists of main chalcocite with variable amounts of bornite, chalcopyrite, native copper, malachite, and cuprite minerals, which occur as hydrothermal breccias, and disseminated, vein, and veinlet forms. Geophysical field studies using resistivity and induction polarization (IP) methods were conducted along nine survey lines in the area. As a result of modeling and interpretation of the acquired geophysical data, high values of IP and resistivity corresponding to mineralization were observed at two depth levels: 0–20 m and more than 40 m. Based on these geological and geophysical investigations, six locations for drilling exploration boreholes were proposed. Drilling data confirmed the mineralization containing high copper values in the two depth levels: the vein‐type mineralization in the surface and shallow depth level, and the stratiform mineralization at the deeper level. Fluid inclusion studies in calcite and quartz from stratiform‐ and vein‐type mineralization show the evidence of mixing, and a linear dilution trend during the ore formation occurred at a wide range of temperatures: 121–308°C and 80–284°C, respectively, and varying salinities of between 3.2–16.8 and 0.8–22 wt% NaCl equivalents. The stable isotope composition of δ³⁴S that falls in a range of ?2.4 to +25.0‰ could be considered biogenetic sulfur from bacterial sulfate reduction and leaching of sulfur from hosting basalt. The δ¹³C values of calcite vary between ?0.6 and ?7.6‰, suggesting a major contribution of marine carbonates associated with igneous carbonates, and the δ¹⁸O_SMOW values of calcite are between +15.2 and +19.9‰, suggesting a contribution of δ¹⁸O‐rich sedimentary rocks and δ¹⁸O‐poor meteoric water. Copper and sulfide‐rich hydrothermal fluid have flowed upward through the local faults and permeable interbeds within the Eocene volcanic sequence and have formed the mineralized veins and horizons. The geophysical results have detected the local faults as the channel ways for mineralization.     

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.     

Micro-scale S isotope studies of the Kharaelakh intrusion, Noril’sk region, Siberia: Constraints on the genesis of coexisting anhydrite and sulfide minerals

The coexistence of magmatic anhydrite and sulfide minerals in non-arc-related mafic magmas has only rarely been documented. Likewise the S isotope fractionation between sulfate and sulfide in mafic rocks has infrequently been measured. In the Kharaelakh intrusion associated with the world-famous Noril’sk ore district in Siberia coexisting magmatic anhydrite and sulfide minerals have been identified. Sulfur isotope compositions of the anhydrite-sulfide assemblages have been measured via both ion microprobe and conventional analyses to help elucidate the origin of the anhydrite-sulfide pairs. Magmatic anhydrite and chalcopyrite are characterized by δ³⁴S values between 18.8‰ and 22.8‰, and 9.3‰ and 13.2‰, respectfully. Coexisting anhydrite and chalcopyrite show Δ values that fall between 8.5‰ and 11.9‰. Anhydrite in the Kharaelakh intrusion is most readily explained by the assimilation of sulfate from country rocks; partial reduction to sulfide led to mixing between sulfate-derived sulfide and sulfide of mantle origin. The variable anhydrite and sulfide δ³⁴S values are a function of differing degrees of sulfate reduction, variable mixing of sulfate-derived and mantle sulfide, incomplete isotopic homogenization of the magma, and a lack of uniform attainment of isotopic equilibrium during subsolidus cooling. The δ³⁴S values of sulfide minerals have changed much less with cooling than have anhydrite values due in large part to the high sulfide/sulfate ratio. Variations in both sulfide and anhydrite δ³⁴S values indicate that isotopically distinct domains existed on a centimeter scale. Late stage hydrothermal anhydrite and pyrite also occur associated with Ca-rich hydrous alteration assemblages (e.g., thomsonite, prehnite, pectolite, epidote, xonotlite). δ³⁴S values of secondary hydrothermal anhydrite and pyrite determined by conventional analyses are in the same range as those of the magmatic minerals. Anhydrite-pyrite Δ values are in the 9.1-10.1‰ range, and are smaller than anticipated for the low temperatures indicated by the silicate alteration assemblages. The small Δ values are suggestive of either sulfate-sulfide isotopic disequilibrium or closure of the system to further exchange between ∼550 and 600 °C. Our results confirm the importance of the assimilation of externally derived sulfur in the generation of the elevated δ³⁴S values in the Kharaelakh intrusion, but highlight the sulfur isotopic variability that may occur in magmatic systems. In addition, our results confirm the need for more precise experimental determination of sulfate-sulfide sulfur isotope fractionation factors in high-T systems.     

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.     

Geological,mineralogical, and oxygen isotope studies of the Chandmani Uul iron oxide–copper–gold deposit in Dornogobi Province,Southeastern Mongolia

The Chandmani Uul deposit is located in Dornogovi province, Southeastern Mongolia. Iron oxide ores are hosted in the andesitic rocks of the Shar Zeeg Formation of Neoproterozoic to Lower‐Cambrian age. Middle‐ to Upper‐Cambrian bodies of granitic rocks have intruded into the host rocks in the western and southern regions of the deposit. The wall rocks around the iron oxide ore bodies were hydrothermally altered to form potassic, epidote, and sericite–chlorite alteration zones, and calcite and quartz veinlets are ubiquitous in the late stage. Since granitic rocks also underwent potassic alteration, the activity of the granitic rocks must have a genetic relation to the ore deposit. The ore mineral assemblage is dominated by iron oxides such as mushketovite, euhedral magnetite with concentric and/or oscillatory zoning textures, and cauliflower magnetite. Lesser amounts of chalcopyrite and pyrite accompany the iron oxides. Among all these products, mushketovite is dominant and is distributed throughout the deposit. Meanwhile, euhedral magnetite appears in limited amounts at relatively shallow levels in the deposit. By contrast, cauliflower magnetite appears locally in the deeper parts of the deposit, and is associated with green‐colored garnet and calcite. Sulfide minerals are ubiquitously associated with these iron oxides. The oxygen isotope (δ¹⁸O) values of all types of magnetite, quartz, and epidote were found to be ?5.9 to ?2.8‰, 10.5 to 14.9‰, and 3.6 to 6.6‰, respectively. The δ¹⁸O values of quartz–magnetite pairs suggest an equilibrium isotopic temperature near 300°C. The calculated values of δ¹⁸O for the water responsible for magnetite ranged from 2 to 10‰. All the data obtained in this study suggest that the iron oxide deposit at the Chandmani Uul is a typical iron oxide–copper–gold deposit, and that this deposit was formed at an intermediate depth with potassic and sericite–chlorite alteration zones under the oxidized conditions of a hematite‐stable environment. The δ¹⁸O range estimated implies that the ore‐forming fluid was supplied by a crystallizing granodioritic magma exsolving fluids at depth with a significant contribution of meteoric water.     

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

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

Iron Isotope Compositions of Natural River and Lake Samples in the Karst Area, Guizhou Province, Southwest China

To better understand the Fe isotope characteristics of natural samples in the Karst area, the Fe isotope compositions of riverine suspended particulates, lake suspended particulates, lake sediments, porewaters, phytoplanktons, and aerosols in the watersheds of Lake Aha (a mineralized water system) and Lake Hongfeng (a mesotrophic water system), which are located in the Karst area, southwest China, were investigated. The studied samples displayed a variable range between δ56Fe=?2.03‰ and 0.36‰. Aerosols and phytoplanktons have similar or slightly heavier Fe isotope compositions relative to the average of igneous rocks. Fe isotope compositions of riverine Suspended Particulate Matter (SPM) were mainly affected by the types of tributaries. Suspended particulates collected from tributaries seriously contaminated with coal mine drainages displayed negative δ56Fe values (?0.89‰ to ?0.31‰) during summer, and there were significant increases of δ56Fe values in winter, except AR2, which was polluted with both coal mine drainage and sewage effluent. Characteristics of lakes have important influences on Fe isotope compositions of suspended particulates, lake sediments, and porewaters. The epilimnetic particulate Fe of Lake Hongfeng had δ56Fe=?0.04‰ to 0.13‰, while lighter Fe isotope compositions were measured for particulate Fe from Lake Aha, ranging from ?0.42‰ to ?0.09‰. Sediments collected from Hou Wu (HW) station of Lake Hongfeng have an average δ56Fe value of 0.09‰ and their corresponding porewaters have lighter Fe isotope compositions, ranging from ?0.57‰ to ?0.31‰; no significant variations have been observed. For the Liang Jiang Kou (LJK) station of Lake Aha, the content of reactive Fe and the concentration of sulfate were all high. Due to the reactive Fe recycling, including dissimilatory Fe reduction, adsorption, and Fe–sulfide formation, porewaters sampled near the sediment surface have been found to have a δ56Fe value as low as ?2.03‰ and an increase up to 0.12‰, with a burial depth of 10?cm. In contrast, an opposite variation trend was found for LJK sediments. Sediments sampled at 1-cm depth had a value of δ56Fe=?0.59‰ and decrease as low as ?1.75‰ with burial depth. This investigation demonstrated that significant Fe isotope fractionations occur in surface environments. Fe isotope compositions of particulate Fe were seriously affected by Fe sources, and Fe biogeochemical recycling has an important influence on Fe isotope fractionations in lake sediments, especially when there are significant amounts of reactive Fe and sulfate.     

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.     

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.     

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.     

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

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

Discovery of Mass Independent Oxygen Isotopic Compositions in Superscale Nitrate Mineral Deposits from Turpan‐Hami Basin,Xinjiang, China and Its Significance

<正>The Turpan-Hami Basin in eastern Xinjiang is one of the driest regions on Earth and a premier environment to form and preserve nitrate.A large nitrate ore field in this basin was found recently.It is estimated there are about 2.5 billion tons of resources of nitrate,and the amount is as much as the Atacama Desert super-scale nitrate deposit in Chile.Nitrate is one of a few minerals with mass-independent fractionation(MIF),and the oxygen isotope MIF is an effective method to determine the source of nitrate.Theδ~(17)O,δ~(18)O of nitrate were measured by fluorination and thermal decomposition method.The date indicated that this is the first time that oxygen isotope MIF has been located in inland nitrate minerals.The results obtained by two methods are similar,⊿~(17)=δ~(17)O-0.52×δ~(18)O=12‰-17‰.The experiment and observation data proved that oxygen isotope MIF of nitrate are the result of photochemical reactions in the troposphere and stratosphere.Thus, evidence from MIF oxygen isotopic compositions indicate that long term atmospheric deposition of nitrate aerosol particles produced by photochemical reactions is the source of the deposits.     

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.     

An Intercomparison Study of the Germanium Isotope Composition of Geological Reference Materials

Recent analytical developments in germanium stable isotope determination by multicollector ICP‐MS have provided new perspectives for the use of Ge isotopes as geochemical tracers. Here, we report the germanium isotope composition of the NIST SRM 3120a elemental reference solution that has been calibrated relative to internal isotopic standard solutions used in the previous studies. We also intercalibrate several geological reference materials as well as geological and meteoritic samples using different techniques, including online hydride generation and a spray chamber for sample introduction to MC‐ICP‐MS, and different approaches for mass bias corrections such as sample–calibrator bracketing, external mass bias correction using Ga isotopes and double‐spike normalisation. All methods yielded relatively similar precisions at around 0.1‰ (2s) for δ^74/70Ge values. Using igneous and mantle‐derived rocks, the bulk silicate Earth (BSE) δ^74/70Ge value was re‐evaluated to be 0.59 ± 0.18‰ (2s) relative to NIST SRM 3120a. Several sulfide samples were also analysed and yielded very negative values, down to ?4.3‰, consistent with recent theoretical study of Ge isotope fractionation. The strong heavy isotope depletion in ore deposits also contrasts with the generally positive Ge isotope values found in many modern and ancient marine sediments.     

Genesis of Pb–Zn Mineralization Beneath the Xiangshan Uranium Orefield,South China: Constraints from H–O–S–Pb Isotopes and Rb–Sr Dating

The volcanic‐hosted Xiangshan uranium orefield is the largest uranium deposit in South China. Recent exploration has discovered extensive Pb–Zn mineralization beneath the uranium orebodies. Detailed geological investigation reveals that the major metallic minerals include pyrite, sphalerite, galena, and chalcopyrite, whilst the major non‐metallic minerals include quartz, sericite, and calcite. New δ¹⁸O_fluid and δD_fluid data indicate that the ore‐forming fluids were mainly derived from magmatic, and the sulfide δ³⁴S values (2.2–6.9‰) suggest a dominantly magmatic sulfur source. The Pb isotope compositions are homogeneous (²⁰⁶Pb/²⁰⁴Pb = 18.120–18.233, ²⁰⁷Pb/²⁰⁴Pb = 15.575–15.698, and ²⁰⁸Pb/²⁰⁴Pb = 37.047–38.446). The ⁸⁷Sr/⁸⁶Sr ratios of sulfide minerals range from 0.7197 to 0.7204, which is much higher than volcanic rocks and fall into the range of metamorphic basement. Lead and strontium isotopic compositions indicate that the metallogenic materials probably were derived from metamorphic basement. Pyrite Rb–Sr dating of the ores yielded 131.3 ± 4.0 Ma, indicating that the Pb–Zn mineralization occurred in the Early Cretaceous.     

Mineralogy,Sulfur Isotope and Fluid Inclusion Studies of Hydrothermal Ore at the Hakurei Deposit,Bayonnaise Knoll,Izu‐Bonin Arc

Sulfide and sulfate ore samples collected from the Hakurei deposit of the Bayonnaise knoll were examined for the occurrence and chemical composition of minerals, including the sulfur isotopes and the microthermometry of fluid inclusions. Massive sulfide ore, mineralized volcanic rock, and anhydrite ore occur in descending order, from the seafloor to the bottom of the cored sample. The massive sulfide ore is dominated by sphalerite and accompanied by tennantite, chalcopyrite, and pyrite with lesser amounts of galena, enargite, and covellite. Amorphous silica is commonly precipitated on the surface of the sulfide minerals. As‐bearing minerals such as tennantite, enargite, and luzonite are common, while galena and Sb‐rich tetrahedrite are scarce. The mineral abundance and chemical composition of the minerals differs from that found in chimneys of the deposit. The sulfur isotope compositions in the minerals are +3.1–5.2‰ for sulfides and +19.6–21.8‰ for sulfate minerals. The homogeneous nature of the sulfur isotopes suggests that sulfur incorporated in the Hakurei deposit came from the reduction of aqueous sulfate in seawater.