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.     

Ore Genesis of the Lunwei Granite‐Related Scheelite Deposit in the Wuyi Metallogenic Belt,Southeast China: Constraints from Geochronology,Fluid Inclusions,and H–O–S Isotopes

A granite‐related scheelite deposit has been recently discovered in the Wuyi metallogenic belt of southeast China. The veinlet–disseminated scheelite occurs mainly in the inner and outer contact zones of the porphyritic biotite granite, spatially associated with potassic feldspathization and silicification. Re–Os dating of molybdenite intergrowths with scheelite yield a well‐constrained isochron age of 170.4 ± 1.2 Ma, coeval with the LA–MC–ICP–MS concordant zircon age of porphyritic biotite granite (167.6 ± 2.2 Ma), indicating that the Lunwei W deposit was formed in the Middle Jurassic (~170 Ma). We identify three stages of ore formation (from early to late): (I) the quartz–K‐feldspar–scheelite stage; (II) the quartz–polymetallic sulfide stage; and (III) the quartz–carbonate stage. Based on petrographic observations and microthermometric criteria, the fluid inclusions in the scheelite and quartz are determined to be mainly aqueous two‐phase (liquid‐rich and gas‐rich) fluid inclusions, with minor gas‐pure and CO₂‐bearing fluid inclusions. Ore‐forming fluids in the Lunwei W deposit show a successive decrease in temperature and salinity from Stage I to Stage III. The homogenization temperature decreases from an average of 299 °C in Stage I, through 251 °C in Stage II, to 212 °C in Stage III, with a corresponding change in salinity from an average of 5.8 wt.%, through 5.2 wt.%, to 3.4 wt.%. The ore‐forming fluids have intermediate to low temperatures and low salinities, belonging to the H₂O–NaCl ± CO₂ system. The δ¹⁸O_H2O values vary from 1.8‰ to 3.3‰, and the δD_V‐SMOW values vary from –66‰ to –76‰, suggesting that the ore‐forming fluid was primarily of magmatic water mixed with various amounts of meteoric water. Sulfur isotope compositions of sulfides (δ³⁴S ranging from –1.1‰ to +2.4‰) and Re contents in molybdenite (1.45–19.25 µg/g, mean of 8.97 µg/g) indicate that the ore‐forming materials originated mainly in the crust. The primary mechanism for mineral deposition in the Lunwei W deposit was a decrease in temperature and the mixing of magmatic and meteoric water. The Lunwei deposit can be classified as a porphyry‐type scheelite deposit and is a product of widespread tungsten mineralization in South China. We summarize the geological characteristics of typical W deposits (the Xingluokeng, Shangfang, and Lunwei deposits) in the Wuyi metallogenic belt and suggest that porphyry and skarn scheelite deposits should be considered the principal exploration targets in this area.     

Genesis of the Nanyangtian scheelite deposit in southeastern Yunnan Province,China: evidence from mineral chemistry,fluid inclusions,and C–O isotopes

The Nanyangtian skarn-type scheelite deposit is an important part of the Laojunshan W–Sn polymetallic metallogenic region in southeastern Yunnan Province, China. The deposit comprises multiple scheelite ore bodies; multilayer skarn-type scheelite ore bodies are dominant, with a small amount of quartz vein-type ore bodies. Skarn minerals include diopside, hedenbergite, grossular, and epidote. Three mineralization stages exist: skarn, quartz–scheelite, and calcite. The homogenization temperatures of fluid inclusions in hydrothermal minerals that formed in different paragenetic phases were measured as follows: 221–423 °C (early skarn stage), 177–260 °C (quartz–scheelite stage), and 173–227 °C (late calcite stage). The measured salinity of fluid inclusions ranged from 0.18% to 16.34% NaCleqv (skarn stage), 0.35%–7.17% NaCleqv (quartz–scheelite stage), and 0.35%–2.24% NaCleqv (late calcite vein stage). Laser Raman spectroscopic studies on fluid inclusions in the three stages showed H₂O as the main component, with N₂ present in minor amounts. Minor amounts of CH₄ were found in the quartz–scheelite stage. It was observed that the homogenization temperature gradually reduced from the early to the late mineralization stages; moreover, δ¹³C_PDB values for ore-bearing skarn in the mineralization period ranged from ? 5.7‰ to ? 6.9‰ and the corresponding δ¹⁸O_SMOW values ranged from 5.8‰ to 9.1‰, implying that the ore-forming fluid was mainly sourced from magmatic water with a minor amount of meteoric water. Collectively, the evidence indicates that the formation of the Nanyangtian deposit is related to Laojunshan granitic magmatism.     

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.     

Fluid Inclusions,Stable Isotopes,and Geochronology of the Haobugao Lead‐Zinc Deposit,Inner Mongolia,China

The Haobugao deposit, located in the southern segment of the Great Xing'an Range, is a famous skarn‐related Pb‐Zn‐(Cu)‐(Fe) deposit in northern China. The results of our fluid inclusion research indicate that garnets of the early stage (I skarn stage) contain three types of fluid inclusions (consistent with the Mesozoic granites): vapor‐rich inclusions (type LV, with V_H2O/(V_H2O + L_H2O) < 50 vol %, and the majority are 5–25 vol %), liquid‐rich two‐phase aqueous inclusions (type VL, with V_H2O/(V_H2O + L_H2O) > 50 vol %, the majority are 60–80 vol %), and halite‐bearing multiphase inclusions (type SL). These different types of fluid inclusions are totally homogenized at similar temperatures (around 320–420°C), indicating that the ore‐forming fluids of the early mineralization stage may belong to a boiling fluid system. The hydrothermal fluids of the middle mineralization stage (II, magnetite‐quartz) are characterized by liquid‐rich two‐phase aqueous inclusions (type VL, homogenization temperatures of 309–439°C and salinities of 9.5–14.9 wt % NaCl eqv.) that coexist with vapor‐rich inclusions (type LV, homogenization temperatures of 284–365°C and salinities of 5.2–10.4 wt % NaCl eqv.). Minerals of the late mineralization stage (III sulfide‐quartz stage and IV sulfide‐calcite stage) only contain liquid‐rich aqueous inclusions (type VL). These inclusions are totally homogenized at temperatures of 145–240°C, and the calculated salinities range from 2.0 to 12.6 wt % NaCl eqv. Therefore, the ore‐forming fluids of the late stage are NaCl‐H₂O‐type hydrothermal solutions of low to medium temperature and low salinity. The δD values and calculated δ¹⁸O_SMOW values of ore‐forming fluids of the deposit are in the range of ?4.8 to 2.65‰ and ?127.3‰ to ?144.1‰, respectively, indicating that ore‐forming fluids of the Haobugao deposit originated from the mixing of magmatic fluid and meteoric water. The S‐Pb isotopic compositions of sulfides indicate that the ore‐forming materials are mainly derived from underlying magma. Zircon grains from the mineralization‐related granite in the mining area yield a weighted ²⁰⁶Pb/²³⁸U mean age of 144.8 ±0.8 Ma, which is consistent with a molybdenite Re‐Os model age (140.3 ±3.4 Ma). Therefore, the Haobugao deposit formed in the Early Cretaceous, and it is the product of a magmatic hydrothermal system.     

Fluid Inclusions and Stable Isotopic Characteristics of the Yaoling Tungsten Deposit in South China: Metallogenetic Constraints

The Yaoling tungsten deposit is a typical wolframite quartz vein‐type tungsten deposit in the South China metallogenic province. The wolframite‐bearing quartz veins mainly occur in Cambrian to Ordovician host rocks or in Mesozoic granitic rocks and are controlled by the west‐north‐west trending extensional faults. The ore mineralization mainly comprises wolframite and variable amounts of molybdenite, chalcopyrite, pyrite, fluorite, and tourmaline. Hydrothermal alteration is well developed at the Yaoling tungsten deposit, including greisenization, silicification, fluoritization, and tourmalinization. Three types of primary/pseudosecondary fluid inclusions have been identified in vein quartz, which is intimately intergrown with wolframite. These include two‐phase liquid‐rich aqueous inclusions (type I), two‐ or three‐phase CO₂‐rich inclusions (type II), and type III daughter mineral‐bearing multiphase high‐salinity aqueous inclusions. Microthermometric measurements reveal consistent moderate homogenization temperatures (peak values from 200 to 280°C), and low to high salinities (1.3–39 wt % NaCl equiv.) for the type I, type II, and type III inclusions, where the CO₂‐rich type II inclusions display trace amounts of CH₄ and N₂. The ore‐forming fluids are far more saline than those of other tungsten deposits reported in South China. The estimated maximum trapping pressure of the ore‐forming fluids is about 1230–1760 bar, corresponding to a lithostatic depth of 4.0–5.8 km. The δD_H2O isotopic compositions of the inclusion fluid ranges from ?66.7 to ?47.8‰, with δ¹⁸O_H2O values between 1.63 and 4.17‰, δ¹³C values of ?6.5–0.8‰, and δ³⁴S values between ?1.98 and 1.92‰, with an average of ?0.07‰. The stable isotope data imply that the ore‐forming fluids of the Yaoling tungsten deposit were mainly derived from crustal magmatic fluids with some involvement of meteoric water. Fluid immiscibility and fluid–rock interaction are thought to have been the main mechanisms for tungsten precipitation at Yaoling.     

Ore Geology,Fluid Inclusion,and S‐ and Pb‐Isotopic Constraints on the Genesis of the Chitudian Zn‐Pb Deposit,Southern Margin of the North China Craton

The Chitudian Zn‐Pb ore deposit, Luanchuan, Henan province, was recently discovered in the southern margin of the North China Craton. The Zn‐Pb orebodies are hosted in the Proterozoic Guandaokou and Luanchuan Groups, occurring as veins in interbedding fracture zones mainly in a WNW‐ and partially in a NS‐direction. The Zn‐Pb ores are characterized by banded, massive, and breccia structures, coarse crystal grains, and a simple mineral composition mainly of galena, sphalerite, pyrite, quartz, dolomite, and calcite. In addition to the vein type orebodies, there are Mo‐ and Zn‐bearing skarn orebodies in the northwest of the Chitudian ore field. Four types of primary fluid inclusions in quartz and calcite were recognized in the Chitudian Zn‐Pb ores, including aqueous, aqueous‐CO₂, daughter‐mineral‐bearing aqueous, and daughter‐mineral‐bearing aqueous‐CO₂ inclusions, with aqueous inclusion being most common. The homogenization temperatures of the fluid inclusions from the main mineralization stage are from 290°C to 340°C, and the salinities mainly from 3.7 to 14.8 wt% NaCl equivalent. In addition to CO₂, CH₄ and H₂S were detected in the vapor phase and HS^‐ in the liquid phase of the fluid inclusions by Laser Raman spectroscopy. The δ³⁴S_V‐CDT values of ore sulfides from the Chitudian deposit range from ?0.32‰ to 8.30‰, and show two modal peaks in the histogram, one from 1‰ to 4‰, and the other from 5‰ to 7‰. The former peak is similar to that of porphyry‐type Mo‐W deposits in the area, whereas the latter is relatively close to the sulfur in the strata. The ore sulfur may have been derived from both the magma and the strata. The Pb‐isotopic compositions of the ore minerals from Chitudian, with ²⁰⁶Pb/²⁰⁴Pb from 17.005 to l7.953, ²⁰⁷Pb/²⁰⁴Pb from 15.414 to 15.587, and ²⁰⁸Pb/²⁰⁴Pb from 37.948 to 39.036, are similar to those of Mesozoic porphyries in the Chitudian ore field, suggesting that the ore‐forming metals were mainly derived from the Mesozoic magmatic intrusions. The Chitudian Zn‐Pb deposit is interpreted to be a distal hydrothermal vein‐type deposit, which was genetically related to the proximal, skarn‐type Mo ore deposits in the region.     

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.     

Constraints on the mineralization processes of the Makeng iron deposit,eastern China: Fluid inclusion,H–O isotope and magnetite trace element analysis

The Makeng iron deposit is located in the Yong’an-Meizhou depression belt in Fujian Province, eastern China. Both skarn alteration and iron mineralization are mainly hosted within middle Carboniferous-lower Permian limestone. Five paragenetic stages of skarn formation and ore deposition have been recognized: Stage 1, early skarn (andradite–grossular assemblage); Stage 2, magnetite mineralization (diopside–magnetite assemblage); Stage 3, late skarn (amphibole–chlorite–epidote–johannsenite–hedenbergite–magnetite assemblage); Stage 4, sulfide mineralization (quartz–calcite–fluorite–chlorite–pyrite–galena–sphalerite assemblage); and Stage 5, carbonate (quartz–calcite assemblage). Fluid inclusion studies were carried out on inclusions in diopside from Stage 2 and in quartz, calcite, and fluorite from Stage 4.Halite-bearing (Type 1) and coexisting two-phase vapor-rich aqueous (Type 3) inclusions in the magnetite stage display homogenization temperatures of 448–564 °C and 501–594 °C, respectively. Salinities range from 26.5 to 48.4 and 2.4 to 6.9 wt% NaCl equivalent, respectively. Two-phase liquid-rich aqueous (Type 2b) inclusions in the sulfide stage yield homogenization temperatures and salinities of 182–343 °C and 1.9–20.1 wt% NaCl equivalent. These fluid inclusion data indicate that fluid boiling occurred during the magnetite stage and that fluid mixing took place during the sulfide stage. The former triggered the precipitation of magnetite, and the latter resulted in the deposition of Pb, Zn, and Fe sulfides. The fluids related to magnetite mineralization have δ¹⁸O_fluid-VSMOW of 6.7–9.6‰ and δD of −96 to −128‰, which are interpreted to indicate residual magmatic water from magma degassing. In contrast, the fluids related to the sulfide mineralization show δ¹⁸O_fluid-VSMOW of −0.85 to −1.04‰ and δD of −110 to −124‰, indicating that they were generated by the mixing of magmatic water with meteoric water. Magnetite grains from Stage 2 exhibit oscillatory zoning with compositional variations in major elements (e.g., SiO₂, Al₂O₃, CaO, MgO, and MnO) from core to rim, which is interpreted as a self-organizing process rather than a dissolution-reprecipitation process. Magnetite from Stage 3 replaces or crosscuts early magnetite, suggesting that later hydrothermal fluid overprinted and caused dissolution and reprecipitation of Stage 2 magnetite. Trace element data (e.g., Ti, V, Ca, Al, and Mn) of magnetite from Stages 2 and 3 indicate a typical skarn origin.     

A Study of Ore-forming Fluids in the Shimensi Tungsten Deposit, Dahutang Tungsten Polymetallic Ore Field, Jiangxi Province, China

The Dahutang tungsten polymetallic ore field is located north of the Nanling W-Sn polymetallic metallogenic belt and south of the Middle—Lower Yangtze River Valley Cu-Mo-Au-Fe porphyry-skarn belt.It is a newly discovered ore field,and probably represents the largest tungsten mineralization district in the world.The Shimensi deposit is one of the mineral deposits in the Dahutang ore field,and is associated with Yanshanian granites intruding into a Neoproterozoic granodiorite batholith.On the basis of geologic studies,this paper presents new petrographic,microthermometric,laser Raman spectroscopic and hydrogen and oxygen isotopic studies of fluid inclusions from the Shimensi deposit.The results show that there are three types of fluid inclusions in quartz from various mineralization stages:liquid-rich two-phase fluid inclusions,vapor-rich two-phase fluid inclusions,and three-phase fluid inclusions containing a solid crystal,with the vast majority being liquid-rich two-phase fluid inclusions.In addition,melt and melt-fluid inclusions were also found in quartz from pegmatoid bodies in the margin of the Yanshanian intrusion.The homogenization temperatures of liquid-rich two-phase fluid inclusions in quartz range from 162 to 363℃ and salinities are 0.5wt%-9.5wt%NaCI equivalent.From the early to late mineralization stages,with the decreasing of the homogenization temperature,the salinity also shows a decreasing trend.The ore-forming fluids can be approximated by a NaCl-H_2O fluid system,with small amounts of volatile components including CO_2,CH_4 and N_2,as suggested by Laser Raman spectroscopic analyses.The hydrogen and oxygen isotope data show that δ5D_(V-smow) values of bulk fluid inclusions in quartz from various mineralization stages vary from-63.8‰ to-108.4‰,and the δ~(18)O_(H2O) values calculated from the δ~(18)O_(V-)smow values of quartz vary from-2.28‰ to 7.21‰.These H-O isotopic data are interpreted to indicate that the ore-forming fluids are mainly composed of magmatic water in the early stage,and meteoric water was added and participated in mineralization in the late stage.Integrating the geological characteristics and analytical data,we propose that the ore-forming fluids of the Shimensi deposit were mainly derived from Yanshanian granitic magma,the evolution of which resulted in highly differentiated melt,as recorded by melt and melt-fluid inclusions in pegmatoid quartz,and high concentrations of metals in the fluids.Cooling of the ore-forming fluids and mixing with meteoric water may be the key factors that led to mineralization in the Dahutang tungsten polymetallic ore field.     

Geology,Fluid Inclusion,and Sulfur Isotope Studies of the Chehugou Porphyry Molybdenum–Copper Deposit,Xilamulun Metallogenic Belt,NE China

The Chehugou Mo–Cu deposit, located 56 km west of Chifeng, NE China, is hosted by Triassic granite porphyry. Molybdenite–chalcopyrite mineralization of the deposit mainly occurs as veinlets in stockwork ore and dissemination in breccia ore, and two ore‐bearing quartz veins crop out to the south of the granite porphyry stock. Based on crosscutting relationships and mineral paragenesis, three hydrothermal stages are identified: (i) quartz–pyrite–molybdenite ± chalcopyrite stage; (ii) pyrite–quartz ± sphalerite stage; and (iii) quartz–calcite ± pyrite ± fluorite stage. Three types of fluid inclusions in the stockwork and breccia ore are recognized: LV, two‐phase aqueous inclusions (liquid‐rich); LVS, three‐phase liquid, vapor, and salt daughter crystal inclusions; and VL, two‐phase aqueous inclusions (gas‐rich). LV and LVS fluid inclusions are recognized in vein ore. Microthermometric investigation of the three types of fluid inclusions in hydrothermal quartz from the stockwork, breccia, and vein ores shows salinities from 1.57 to 66.75 wt% NaCl equivalents, with homogenization temperatures varying from 114°C to 550°C. The temperature changed from 282–550°C, 220–318°C to 114–243°C from the first stage to the third stage. The homogenization temperatures and salinity of the LV, LVS and VL inclusions are 114–442°C and 1.57–14.25 wt% NaCl equivalent, 301–550°C and 31.01–66.75 wt% NaCl equivalent, 286–420°C and 4.65–11.1 wt% NaCl equivalent, respectively. The VL inclusions coexist with the LV and LVS, which homogenize at the similar temperature. The above evidence shows that fluid‐boiling occurred in the ore‐forming stage. δ³⁴S values of sulfide from three type ores change from ?0.61‰ to 0.86‰. These δ³⁴S values of sulfide are similar to δ³⁴S values of typical magmatic sulfide sulfur (c. 0‰), suggesting that ore‐forming materials are magmatic in origin.     

A Fluid Inclusion Study of Vein-type Copper Mineralization in the East Wulasigou Pb–Zn–Cu Deposit, Altay, Northwestern China

The Wulasigou Cu-Pb-Zn deposit,located 15 km northwest of Altay city in Xinjiang,is one of many Cu-Pb-Zn polymetallic deposits in the Devonian Kelan volcanic-sedimentary basin in southern Altaids.Two mineralizing periods can be distinguished:the marine volcanic sedimentary PbZn mineralization period,and the metamorphic hydrothermal Cu mineralization period,which is further divided into an early bedded foliated quartz vein stage(Q1) and a late sulfide-quartz vein stage(Q2) crosscutting the foliation.Four types of fluid inclusions were recognized in the Q1 and Q2 quartz from the east orebodies of the Wulasigou deposit:H_2O-CO_2 inclusions,carbonic fluid inclusions,aqueous fluid inclusions,and daughter mineral-bearing fluid inclusions.Microthermometric studies show that solid CO_2 melting temperatures(T_(m,CO2)) of H_2O-CO_2 inclusions in Ql are from-62.3℃ to-58.5C,clathrate melting temperatures(T_(m,clath)l) are from 0.5 C to 7.5 C,partial homogenization temperatures(T_(h,CO2)) vary from 3.3℃ to 25.9℃(to liquid),and the total homogenization temperatures(T_(h,tot)) vary from 285℃ to 378℃,with the salinities being 4.9%-15.1%NaCl eqv.and the CO_2-phase densities being 0.50-0.86 g/cm~3.H_2O-CO_2 inclusions in Q2 have T_(m,CO_2) from-61.9℃ to-56.9℃,T_(m,clath)from 1.3℃ to 9.5℃,T_(h,CO2) from 3.4℃ to 28.7℃(to liquid),and T_(h,tot) from 242℃ to 388℃,with the salinities being 1.0%-15.5%NaCl eqv.and the CO_2-phase densities being 0.48-0.89 g/cm~3.The minimum trapping pressures of fluid inclusions in Q1 and Q2 are estimated to be 260-360 MPa and180-370 MPa,respectively.The δ~(34)S values of pyrite from the volcanic sedimentary period vary from2.3‰ to 2.8‰(CDT),and those from the sulfide-quartz veins fall in a narrow range of-1.9‰ to 2.6‰(CDT).The δD values of fluid inclusions in Q2 range from-121.0‰ to-100.8‰(SMOW),and theδ~(18)O_(H2O) values calculated from δ~(18)O of quartz range from-0.2‰ to 8.3‰(SMOW).The δD-δ~(18)O_(H2O)data are close to the magmatic and metamorphic fields.The fluid inclusion and stable isotope data documented in this study indicate that the vein-type copper mineralization in the Wulasigou Pb-Zn-Cu deposit took place in an orogenic-metamorphic enviroment.     

Fluid Inclusion and Carbon-Oxygen Isotope Studies of the Hujiayu Cu Deposit, Zhongtiao Mountains, China: Implications for Syn-metamorphic Copper Remobilization

The Hujiayu Cu deposit,representative of the "HuBi-type" Cu deposits in the Zhongtiao Mountains district in the southern edge of the North China Craton,is primarily hosted in graphitebearing schists and carbonate rocks.The ore minerals comprise mainly chalcopyrite,with minor sphalerite,siegenite[(Co,Ni)_3S_4],and clausthalite[Pb(S,Se)].The gangue minerals are mainly quartz and dolomite,with minor albite.Four fluid inclusion types were recognized in the chalcopyrite-pyrite-dolomite-quartz veins,including CO_2-rich inclusions(type Ⅰ),low-salinity,liquid-dominated,biphase aqueous inclusions(type Ⅱ),solid-bearing aqueous inclusions(type Ⅲ),and solid-bearing aqueous-carbonic inclusions(type Ⅳ).Type I inclusion can be further divided into two sub-types,i.e.,monophase CO_2 inclusions(type Ⅰa) and biphase CO_2-rich inclusions(with a visible aqueous phase),and type Ⅲ inclusion is divided into a subtype with a halite daughter mineral(type Ⅲa) and a subtype with multiple solids(type Ⅲb).Various fluid inclusion assemblages(FIAs) were identified through petrographic observations,and were classified into four groups.The group-1 FIA,consisting of monophase CO_2 inclusions(type Ⅰa),homogenized into the liquid phase in a large range of temperatures from-1 to 28℃,suggesting post-entrapment modification.The group-2 FIA consists of type Ⅰb,Ⅲb and Ⅳ inclusions,and is interpreted to reflect fluid immiscibility.The group-3 FIA comprises type Ⅱ and Ⅲa inclusions,and the group-4FIA consists of type Ⅱ inclusions with consistent phase ratios.The group-1 and group-2 FIAs are interpreted to be entrapped during mineralization,whereas group-3 and group-4 FIAs probably represent the post-mineralization fluids.The solid CO_2 melting temperatures range from-60.6 to56.6℃ and from-66.0 to-63.4℃ for type Ⅰa and type Ⅳ inclusions,respectively.The homogenization temperatures for type Ⅱ inclusions range from 132 to 170℃ for group-3 FIAs and115 to 219℃ for group-4 FIAs.The halite melting temperatures range from 530 to 562℃ for typeⅢ b and Ⅳ inclusions,whereas those for type Ⅲa inclusions range from 198 to 398℃.Laser Raman and SEM-EDS results show that the gas species in fluid inclusions are mainly CO_2 with minor CH_4,and the solids are dominated by calcite and halite.The calcite in the hosting marble and dolomite in the hydrothermal veins have δ~(13)C_(V-pdb) values of-0.2 to 1.2‰ and-1.2 to-6.3‰,and δ~(18)O_(v-smow) values of 14.0 to 20.8 ‰ and 13.2 to 14.3‰,respectively.The fluid inclusion and carbon-oxygen isotope data suggest that the ore-forming fluids were probably derived from metamorphic fluids,which had reacted with organic matter in sedimentary rocks or graphite and undergone phase separation at 1.4-1.8 kbar and 230-240℃,after peak metamorphism.It is proposed that the Hujiayu Cu deposit consists of two mineralization stages.The early stage mineralization,characterized by disseminated and veinlet copper sulfides,probably took place in an environment similar to sediment-hosted stratiform copper mineralization.Ore minerals formed in this precursor mineralization stage were remobilized and enriched in the late metamorphic hydrothermal stage,leading to the formation of thick quartz-dolomite-sulfides veins.     

Geology,fluid inclusion and stable isotopes (O,S) of the Hetaoping distal skarn Zn-Pb deposit,northern Baoshan block,SW China

The Hetaoping zinc–lead deposit is located in the northern Baoshan block, Sanjiang region, SW China. The ore deposit comprises massive orebodies in the lower part and lenticular and vein-like orebodies in the upper part, both of which are hosted in the marbleized Upper Cambrian limestone and slate of the Hetaoping Formation. Three mineralization stages of Hetaoping skarn system have been recognized based on petrographic observation, which are pre-ore stage (pyroxene–garnet–actinolite–epidote–magnetite), syn-ore stage (sulfides–quartz–calcite–fluorite), and post-ore stage (calcite–quartz–chlorite). Andradite and hedenbergite are dominant in pre-ore garnet and pyroxene, respectively. Ore minerals consist of mainly pyrite, sphalerite, chalcopyrite, bornite and galena. Three types of fluid inclusions have been identified in Hetaoping, including primary two-phase (A type), primary three-phase (B type) and secondary two-phase (C type) inclusions. Based on fluid inclusion microthermometric study, the fluids forming the Hetaoping skarn minerals and sulfides evolved from high-moderate temperature (255–498 °C) and low-moderate salinity (5.0–18.0 wt.% NaCl equiv) in pre-ore stage, through moderate-low temperature (152–325 °C) and low salinity (0.4–14.2 wt.% NaCl equiv) in syn-ore stage, to low temperature (109–205 °C) and low salinity (0.9–10.0 wt.% NaCl equiv) in post-ore stage. The sulfide δ³⁴S values range from 3.7 to 7.1‰ (mean = 5.2‰, n = 29), indicative of a dominantly magmatic sulfur origin. Silicate and carbonate oxygen isotopes give calculated δ¹⁸O_H2O ranges of 3.9–11.1‰ in prograde stage, − 0.9 to 4.6‰ in early retrograde stage, and − 1.3 to 2.9‰ in late retrograde stage (syn-ore stage), The oxygen isotope data reveal that the prograde fluid in Hetaoping could be primarily magmatic, which has been mixed significantly with meteoric water in the late retrograde stage. Such a fluid mixing process is considered to be a key factor controlling ore precipitation.     

Geochronology and Ore‐Forming Fluids of the Baizhangyan W–Mo Deposit in the Chizhou Area,Middle‐Lower Yangtze Valley,SE‐China

The Baizhangyan skarn‐porphyry type W–Mo deposit is located in a newly defined Mo–W–Pb–Zn metallogenic belt, which is in the south of Middle‐Lower Yangtze Valley Cu–Fe–Au polymetallic metallogenic belt in SE China. The W–Mo orebodies occur mainly within the contact zone between fine‐grained granite and Sinian limestone strata. There are two types of W–Mo mineralization: major skarn W–Mo mineralization and minor granite‐hosted disseminated Mo mineralization which was traced by drilling at depth. Eight molybdenite samples from Mo‐bearing ores yield Re–Os dates that overlap within analytical error, with a weighted average age of 134.1 ± 2.2 Ma. These dates are in close agreement with SIMS U–Pb concordant zircon age for fine‐grained granite at 133.3 ± 1.3 Ma, indicating that crystallization of the granite and hydrothermal molybdenite formation were coeval and likely cogenetic. The Baizhangyan W–Mo deposit formed in the Early Cretaceous extensional tectonic setting at the Middle‐Lower Yangtze Valley metallogenic belt and the Jaingnan Ancient Continent. Based on mineral compositions and crosscutting relationships of veinlets, hydrothermal alteration and mineralization, the ore mineral paragenesis of the Baizhangyan deposit is divided into four stages: skarn stage (I), oxide stage (II), sulfide stage (III), and carbonate stage (IV). Fluid inclusions in garnet, scheelite, quartz and calcite from W–Mo ores are mainly aqueous‐rich (L + V) type inclusions. Following garnet deposition at stage I, the high‐temperature fluids gave way to progressively cooler, more dilute fluids associated with tungsten–molybdenite–base metal sulfide deposition (stage II and stage III) (162–360°C, 2.7–13.2 wt % NaCl equivalent) and carbonate deposition (stage IV) (137–190°C, 0.9–5 wt % NaCl equiv.). Hydrogen‐oxygen isotope data from minerals of different stages suggest that the ore‐forming fluids consisted of magmatic water, mixed in various proportions with meteoric water. From stage I to stage IV, there is a systematic decrease in the homogenization temperature of the fluid‐inclusion fluids and calculated δ¹⁸O values of the fluids. These suggest that increasing involvement of formation water or meteoric water during the fluid ascent resulted in successive deposition of scheelite and molybdenite at Baizhangyan.     

Geochemical Characteristics and Sources of Ore-forming Fluids of the Mayuan Pb-Zn Deposit, Nanzheng, Shaanxi, China

The Mayuan stratabound Pb-Zn deposit in Nanzheng,Shaanxi Province,is located in the northern margin of the Yangtze Plate,in the southern margin of the Beiba Arch.The orebodies are stratiform and hosted in breciated dolostone of the Sinian Dengying Formation.The ore minerals are primarily sphalerite and galena,and the gangue minerals comprise of dolomite,quartz,barite,calcite and solid bitumen.Fluid inclusions from ore-stage quartz and calcite have homogenization tempreatures from 98 to 337℃ and salinities from 7.7 wt%to 22.2 wt%(NaCl equiv.).The vapor phase of the inclusions is mainly composed of CH_4 with minor CO_2 and H_2S.The δD_(fluid) values of fluid inclusions in quartz and calcite display a range from-68‰ to-113‰(SMOW),and the δ~(18)O_(fluid)values calculated from δ~(18)O_(quartz) and δ~(18)O_(calcite) values range from 4.5‰ to 16.7‰(SMOW).These data suggest that the ore-forming fluids may have been derived from evaporitic sea water that had reacted with organic matter.The δ~(13)C_(CH4) values of CH_4 in fluid inclusions range from-37.2‰ to-21.0‰(PDB),suggesting that the CH_4 in the ore-forming fluids was mainly derived from organic matter.This,together with the abundance of solid bitumen in the ores,suggest that organic matter played an important role in mineralization,and that the thermochemical sulfate reduction(TSR) was the main mechanism of sulfide precipitation.The Mayuan Pb-Zn deposit is a carbonate-hosted epigenetic deposit that may be classified as a Mississippi Valley type(MVT) deposit.     

Reconciling fluid inclusion types,fluid processes,and fluid sources in skarns: an example from the Bismark Deposit,Mexico

The Bismark deposit (8.5 Mt at 8% Zn, 0.5% Pb, 0.2% Cu, and 50 g/t Ag) located in northern Mexico is an example of a stock-contact skarn end member of a continuum of deposit types collectively called high-temperature, carbonate-replacement deposits. The deposit is hosted by massive sulfide within altered limestone adjacent to the Bismark quartz monzonite stock (~42 Ma) and the Bismark fault. Alteration concurrently developed in both the intrusion and limestone. The former contains early potassic alteration comprising K-feldspar and biotite, which was overprinted by kaolinite-rich veins and alteration and later quartz, sericite, and pyrite with minor sphalerite and chalcopyrite. Prograde exoskarn alteration in the limestone consists of green andradite and diopside, and transitional skarn comprising red-brown andradite, green hedenbergite and minor vesuvinite, calcite, fluorite, and quartz. The main ore stage post-dates calc-silicate minerals and comprises sphalerite and galena with gangue pyrite, pyrrhotite, calcite, fluorite, and quartz. The entire hydrothermal system developed synchronously with faulting. Fluid inclusion studies reveal several distinct temporal, compositional, and thermal populations in pre-, syn- and post-ore quartz, fluorite, and calcite. The earliest primary fluid inclusions are coexisting vapor-rich (type 2A) and halite-bearing (type 3A; type 3B contain sylvite) brine inclusions (32 to >60 total wt% salts) that occur in pre-ore fluorite. Trapping temperatures are estimated to have been in excess of 400 °C under lithostatic pressures of ~450 bar (~1.5 km depth). Primary fluid inclusions trapped in syn-ore quartz display critical to near critical behavior (type 1C), have moderate salinity (8.4 to 10.9 wt% NaCl equiv.) and homogenization temperatures (Th) ranging from 351 to 438 °C. Liquid-rich type 1A and 1B (calcite-bearing) inclusions occur as primary to secondary inclusions predominantly in fluorite and show a range in Th (104–336 °C) and salinity (2.7–11.8 wt% NaCl equiv.), which at the higher Th and salinity ranges overlap with type 1C inclusions. Oxygen isotope analysis was carried out on garnet, quartz, and calcite (plus carbon isotopes) in pre-, syn-, post-ore, and peripheral veins. Pre-ore skarn related garnets have a δ¹⁸O_mineral range between 3.9 and 8.4‰. Quartz from the main ore stage range between 13.6 and 16.0‰. Calcite from the main ore stage has δ¹³C values of –2.9 to –5.1‰ and δ¹⁸O values of 12.3 to 14.1‰, which are clearly distinct from post-ore veins and peripheral prospects that have much higher δ¹⁸O (16.6–27.3‰) and δ¹³C (1.3–3.1‰) values. Despite the numerous fluid inclusion types, only two fluid sources can be inferred, namely a magmatic fluid and an external fluid that equilibrated with limestone. Furthermore, isotopic data does not indicate any significant mixing between the two fluids, although fluid inclusion data may be interpreted otherwise. Thus, the various fluid types were likely to have formed from varying pressure–temperature conditions through faulting during exsolution of magmatic fluids. Late-stage hydrothermal fluid activity was dominated by the non-magmatic fluids and was post-ore.     

Alteration and mineralization at the Zhibula Cu skarn deposit,Gangdese belt,Tibet

The Zhibula Cu skarn deposit contains 0.32 Mt. Cu metal with an average grade of 1.64% and is located in the Gangdese porphyry copper belt in southern Tibet. The deposit is a typical metasomatic skarn that is related to the interaction of magmatic–hydrothermal fluids and calcareous host rock. Stratiform skarn orebodies occur at the contact between tuff and marble in the Lower Jurassic Yeba Formation. Alteration zones generally grade from a fresh tuff to a garnet-bearing tuff, a garnet pyroxene skarn, and finally to a wollastonite marble. Minor endoskarn alteration zonations are also observed in the causative intrusion, which grade from a fresh granodiorite to a weakly chlorite-altered granodiorite, a green diopside-bearing granodiorite, and to a dark red-brown garnet-bearing granodiorite. Prograde minerals, which were identified by electron probe microanalysis include andradite–grossularite of various colors (e.g., red, green, and yellow) and green diopside. Retrograde metamorphic minerals overprint the prograde skarn, and are mainly composed of epidote, quartz, and chlorite. The ore minerals consist of chalcopyrite and bornite, followed by magnetite, molybdenite, pyrite, pyrrhotite, galena, and sphalerite. Three types of fluid inclusions are recognized in the Zhibula deposit, including liquid-rich two-phase inclusions (type L), vapor-rich two-phase inclusions (type V), and daughter mineral-bearing three-phase inclusions (type S). As the skarn formation evolved from prograde (stage I) to early retrograde (stage II) and later retrograde (stage III), the ore-forming fluids correspondingly evolved from high temperature (405–667 °C), high salinity (up to 44.0 wt.% NaCl equiv.), and high pressure (500–600 bar) to low-moderate temperature (194–420 °C), moderate-high salinity (10.1–18.3 and 30.0–44.2 wt.% NaCl equiv.), and low-moderate pressure (250–350 bar). Isotopic data of δ³⁴S (− 0.1‰ to − 6.8‰, estimated δ³⁴S_fluids = − 0.7‰), δD_H2O (− 91‰ to − 159‰), and δ¹⁸O_H2O (1.5‰ to 9.2‰) suggest that the ore-forming fluid and material came from magmatic–hydrothermal fluids that were associated with Miocene Zhibula intrusions. Fluid immiscibility likely occurred at the stage I and stage II during the formation of the skarn and mineralization. Fluid boiling occurred during the stage III, which is the most important Cu deposition mechanism for the Zhibula deposit.     

Genesis of the Weiquan Ag–Polymetallic Deposit in East Tianshan, China: Evidence from Zircon U–Pb Geochronology and C–H–O–S–Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ~(13)C values of the calcite samples range from-2.5‰ to 2.3‰, the δ~(18)O_(H2 O) and δD_(VSMOW) values of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ~(13)C, δ~(18)O_(H2 O) and δD_(V-SMOW) values of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ~(34)S_(V-CDT) values of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The ~(206)Pb/~(204)Pb, ~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb, and ~(208)Pb/~(204)Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.     

Geology,Fluid Inclusions,and Isotopic Geochemistry of the Jinman Sediment‐Hosted Copper Deposit in the Lanping Basin,China

The Jinman Cu polymetallic deposit is located within Middle Jurassic sandstone and slate units in the Lanping Basin of southwestern China. The Cu mineralization occurs mainly as sulfide‐bearing quartz–carbonate veins in faults and fractures, controlled by a Cenozoic thrust–nappe system. A detailed study of fluid inclusions from the Jinman deposit distinguishes three types of fluid inclusions in syn‐ore quartz and post‐ore calcite: aqueous water (type A), CO₂–H₂O (type B), and CO₂‐dominated (type C) fluid inclusions. The homogenization temperatures of CO₂–H₂O inclusions vary from 208°C to 329°C, with corresponding salinities from 0.6 to 4.6 wt.% NaCl equivalent. The homogenization temperatures of the aqueous fluid inclusions mainly range from 164°C to 249°C, with salinities from 7.2 to 20.2 wt.% NaCl equivalent. These characteristics of fluid inclusions are significantly different from those of basinal mineralization systems, but similar to those of orogenic or magmatic mineralization systems. The H and O isotope compositions suggest that the ore‐forming fluid is predominantly derived from magmatic water, with the participation of basinal brine. The δ³⁴S values are widely variable between ?9.7 ‰ and 9.7 ‰, with a mode distribution around zero, which may be interpreted by the variation in physico‐chemical conditions or by compositional variation of the sources. The mixing of a deeply sourced CO₂‐rich fluid with basinal brine was the key mechanism responsible for the mineralization of the Jinman deposit.