Genesis of the Huangshaping W–Mo–Cu–Pb–Zn polymetallic deposit in Southeastern Hunan Province,China: Constraints from fluid inclusions,trace elements,and isotopes

The Huangshaping polymetallic deposit is located in southeastern Hunan Province, China. It is a world-class W–Mo–Pb–Zn–Cu skarn deposit in the Nanling Range Metallogenic Belt, with estimated reserves of 74.31 Mt of W–Mo ore at 0.28% WO₃ and 0.07% Mo, 22.43 Mt of Pb–Zn ore at 3.6% Pb and 8.00% Zn, and 20.35 Mt of Cu ore at 1.12% Cu. The ore district is predominantly underlained by carbonate formations of the Lower Carboniferous period, with stocks of quartz porphyry, granite porphyry, and granophyre. Skarns occurred in contact zones between stocks and their carbonate wall rocks, which are spatially associated with the above-mentioned three types of ores (i.e., W–Mo, Pb–Zn, and Cu ores).Three types of fluid inclusions have been identified in the ores of the Huangshaping deposit: aqueous liquid–vapor inclusions (Type I), daughter-mineral-bearing aqueous inclusions (Type II), and H₂O–CO₂ inclusions (Type III). Systematic microthermometrical, laser Raman spectroscopic, and salinity analyses indicate that high-temperature and high-salinity immiscible magmatic fluid is responsible for the W–Mo mineralization, whereas low-temperature and low-salinity magmatic-meteoric mixed fluid is responsible for the subsequent Pb–Zn mineralization. Another magmatic fluid derived from deep-rooted magma is responsible for Cu mineralization.Chondrite-normalized rare earth element patterns and trace element features of calcites from W–Mo, Pb–Zn, and Cu ores are different from one another. Calcite from Cu ores is rich in heavy rare earth elements (187.4–190.5 ppm), Na (0.17%–0.19%), Bi (1.96–64.60 ppm), Y (113–135 ppm), and As (9.1–29.7 ppm), whereas calcite from W–Mo and Pb–Zn ores is rich in Mn (> 10.000 ppm) and Sr (178–248 ppm) with higher Sr/Y ratios (53.94–72.94). δ¹⁸O values also differ between W–Mo/Pb–Zn ores (δ¹⁸O = 8.10‰–8.41‰) and Cu ores (δ¹⁸O = 4.34‰–4.96‰), indicating that two sources of fluids were, respectively, involved in the W–Mo, Pb–Zn, and Cu mineralization.Sulfur isotopes from sulfides also reveal that the large variation (4‰–19‰) within the Huangshaping deposit is likely due to a magmatic sulfur source with a contribution of reduced sulfate sulfur host in the Carboniferous limestone/dolomite and more magmatic sulfur involved in the Cu mineralization than that in W–Mo and Pb–Zn mineralization. The lead isotopic data for sulfide (galena: ²⁰⁶Pb/²⁰⁴Pb = 18.48–19.19, ²⁰⁷/²⁰⁴Pb = 15.45–15.91, ²⁰⁸/²⁰⁴Pb = 38.95–39.78; sphalerite: ²⁰⁶Pb/²⁰⁴Pb = 18.54–19.03, ²⁰⁷/²⁰⁴Pb = 15.60–16.28, ²⁰⁸/²⁰⁴Pb = 38.62–40.27; molybdenite: ²⁰⁶Pb/²⁰⁴Pb = 18.45–19.21, ²⁰⁷/²⁰⁴Pb = 15.53–15.95, ²⁰⁸/²⁰⁴Pb = 38.77–39.58 chalcopyrite: ²⁰⁶Pb/²⁰⁴Pb = 18.67–19.38, ²⁰⁷/²⁰⁴Pb = 15.76–19.90, and ²⁰⁸/²⁰⁴Pb = 39.13–39.56) and oxide (scheelite: ²⁰⁶Pb/²⁰⁴Pb = 18.57–19.46, ²⁰⁷/²⁰⁴Pb = 15.71–15.77, ²⁰⁸/²⁰⁴Pb = 38.95–39.13) are different from those of the wall rock limestone (²⁰⁶Pb/²⁰⁴Pb = 18.34–18.60, ²⁰⁷/²⁰⁴Pb = 15.49–15.69, ²⁰⁸/²⁰⁴Pb = 38.57–38.88) and porphyries (²⁰⁶Pb/²⁰⁴Pb = 17.88–18.66, ²⁰⁷/²⁰⁴Pb = 15.59–15.69, ²⁰⁸/²⁰⁴Pb = 38.22–38.83), suggesting Pb²⁰⁶-, U²³⁸-, and Th ²³²-rich material are involved in the mineralization. The Sm–Nd isotopes of scheelite (ε_Nd(t) = − 6.1 to − 2.9), garnet (ε_Nd(t) = − 6.8 to − 6.1), and calcite (ε_Nd(t) = − 6.3) from W–Mo ores as well as calcite (ε_Nd(t) = − 5.4 to − 5.3) and scheelite (ε_Nd(t) = − 2.9) from the Cu ores demonstrate suggest more mantle-derived materials involved in the Cu mineralization.In the present study we conclude that two sources of ore-forming fluids were involved in production of the Huangshaping W–Mo–Pb–Zn–Cu deposit. One is associated with the granite porphyry magmas responsible for the W–Mo and then Pb–Zn mineralization during which its fluid evolved from magmatic immiscible to a magmatic–meteoritic mixing, and the other is derived from deep-rooted magma, which is related to Cu-related mineralization.     

Metallogenesis and hydrothermal evolution of Middle Jurassic porphyry Mo deposits in the southern Zhangguangcai Range,NE China: evidence from fluid inclusions,H–O–S isotopes,and Re–Os geochronology

A major metallogenic belt with substantial resources of gold, lead, zinc, copper, and molybdenum is present in the southern Zhangguangcai Range, NE China. Several large porphyry Mo deposits are located in this belt, as for example at Jidetun, Fu’anpu, and Daheishan. Five molybdenite samples from the Jidetun deposit yielded an Re–Os isochron age of 168.6 ± 2.1 Ma (mean standard weighted deviation = 0.20), and this is consistent with the Re–Os isochron ages of the other Mo deposits in the southern Zhangguangcai Range, giving a Middle Jurassic age for metallogenesis. The Jidetun, Fu’anpu, and Daheishan deposits all tend to have weakly enriched ³⁴S values of 0.80‰–3.20‰ and relatively low Re contents ranging from 3.073 to 43.567 ppm, which indicates the ore-forming materials were derived mainly from granitic magmas that had an origin in the mixture of crust and mantle. Three stages of mineralization can be identified in the deposits at Jidetun, Fu’anpu, and Daheishan. The original ore-forming fluids in stage I were characterized by high-temperature magmatic hydrothermal fluids that were most likely derived by exsolution from the Middle Jurassic ore-bearing magmas. However, two different fluid systems, NaCl–H₂O–CO₂ fluids and NaCl–H₂O fluids, were widespread in stage I of porphyry Mo deposits in the southern Zhangguangcai Range. Taking into account the regional geological characteristics and tectonic setting, we suggest that two different emplacement modes of the ore-bearing magmas explain the different fluid systems in stage I: the first magmas were emplaced along the contact zones between the strata and earlier granitoids, whereas the second magmas were emplaced entirely within the earlier granitoid intrusions. The stage II and III fluids were characterized by relatively lower temperatures and low H–O isotopic values, indicating a gradual evolution from magmatic to meteoric sources.     

Geology,fluid inclusions,and geochemistry of the Zhazixi Sb–W deposit,Hunan, South China

The Zhazixi Sb–W deposit in the Xuefeng uplift, South China, exhibits a unique metal association of W and Sb, where the W orebodies are hosted by interlayer fractures and the Sb orebodies are contained within NW-trending faults. This study proposes that the W and Sb mineralization took place in two separate periods. The mineral paragenesis of the W mineralization reveals a mass of quartz, scheelite and minor calcite. The mineral assemblage of the Sb mineralization developed after W mineralization and consists of predominantly quartz and stibnite, and small amounts of native Sb, berthierite, chalcostibnite, pyrite, and chalcopyrite. Fluid inclusions in quartz and coexisting scheelite are dominated by two-phase, liquid-rich, aqueous inclusions at room temperature. Microthermometric studies suggest that ore-forming fluids for W mineralization are characterized by moderate temperatures (170–270 °C), low salinity (3–7 wt% NaCl equiv.), low density (0.75–0.95 g/cm³), and moderate to high pressure (57.2–99.7 MPa) and these fluids experienced a cooling and dilution evolution during W mineralization. Ore-forming fluids for Sb mineralization are epithermal types with low temperatures (150–230 °C), low salinity (4–6 wt% NaCl equiv.), moderate density (0.82–0.94 g/cm³), and high pressure (42.2–122.5 MPa) and these fluids display an evident decline in homogenization temperature during Sb mineralization. Laser Raman analyses of the vapor phase indicate that the ore-forming fluids for both W and Sb mineralization contain a small amount of CO₂.The ore-forming fluids for Sb mineralization are identified as predominantly originating from the continental crust, as suggested by the low ³He values (0.009 × 10⁻¹² cc.STP/g) and ³He/⁴He ratios (0.002–0.056 Ra) as well as high ³⁶Ar values (1.93 × 10⁻⁹ cc.STP/g) and ⁴⁰Ar/³⁶Ar ratios (909.5–2279.7). The source of S is identified to be the Neoproterozoic Wuqiangxi Formation, as traced by the δ³⁴S_V-CDT values of stibnite (3.1–9.4‰). The ²⁰⁸Pb/²⁰⁴Pb (37.643–40.222), ²⁰⁷Pb/²⁰⁴Pb (15.456–15.681), and ²⁰⁶Pb/²⁰⁴Pb (17.093–20.042) ratios suggest a mixture of lower crustal and supracrustal Pb sources.It is thus concluded that the ore genesis of the Zhazixi Sb–W deposit is related to the intracontinental orogeny during the early Mesozoic. Fluid mixing is considered to be the critical mechanism involved in W mineralization, whereas a fluid cooling process is responsible for Sb mineralization. Furthermore, the absence of Au is attributed to the low Σa_s content in Sb-mineralizing fluids.     

Metallogeny of the Shilu Fe–Co–Cu deposit,Hainan Island,South China: Constraints from fluid inclusions and stable isotopes

The Shilu deposit is a world-class Fe–Co–Cu orebody located in the Changjiang area of the western part of Hainan Island, South China. The distribution of Fe, Co, and Cu orebodies is controlled by strata of the No. 6 Formation in the Shilu Group and the Beiyi synclinorium. Based on a petrological study of the host rocks and their alteration assemblages, and textural and structural features of the ores, four mineralization stages have been identified: (1) the sedimentary ore-forming period; (2) the metamorphic ore-forming period; (3) the hydrothermal mineralization comprising the skarn and quartz–sulfide stage; and (4) the supergene period. The fluid inclusions in sedimentary quartz and/or chert indicate low temperatures (ca. 160 °C) and low salinities from 0.7 to 3.1 wt.% NaCl_eq, which corresponds to densities of 0.77 to 0.93 g/cm³. CO₂-bearing or carbonic inclusions have been interpreted to result from regional metamorphism. Homogenization temperatures of fluid inclusions for the skarn stage have a wide range from 148 °C to 497 °C and the salinities of the fluid inclusions range from 1.2 to 22.3 wt.% NaCl_eq, which corresponds to densities from 0.56 to 0.94 g/cm³. Fluid inclusions of the quartz–sulfide stage yield homogenization temperatures of 151–356 °C and salinities from 0.9 to 8.1 wt.% NaCl_eq, which equates to fluid densities from 0.63 to 0.96 g/cm³.Sulfur isotopic compositions indicate that sulfur of the sedimentary anhydrite and Co-bearing pyrite, and the quartz–sulfide stage, was derived from seawater sulfate and thermochemical sulfate reduction of dissolved anhydrite at temperatures of 200 °C and 300 °C, respectively. H and O isotopic compositions of the skarn and quartz–sulfide stage demonstrate that the ore-forming fluids were largely derived from magmatic water, with minor inputs from metamorphic or meteoric water. The Shilu iron ore deposit has an exhalative sedimentary origin, but has been overprinted by regional deformation and metamorphism. The Shilu Co–Cu deposit has a hydrothermal origin and is temporally and genetically associated with Indosinian granitoid rocks.     

K–Ar ages of plutonism and mineralization at the Shizhuyuan W–Sn–Bi–Mo deposit,Hunan Province,China

The Qianlishan granite complex, situated 16 km southeast of Chenzhou City, Hunan Province, China, hosts the Shizhuyuan W–Sn–Bi–Mo deposit. This complex, which intruded the Protozoic metasedimentary rocks and the Devonian clastic sedimentary and carbonate rocks, consists of mainly medium- to coarse-grained biotite granites and minor amounts of fine-grained biotite granite in addition to granite and quartz porphyry. K–Ar ages suggest three episodes of plutonism: the medium- to coarse-grained biotite granite (before 152 Ma), the fine-grained biotite granite (137 Ma), and the granite porphyry (129–131 Ma). Muscovite ages of the greisen are 145–148 Ma, suggesting that the W–Sn–Bi–Mo mineralization was related to the main, medium- to coarse-grained biotite granites. The K–Ar age of the hydrothermal vein mineralization is 92 Ma and is probably related to the porphyries.     

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.     

Magmatic–hydrothermal processes in Sangdong W–Mo deposit,Korea: Study of fluid inclusions and 39Ar–40Ar geochronology

The Sangdong scheelite–molybdenite deposit in northeast South Korea consists of strata-bound orebodies in intercalated carbonate-rich layers in the Cambrian Myobong slate formation. Among them, the M1 layer hosts the main orebody below which lie layers of F1–F4 host footwall orebodies. Each layer was first skarnized with the formation of a wollastonite + garnet + pyroxene assemblage hosting minor disseminated scheelite. The central parts of the layers were subsequently crosscut by two series of quartz veining events hosting minor scheelite and major scheelite–molybdenite ores, respectively. The former veins associate amphibole–magnetite (amphibole) alteration, whereas the latter veins host quartz–biotite–muscovite (mica) alteration. Deep quartz veins with molybdenite mineralization are hosted in the Cambrian Jangsan quartzite formation beneath the Myobong formation. In the Sunbawi area, which is in close proximity to the Sangdong deposit, quartz veins with scheelite mineralization are hosted in Precambrian metamorphic basement. Three muscovite ³⁹Ar–⁴⁰Ar ages between 86.6 ± 0.2 and 87.2 ± 0.3 Ma were obtained from M1 and F2 orebodies from the Sangdong deposit and Sunbawi quartz veins. The Upper Cretaceous age of the orebodies is concordant with the published ages of the hidden Sangdong granite, 87.5 ± 4.5 Ma. This strongly suggests that the intrusion is causative for the Sangdong W–Mo ores and Sunbawi veins.Fluid inclusions in the quartz veins from the M1 and F2 orebodies, the deep quartz-molybdenite veins, and the Sunbawi veins are commonly liquid-rich aqueous inclusions having bubble sizes of 10–30 vol%, apparent salinities of 2–8 wt% NaCl eqv., and homogenization temperatures of 180–350 °C. The densities of the aqueous inclusions are 0.70–0.94 g/cm³. No indication of fluid phase separation was observed in the vein. To constrain the formation depth in the Sangdong deposit, fluid isochores are combined with Ti–in–quartz geothermometry, which suggests that the M1 and F2 orebodies were formed at depths of 1–3 km and 5–6 km below the paleosurface, respectively. The similarity of the Cs (cesium) concentrations and Rb/Sr ratios in the fluid inclusions of the respective orebodies indicate an origin from source magmas having similar degrees of fractionation and enrichment of incompatible elements such as W and Mo. High S concentrations in the fluids and possibly organic C in the sedimentary source likely promoted molybdenite precipitation in the Sangdong orebodies, whereas the scheelite deposition in the deep quartz–molybdenite veins hosted in the quartzite is limited by a lack of Ca and Fe in the hydrothermal fluids. The molybdenite deposition in the Sunbawi quartz–molybdenite veins hosted in the Precambrian metamorphic basement rocks was possibly limited by a lack of reducing agents such as organic C.     

Zircon U–Pb,molybdenite Re–Os and muscovite Ar–Ar isotopic dating of the Xitian W–Sn polymetallic deposit,eastern Hunan Province,South China and its geological significance

The Xitian tungsten–tin (W–Sn) polymetallic deposit, located in eastern Hunan Province, South China, is a recently explored region containing one of the largest W–Sn deposits in the Nanling W–Sn metallogenic province. The mineral zones in this deposit comprise skarn, greisen, structurally altered rock and quartz-vein types. The deposit is mainly hosted by Devonian dolomitic limestone at the contact with the Xitian granite complex. The Xitian granite complex consists of Indosinian (Late Triassic, 230–215 Ma) and Yanshanian (Late Jurassic–Early Cretaceous, 165–141 Ma) granites. Zircons from two samples of the Xitian granite dated using laser ablation-inductively coupled mass spectrometer (LA-ICPMS) U–Pb analysis yielded two ages of 225.6 ± 1.3 Ma and 151.8 ± 1.4 Ma, representing the emplacement ages of two episodic intrusions of the Xitian granite complex. Molybdenites separated from ore-bearing quartz-veins yielded a Re–Os isochron age of 149.7 ± 0.9 Ma, in excellent agreement with a weighted mean age of 150.3 ± 0.5 Ma. Two samples of muscovites from ore-bearing greisens yielded ⁴⁰Ar/³⁹Ar plateau ages of 149.5 ± 1.5 Ma and 149.4 ± 1.5 Ma, respectively. These isotopic ages obtained from hydrothermal minerals are slightly younger than the zircon U–Pb age of 151.8 ± 1.4 Ma of the Yanshanian granite in the Xitian area, indicating that the W–Sn mineralization is genetically related to the Late Jurassic magmatism. The Xitian deposit is a good example of the Early Yanshanian regional W–Sn ore-forming event (160–150 Ma) in the Nanling region. The relatively high Re contents (8.7 to 44.0 ppm, average of 30.5 ppm) in molybdenites suggest a mixture of mantle and crustal sources in the genesis of the ore-forming fluids and melts. Based upon previous geochemical studies of Early Yanshanian granite and regional geology, we argue that the Xitian W–Sn polymetallic deposit can be attributed to back-arc lithosphere extension in the region, which was probably triggered by the break-off of the flat-slab of the Palae-Pacific plate beneath the lithosphere.     

Hydrothermal evolution of the Sar-Cheshmeh porphyry Cu–Mo deposit,Iran: Evidence from fluid inclusions

The Sar-Cheshmeh porphyry Cu–Mo deposit is located in Southwestern Iran (∼65 km southwest of Kerman City) and is associated with a composite Miocene stock, ranging in composition from diorite through granodiorite to quartz-monzonite. Field observations and petrographic studies demonstrate that the emplacement of the Sar-Cheshmeh stock took place in several pulses, each with associated hydrothermal activity. Molybdenum was concentrated at a very early stage in the evolution of the hydrothermal system and copper was concentrated later. Four main vein Groups have been identified: (I) quartz+molybdenite+anhydrite±K-feldspar with minor pyrite, chalcopyrite and bornite; (II) quartz+chalcopyrite+pyrite±molybdenite±calcite; (III) quartz+pyrite+calcite±chalcopyrite±anhydrite (gypsum)±molybdenite; (IV) quartz±calcite±gypsum±pyrite±dolomite. Early hydrothermal alteration produced a potassic assemblage (orthoclase-biotite) in the central part of the stock, propylitic alteration occurred in the peripheral parts of the stock, contemporaneously with potassic alteration, and phyllic alteration occurred later, overprinting earlier alteration. The early hydrothermal fluids are represented by high temperature (350–520 °C), high salinity (up to 61 wt% NaCl equivalent) liquid-rich fluid inclusions, and high temperature (340–570 °C), low-salinity, vapor-rich inclusions. These fluids are interpreted to represent an orthomagmatic fluid, which cooled episodically; the brines are interpreted to have caused potassic alteration and deposition of Group I and II quartz veins containing molybdenite and chalcopyrite. Propylitic alteration is attributed to a liquid-rich, lower temperature (220–310 °C), Ca-rich, evolved meteoric fluid. Influx of meteoric water into the central part of the system and mixing with magmatic fluid produced albitization at depth and shallow phyllic alteration. This influx also caused the dissolution of early-formed copper sulphides and the remobilization of Cu into the sericitic zone, the main zone of the copper deposition in Sar-Cheshmeh, where it was redeposited in response to a decrease in temperature.     

Refertilization of serpentinites in the Sulu UHP terrane,Eastern China: constraints from geochronology,mineral composition,geochemistry, and Re–Os isotopes

ABSTRACT

Serpentinites from Junan (JN), Rizhao (RZ), and Rongcheng (RC) in the Sulu ultra-high-pressure (UHP) terrane, China, were analysed for U–Pb zircon geochronology, mineral chemistry, whole-rock major and trace element chemistry (including rare-earth elements (REEs) and platinum-group elements (PGEs)), and Re–Os isotopes, in order to better constrain their petrogenesis and geodynamic process. The serpentinite zircons yield two age groups: 731 ± 10 to 780 ± 10 Ma for relic magmatic zircon cores, which may indicate early crystallization and emplacement of the peridotite in the Yangtze crust, and 209 ± 2 to 218 ± 3 Ma for metamorphic zircon, which coincides with Triassic UHP metamorphism. The spinels in the serpentinites exhibit significant Cr# variation (0.6–0.91) and have undergone multi-stage metamorphism. The serpentinites are characterized by enrichment in incompatible trace elements, low Ni and IPGE concentrations, and high Pd/Ir ratios, and the bulk-rock major elements plot in the ultramafic cumulate region. Their Re and Os concentrations are similar to those of typical orogenic peridotite, but they have high ¹⁸⁷Os/¹⁸⁸Os ratios (0.12433–0.14423). We believe that the serpentinite’s protolith consisted of cumulates from an asthenosphere-derived melt that intruded into the continental crust of the Yangtze craton in the Neoproterozoic. These cumulates were later subducted and metamorphosed during the subduction of the Yangtze craton in the Triassic. The serpentinites underwent melt–rock interactions and fluid enrichment, both prior to and during serpentinization.     

Genesis of the Huangshannan high-Ni tenor magmatic sulfide deposit in the Eastern Tianshan,northwest China: Constraints from PGE geochemistry and Os–S isotopes

The Huangshannan magmatic Ni-Cu sulfide deposit is one of a group of Permian magmatic Ni-Cu deposits located in the southern Central Asian Orogenic belt in the Eastern Tianshan, northwest China. It is characterized by elevated Ni tenor (concentrations in recalculated 100% sulfide) in sulfide within ultramafic rocks (9–19 wt%), with values much higher than other deposits in the region. Sulfides of the Huangshannan deposit are composed of pentlandite, chalcopyrite, and pyrrhotite and the host rock is relatively fresh, indicating that the high-Ni tenor is a primary magmatic feature rather than formed by alteration processes. It is shown that sulfides with high-Ni tenor can be generated by sulfide-olivine equilibrium at an oxygen fugacity of QFM +0.5, for magmas containing 450 ppm Ni and 20% olivine. Ores with >10 wt% sulfur have relatively low PGE and Ni tenors compared to other ores, R factor (mass ratio of silicate to sulfide liquid) modeling of Ni indicates that they formed at moderate R values (150–600). Based on this constraint on R values, ores with <10 wt% sulfides in the Huangshannan deposit can be segregated from a similar parental magma with 0.05 ppb Os, 0.023 ppb Ir, and 0.5 ppb Pd at R values between 600 and 3000. This, coupled with the supra-cotectic proportions of sulfide liquid to cumulus silicates in the Huangshannan ores imply mechanical transport and deposition of sulfide liquid in a magma pathway or conduit, in which sulfides must have interacted with large volumes of silicate magma. Platinum and Pd depletion relative to other platinum group elements (PGEs) are observed in fresh and sulfide-rich samples (S > 4.5 wt%). As sulfide-rich samples are also depleted in Cu, and as interstitial sulfides in those samples are physically interconnected at a scale of several cms, the low Pt and Pd anomalies are attributed to solid Pt and Pd phases crystallization and retention with the monosulfide solid solution (MSS) and Cu-rich sulfide liquid percolation during MSS fractionation. This finding indicates that Pt anomalies in sulfide-rich rocks from magmatic Ni-Cu deposits in the Eastern Tianshan are the result of sulfide fractionation rather than a hydrothermal effect. ¹⁸⁷Os/¹⁸⁸Os_(278Ma) values of the lherzolite samples vary from 0.27 to 0.37 and γOs_(278Ma) values vary from 110 to 189, indicating significant magma interaction with crustal sulfides, rich in radiogenic Os. Well constrained γOs values and δ³⁴S values (−0.4 to 0.8‰) indicate that crustal contamination occurred at depth before the arrival of the magma in the Huangshannan chamber. Regionally, deposits with high-Ni tenor have not been reported other than the Huangshannan deposit; however, many intrusions with high-Ni contents in olivine are present in NW China, such as the Erhongwa, Poyi and Poshi intrusions. Those intrusions are capable of forming high-Ni tenor sulfides due to olivine-sulfide-silicate equilibrium and relative high-Ni content in parent magma, making them attractive exploration targets.     

Stable isotope geochemistry and Re–Os ages of the Yinan gold deposit,Shandong Province,northeastern China

The Yinan gold deposit in the Luxi area of Shandong Province in northeastern China is a skarn-type ore deposit. In this article, we present results from sulphur, lead, carbon–oxygen, and helium–argon isotope chemistry to characterize the ore genesis and source features. We also present rhenium–osmium ages from molybdenite to evaluate the timing of ore formation. The δ³⁴S values of pyrite from the ore deposit range from 0.7‰ to 5.60‰ with a mean at 2.70‰, close to mantle and meteorite sulphur. Among Pb isotopes, ²⁰⁶Pb/²⁰⁴Pb values range from 18.375 to 18.436, ²⁰⁷Pb/²⁰⁴Pb values from 15.694 to 15.8, and ²⁰⁸Pb/²⁰⁴Pb values from 38.747 to 39.067. The δ¹³C values of calcite associated with the ores range from ?0.2‰ to ?0.5‰ and their δ¹⁸O values show variation from 9.4‰ to 12.6‰, suggesting a mixed fluid source. The ³He/⁴He and ⁴⁰Ar/³⁶Ar ratios of fluids trapped in pyrite are in the range of 0.27–1.11 Ra and 439.4–826, respectively, with calculated proportion of the mantle-derived He ranging from 3.25% to 14.03% and atmosphere argon ranging from 35.8% to 67.3%. The data suggest that the ore-forming fluids were derived from the crust and were mixed with a distinct contribution of mantle helium. The Re and Os values vary from 32 × 10^?6 to 93.02 × 10^?6 and from 0.01 × 10^?9 to 0.34 × 10^?9, respectively. The model ages of molybdenite range from 126.96 ± 1.82 Ma to 129.49 ± 2.04 Ma, with a weighted mean age of 128.08 ± 0.75 Ma and isochron age of 130.3 ± 3 Ma. These ages are close to the age of the associated quartz diorite porphyrite pluton, suggesting a close relationship between Cretaceous magmatism and metallogeny in NE China. A comparison of the Yinan gold deposit in the Luxi area with those of the Jiaodong area shows that the contrast in metallogenic features between the two are linked with the tectonic and geodynamic history.     

Re–Os molybdenite ages and zircon Hf isotopes of the Gangjiang porphyry Cu–Mo deposit in the Tibetan Orogen

The Miocene porphyry Cu–(Mo) deposits in the Gangdese orogenic belt in southern Tibet were formed in a post-subduction collisional setting. They are closely related to the Miocene adakite-like porphyries which were probably derived from a thickened basaltic lower crust. Furthermore, mantle components have been considered to have played a crucial role in formation of these porphyry deposits (Hou et al. Ore Geol Rev 36: 25–51, 2009; Miner Deposita doi:10.1007/s00126-012-0415-6, 2012). In this study, we present zircon Hf isotopes and molybdenite Re–Os ages on the newly discovered Gangjiang porphyry Cu–Mo deposit in southern Tibet to constrain the magma source of the intrusions and the timing of mineralization. The Gangjiang porphyry Cu–Mo deposit is located in the Nimu ore field in the central Gangdese porphyry deposits belt, southern Tibet. The copper and molybdenum mineralization occur mainly as disseminations and veins in the overlapped part of the potassic and phyllic alteration zones, and are predominantly hosted in the quartz monzonite stock and in contact with the rhyodacite porphyry stock. SIMS zircon U–Pb dating of the pre-mineral quartz monzonite stock and late intra-mineral rhyodacite porphyry yielded ages of 14.73?±?0.13 Ma (2σ) and 12.01?±?0.29 Ma (2σ), respectively. These results indicate that the magmatism could have lasted as long as about 2.7 Ma for the Gangjiang deposit. The newly obtained Re–Os model ages vary from 12.51?±?0.19 Ma (2σ) to 12.85?±?0.18 Ma (2σ) for four molybdenite samples. These Re–Os ages are roughly coincident with the rhyodacite porphyry U–Pb zircon age, and indicate a relatively short-lived episode of ore deposition (ca. 0.3 Ma). In situ Hf isotopic analyses on zircons by using LA-MC-ICP-MS indicate that the ε _Hf(t) values of zircons from a quartz monzonite sample vary from +2.25 to +4.57 with an average of +3.33, while zircons from a rhyodacite porphyry sample vary from +5.53 to +7.81 with an average of +6.64. The Hf data indicate that mantle components could be partly involved in the deposit formation, and that mantle contributions might have increased over time from ca. 14.7 to 12.0 Ma. Combined with previous works, it is proposed that the Gangjiang deposit could have resulted from the convective thinning of the lithospheric root, and the input of upper mantle components into the magma could have played a key role in the formation of the porphyry deposits in the Miocene Gangdese porphyry copper belt in the Tibetan Orogen.     

Late Cretaceous metallogeny in the Zhongdian area: Constraints from Re–Os dating of molybdenite and pyrrhotite from the Hongshan Cu deposit,Yunnan, China

The Zhongdian area in Yunnan, southwestern China, located at the southern end of the Yidun volcano-magmatic arc that was formed during the Triassic westward subduction of the Gaze-Litang Ocean, hosts numerous Triassic large porphyry and skarn deposits. The arc suffered Jurassic to Cretaceous arc-continental orogenic collision and Cenozoic intracontinental strike-slip shearing. The Hongshan Cu (–Mo–Pb–Zn) deposit is potentially a large deposit and contains two ore types: 1) predominant layered skarn Cu–(Pb–Zn) ores along marble-hornfels contacts; and 2) minor crosscutting vein-type Cu–Mo mineralization. Previous research forwards a two-stage genetic model without sufficient dating evidence, supposing the skarn mineralization is related to the Triassic calc-alkalic intrusions and the vein-type mineralization related to Cretaceous quartz monzonite porphyries. Re–Os dating of molybdenite from vein-type ores and quartz monzonite porphyries and that of pyrrhotite from skarn ores are presented here to constrain the mineralization age and rebuild the genetic model. Analyses of eight molybdenite samples yield an isochron age of 79.7 ± 3.1 Ma (MSWD = 9.2) for the vein-type mineralization and a model age of 81.9 ± 1.1 Ma for the quartz monzonite porphyries. Isotope data on seven pyrrhotite samples from the skarn ores yield an isochron age of 79 ± 16 Ma z(MSWD = 8.4). The Re–Os ages for the two ore types are concordant within analytical errors, indicating that the Hongshan deposit was formed in the Late Cretaceous. Elevated Re contents in molybdenite (13.65 to 63.91 μg/g) and extremely radiogenic initial ¹⁸⁷Os/¹⁸⁸Os ratios in pyrrhotite (0.7673 to 0.8184; weighted average 0.796 ± 0.038), together with elevated γ_Os values in pyrrhotite (507 to 547; average 528) imply a significant crustal component in the ore-forming materials that was likely derived from a lower crustal reservoir. Combined with the tectonic evolution of the Zhongdian area and geochemical characteristics of corresponding intrusions, the ages of mineralization obtained in this study indicate that the Hongshan deposit was formed in a post-collision setting with a genetic relationship to the emplacement of the quartz monzonite porphyry. These results provide significant new information for the study and exploration of the Late Cretaceous metallogeny in the Zhongdian area.     

Genesis of the Au–Bi–Cu–As, Cu–Mo ± W, and base–metal Au–Ag mineralization at the Mountain Freegold (Yukon, Canada): constraints from Ar–Ar and Re–Os geochronology and Pb and stable isotope compositions

The genesis of mineralized systems across the Mountain Freegold area, in the Dawson Range Cu–Au?±?Mo Belt of the Tintina Au province was constrained using Pb and stable isotope compositions and Ar–Ar and Re–Os geochronology. Pb isotope compositions of sulfides span a wide compositional range (²⁰⁶Pb/²⁰⁴Pb, 18.669–19.861; ²⁰⁸Pb/²⁰⁴Pb, 38.400–39.238) that overlaps the compositions of the spatially associated igneous rocks, thus indicating a magmatic origin for Pb and probably the other metals. Sulfur isotopic compositions of sulfide minerals are broadly similar and their δ³⁴S (Vienna-Canyon Diablo Troilite (V-CDT)) values range from ?1.4 to 3.6 ‰ consistent with the magmatic range, with the exception of stibnite from a Au–Sb–quartz vein, which has δ³⁴S values between ?8.1 and ?3.1 ‰. The δ³⁴S values of sulfates coexisting with sulfide are between 11.2 and 14.2 ‰; whereas, those from the weathering zone range from 3.7 to 4.3 ‰, indicating supergene sulfates derived from oxidation of hypogene sulfides. The δ¹³C (Vienna Peedee Belemnite (VPDB)) values of carbonate range from ?4.9 to 1.1 ‰ and are higher than magmatic values. The δ¹⁸O (V-SMOW) values of magmatic quartz phenocrysts and magmatic least-altered rocks vary between 6.2 and 10.1 ‰ and between 5.0 and 10.1 ‰, respectively, whereas altered magmatic rocks and hydrothermal minerals (quartz and magnetite) are relatively ¹⁸O-depleted (4.2 to 7.9 ‰ and ?6.3 to 1.5 ‰, respectively). Hydrogen isotope compositions of both least-altered and altered igneous rock samples are D-depleted (from ?133 to ?161 ‰ Vienna-Standard Mean Ocean Water (V-SMOW)), consistent with differential magma degassing and/or post-crystallization exchange between the rocks and meteoric ground water. Zircon from a chlorite-altered dike has a U–Pb crystallization age of 108.7?±?0.4 Ma; whereas, the same sample yielded a whole-rock Ar–Ar plateau age of 76.25?±?0.53 Ma. Likewise, molybdenite Re–Os model ages range from 75.8 to 78.2 Ma, indicating the mineralizing events are genetically related to Late Cretaceous volcano-plutonic intrusions in the area. The molybdenite Re–Os ages difference between the nearby Nucleus (75.9?±?0.3 to 76.2?±?0.3 Ma) and Revenue (77.9?±?0.3 to 78.2?±?0.3 Ma) mineral occurrences suggests an episodic mineralized system with two pulses of hydrothermal fluids separated by at least 2 Ma. This, in combination with geological features suggest the Nucleus deposit represents the apical and younger portion of the Revenue–Nucleus magmatic-hydrothermal system and may suggest an evolution from the porphyry to the epithermal environments.     

Mineralization,alteration, structure,and Re–Os age of the Lanjiagou porphyry Mo deposit,North China Craton

Lanjiagou is a porphyry Mo deposit in terms of its alteration zonation and mineralization associated with granitic intrusions and predominance of quartz vein-hosted molybdenum mineralization. It is the largest Mo deposit in North China Craton (404,000 t). There is an intimate spatial/temporal association between all stages of mineralization and Early Jurassic granitic intrusions at Lanjiagou. Most of the molybdenum was emplaced during the principal hydrothermal (PH) stage (184.6 ± 1.3 – 185.6 ± 1.4 Ma), contemporaneously with intrusion of fine-grained porphyritic granite (188.9 ± 1.2 Ma) into a granite batholith (193 ± 3 Ma). The PH mineralization stage is mainly hosted by a quartz-dominated stockwork associated with phyllic alteration in the fine-grained porphyritic granite. This stage was followed by the late hydrothermal (LH) activity. Thick Mo-rich quartz veins were emplaced during the LH stage and cut the porphyry ore bodies. A ring breccia zone formed during the last hydrothermal stage and apparently cuts both the porphyry and the quartz vein ore bodies. The main hydrothermal vein stages have predominantly concentric and radial vein orientations centred on the ring breccia zone. Most of the concentric veins have shallow dips, whereas the radial veins are subvertical. The LH veins have predominantly NEE and NW orientations in the deposit and are moderately inclined. We surmise that the veining was controlled by the local stress regime generated by the intrusion of a large, deep pluton that we interpreted to be the source of the granites, the breccia zone, and the molybdenum mineralization. Resurgence within the magma chamber reactivated the steep concentric structures in a reverse sense, and accumulation of magmatic and/or fluid pressure resulted in explosive brecciation, producing the ring breccia zone. A predominantly late set of NW-trending, post-ore felsic dikes, associated with the regional structures, are a consequence of far-field stresses exceeding local stresses in the deposit.     

Re–Os isotopic dating of molybdenite and pyrite in the Baishan Mo–Re deposit, eastern Tianshan, NW China, and its geological significance

The Baishan Mo–Re deposit is located in the eastern section of the eastern Tianshan orogenic belt, NW China. The deposit has a grade of 0.06% Mo and a high content of rhenium of 1.4 g/t. Rhenium and osmium isotopes in sulfide minerals from the Baishan deposit are used to determine the age of mineralization. Rhenium concentrations in molybdenite samples are between 74 and 250 g/g. Analysis of eight molybdenite samples yields an isochron age of 224.8±4.5 Ma (2). Pyrite samples have rhenium and osmium concentrations varying in the range 33.4–330.6 ng/g and 0.08–0.81 ng/g, respectively. Isotope data on seven pyrite samples yield an isochron age of 225±12 Ma (2) on the ¹⁸⁷Re/¹⁸⁸Os versus ¹⁸⁷Os/¹⁸⁸Os plot and an age of 233±14 Ma (2) on the ¹⁸⁷Os versus ¹⁸⁷Re correlation diagram. The ages of molybdenite and pyrite are consistent within the analytical errors. Combined with field observations, the data indicate that Mo–Re mineralization in the Baishan deposit is produced by a magmatic-hydrothermal event in an intracontinental extensional setting after late Paleozoic orogeny. The initial ¹⁸⁷Os/¹⁸⁸Os ratio of pyrite is 0.3±0.07. The ³⁴S values of molybdenite vary from +0.5 to +3.6. Both data indicate that mineralization is derived mainly from a mantle source.Editorial handling: J. Richards     

Late Jurassic Sn metallogeny in eastern Guangdong,SE China coast: Evidence from geochronology,geochemistry and Sr–Nd–Hf–S isotopes of the Dadaoshan Sn deposit

The newly discovered Dadaoshan Sn deposit is located in the eastern Guangdong Sn–W province, coastal SE China. The Sn mineralization, hosted in Jurassic porphyritic granite and the Lower Jurassic Jinji Formation sedimentary wall rocks, is considered to be granite-related. In this study, the porphyritic granite was LA–ICP–MS zircon U–Pb dated to be 153.2 ± 1.2 Ma, consistent with the syn-mineralization molybdenite Re–Os age of 152.6 ± 1.8 Ma. The porphyritic granite samples are weakly peraluminous (A/CNK = 1.0–1.1) and high-K calc-alkaline. The rocks contain high SiO₂ (72.9–75.6 wt%), moderate Rb/Sr (5–9) and low ΣREE (136–223 ppm). They are enriched in F, Li, Rb and Sn, depleted in Ba, Sr, P, Zr, Th, Nb and Y, and have distinct negative Eu anomalies (δEu = 0.09–0.18), suggesting that the porphyritic granite is highly fractionated I-type granite. The calculated initial ⁸⁷Sr/⁸⁶Sr (0.711582–0.715173), relatively low ɛ_Nd(t) (−9.48 to −8.54; T_DM2 = 1638–1814 Ma), and the zircon ε_Hf(t) (−14.2 to −5.1; two-stage model ages = 1528–2103 Ma) all suggest that the granite was mainly crustal-derived with little mantle input. Sulfur isotopic compositions for the sulfides (arsenopyrite and chalcopyrite: δ³⁴S = −1.1 to 1.4‰, average = −0.1) imply a dominantly magmatic sulfur source. The calculated zircon Ce⁴⁺/Ce³⁺ and Eu_N/Eu_N¹ ratios of the Dadaoshan granite range from 1.0 to 112 (mean = 31.7) and from 0.04 to 0.37 (mean = 0.14), respectively, indicating a low oxygen fugacity for the magma. The reducing and highly fractionated nature of the Dadaoshan granitic magma may have played a key role in the Sn mineralization.It was previously argued that the Jurassic Sn–W mineralization and its causative magmatism were largely confined in the South China interior, e.g., the Nanling Range. Our new data suggest that the Late Jurassic Sn–W mineralization and its causative magmatism actually extended to the SE China coastal area. The Dadaoshan granite may have been generated from partial crustal melting led by underplating of mantle-derived magmas in an extensional environment. Regional extension may have been related to the west-directed, flat-slab subduction and delamination of the Paleo-Pacific (Izanagi) plate beneath the South China block. Another suite of Early Cretaceous Sn–W-bearing granitic rocks in eastern Guangdong may have mainly been crustal-derived with minor mantle input, and likely occurred under back-arc extensional setting led by the Paleo-Pacific subduction rollback.     

Collision-related genesis of the Sharang porphyry molybdenum deposit,Tibet: Evidence from zircon U–Pb ages,Re–Os ages and Lu–Hf isotopes

Sharang is a low-fluorine, calc-alkaline porphyry Mo deposit hosted mainly in a granite porphyry of a multi-stage plutonic complex in the northern Gangdese metallogenic belt, largely with stockwork and ribbon-textured mineralization. The observed age estimates suggest that the formation of the magmatic host complex (52.9–51.6 Ma) and the ore deposit itself (52.3 Ma) occurred during the main stage of the India–Asia collision. The host rocks are characterized by lower zircon ε_Hf(t) values than those of the pre-ore and post-ore rocks. This suggests that the Lhasa terrane basement might play an important role in the formation of Sharang ore-forming intrusions. In view of the framework of magmatic–metallogenic events we suggest that slab roll-back may have induced melting of juvenile crust and ancient continental complexes during the India–Asia collision. This proposal focuses exploration for additional molybdenum deposits on the collision zone.