Geological characteristics and genesis of the Laoshankou Fe–Cu–Au deposit in Junggar,Xinjiang, Central Asian Orogenic Belt

The Laoshankou Fe–Cu–Au deposit is located at the northern margin of Junggar Terrane, Xinjiang, China. This deposit is hosted in Middle Devonian andesitic volcanic breccias, basalts, and conglomerate-bearing basaltic volcanic breccias of the Beitashan Formation. Veined and lenticular Fe–Cu–Au orebodies are spatially and temporally related to diorite porphyries in the ore district. Wall–rock alteration is dominated by skarn (epidote, chlorite, garnet, diopside, actinolite, and tremolite), with K–feldspar, carbonate, albite, sericite, and minor quartz. On the basis of field evidence and petrographic observations, three stages of mineralization can be distinguished: (1) a prograde skarn stage; (2) a retrograde stage associated with the development of Fe mineralization; and (3) a quartz–sulfide–carbonate stage associated with Cu–Au mineralization. Electron microprobe analysis shows that garnets and pyroxenes are andradite and diopside-dominated, respectively. Fluid inclusions in garnet yield homogenization temperatures (T_h) of 205–588 °C, and salinities of 8.95–17.96 wt.% NaCl equiv. In comparison, fluid inclusions in epidote and calcite yield T_h of 212–498 and 150–380 °C, and salinities of 7.02–27.04 and 13.4–18.47 wt.% NaCl equiv., respectively. Garnets yield values of 6.4‰ to 8.9‰ δ¹⁸O_fluid, whereas calcites yield values of − 2.4‰ and 4.2‰ δ¹⁸O_fluid, and − 0.9‰ to 2.4‰ δ¹³C_PDB, indicating that the ore-forming fluids were dominantly magmatic fluids in the early stage and meteoric water in the late stage. The δ³⁴S values of sulfides range from − 2.6‰ to 5.4‰, indicating that the sulfur in the deposit was probably derived from deep-seated magmas. The diorite porphyry yields LA–MC–ICP–MS zircon U–Pb age of 379.7 ± 3.0 Ma, whereas molybdenites give Re–Os weighted mean age of 383.2 ± 4.5 Ma (MSWD = 0.06). These ages suggest that the mineralization-related diorite porphyry was emplaced during the Late Devonian, coincident with the timing of mineralization within the Laoshankou Fe–Cu–Au deposit. The geological and geochemical evidence presented here suggest that the Laoshankou Fe–Cu–Au deposit is a skarn deposit.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

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.     

Origin and evolution of hydrothermal fluids in the Taochong iron deposit,Middle–Lower Yangtze Valley,Eastern China: Evidence from microthermometric and stable isotope analyses of fluid inclusions

The Middle–Lower Yangtze River Valley is one of the most important metallogenic belts in China, hosting numerous Cu–Fe–Au–Mo deposits. The Taochong deposit is located in the northern part of the Fanchang iron ore district of the Middle–Lower Yangtze River metallogenic belt. The Fe-orebody is hosted by Middle Carboniferous to Lower Permian limestones. Skarns and Fe-orebodies occur as tabular bodies along interlayer-gliding faults, at some distance from the inferred granitic intrusions. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity—the skarn, iron oxide (main mineralization stage), and carbonate stages—all contributed to the formation of the Taochong iron deposit. The skarn stage is characterized by the formation of garnet and pyroxene, with high-temperature, hypersaline hydrothermal fluids with isotopic compositions similar to those of typical magmatic fluids. These fluids were probably generated by the separation of brine from a silicate melt instead of the product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by actinolite, chlorite, quartz, calcite and hematite. The hydrothermal fluids at this stage are represented by saline fluid inclusions that coexist with vapor-rich inclusions with anomalously low δD values (− 66‰ to − 94‰). The decrease in ore fluid δ¹⁸O_water with time and decreasing depth is consistent with the decreases in fluid salinity and temperature. The fluid δD values also show a decreasing trend with decreasing depth. Both fluid inclusion and stable isotopic data suggest that the ore fluid during the main period of mineralization was evolved by the boiling of various mixtures of magmatic brine and meteoric water. This process was probably induced by a drop in pressure from lithostatic to hydrostatic. The carbonate stage is represented by calcite veins that cut across the skarn and orebody, locally producing a dense stockwork. This observation indicates the veins formed during the waning stages of hydrothermal activity. The fluids from this stage are mainly represented by a variety of low-salinity fluid inclusions, as well as fewer high-salinity inclusions. These particular fluids have the lowest δ¹⁸O_water values (− 2.2‰ to 0.4‰) and a wide of range of δD values (− 40‰ to − 81‰), which indicate that they were originated from a mixture of residual fluids from the oxide stage, various amounts of meteoric water, and possibly condensed vapor. Low-temperature boiling probably occurred during this stage.We also discuss the reasons behind the anomalously low δD values in fluid inclusion water extracted by thermal decrepitation from quartz at high temperatures, and suggest that calcite data provide a possible benchmark for adjusting low δD values found in quartz intergrown with calcite.     

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

Geology and genesis of Kafang Cu–Sn deposit,Gejiu district,SW China

Kafang is one of the main ore deposits in the world-class Gejiu polymetallic tin district, SW China. There are three main mineralization types in the Kafang deposit, i.e., skarn Cu–Sn ores, stratiform Cu ores hosted by basalt and stratiform Cu–Sn ores hosted by carbonate. The skarn mainly consists of garnet and pyroxene, and retrograde altered rocks. These retrograde altered rocks are superimposed on the skarn and are composed of actinolite, chlorite, epidote and phlogopite. Major ore minerals are chalcopyrite, pyrrhotite, cassiterite, pyrite and scheelite. Sulfur and Pb isotopic components hint that the sources of different types of mineralization are distinctive, and indicate that the skarn ore mainly originated from granitic magma, whereas the basalt-hosted Cu ores mainly derived from basalt. Microthermometry results of fluid inclusions display a gradual change during the ore-forming process. The homogenization temperature of different types of inclusions continuously decreases from early to late mineralization stages. The salinities and freezing temperatures exhibit similar evolutionary tendencies with the T _{homogenization}, while the densities of the different types keep constant, the majority being less than 1. Oxygen and hydrogen isotopic values (δ¹⁸O and δD) of the hydrothermal fluids fall within ranges of 3.1 to 7.7‰ with an average of 6.15‰, calculated at the corresponding homogenization temperature, and − 73 and − 98‰ with an average of − 86.5‰, respectively. Microthermometry data and H–O isotopes indicate that the ore-forming fluid of the Kafang deposit is mainly derived from magma in the early stage and a mixture of meteoric and magmatic water in late stage. Molybdenite Re–Os age of the skarn type mineralization is 83.4 ± 2.1 Ma, and the stratiform ores hosted by basalt is 84.2 ± 7.3 Ma, which are consistent with the LA-ICP-MS zircon age of the Xinshan granite intrusion (83.1 ± 0.4 Ma). The evidence listed above reflects the fact that different ore styles in the Kafang deposit belong to the same mineralization system.     

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.     

Ore genesis and hydrothermal evolution of the Huanggang skarn iron–tin polymetallic deposit,southern Great Xing'an Range: Evidence from fluid inclusions and isotope analyses

The southern Great Xing'an Range is one of the most important metallogenic belts in northern China, and contains numerous Pb–Zn–Ag–Cu–Sn–Fe–Mo deposits. The Huanggang iron–tin polymetallic skarn deposit is located in the Sn-polymetallic metallogenic sub-belt. Skarns and iron orebodies occur as lenses along the contact between granite plutons and the Lower Permian Huanggangliang Formation marble or Dashizhai Formation andesite. Field evidence and petrographic observations indicate that the three stages of hydrothermal activity, i.e., skarn, oxide and sulfide stages, all contributed to the formation of the Huanggang deposit.The skarn stage is characterized by the formation of garnet and pyroxene, and high-temperature, hypersaline hydrothermal fluids with isotopic compositions that are similar to those of typical magmatic fluids. These fluids most likely were generated by the separation of brine from a silicate melt instead of being a product of aqueous fluid immiscibility. The iron oxide stage coincides with the replacement of garnet and pyroxene by amphibole, chlorite, quartz and magnetite. The hydrothermal fluids of this stage are represented by L-type fluid inclusions that coexist with V-type inclusions with anomalously low δD values (approximately − 100 to − 116‰). The decrease in ore fluid δ¹⁸O_H2O values with time coincides with marked decreases in the fluid salinity and temperature. Based on the fluid inclusion and stable isotopic data, the ore fluid evolved by boiling of the magmatic brine. The sulfide stage is characterized by the development of sphalerite, chalcopyrite, fluorite, and calcite veins, and these veins cut across the skarns and orebodies. The fluids during this stage are represented by inclusions with a variable but continuous sequence of salinities, mainly low-salinity inclusions. These fluids yield the lowest δ¹⁸O_H2O values and moderate δD values ( − 1.6 to − 2.8‰ and − 101 to − 104‰, respectively). The data indicate that the sulfide stage fluids originated from the mixing of residual oxide-stage fluids with various amounts of meteoric water. Boiling occurred during this stage at low temperatures.The sulfur isotope (δ³⁴S) values of the sulfides are in a narrow range of − 6.70 to 4.50‰ (mean = − 1.01‰), and the oxygen isotope (δ¹⁸O) values of the magnetite are in a narrow range of 0.1 to 3.4‰. Both of these sets of values suggest that the ore-forming fluid is of magmatic origin. The lead isotope compositions of the ore (²⁰⁶Pb/²⁰⁴Pb = 18.252–18.345, ²⁰⁷Pb/²⁰⁴Pb = 15.511–15.607, and ²⁰⁸Pb/²⁰⁴Pb = 38.071–38.388) are consistent with those of K-feldspar granites (²⁰⁶Pb/²⁰⁴Pb = 18.183–18.495, ²⁰⁷Pb/²⁰⁴Pb = 15.448–15.602, ²⁰⁸Pb/²⁰⁴Pb = 37.877–38.325), but significantly differ from those of Permian marble (²⁰⁶Pb/²⁰⁴Pb = 18.367–18.449, ²⁰⁷Pb/²⁰⁴Pb = 15.676–15.695, ²⁰⁸Pb/²⁰⁴Pb = 38.469–38.465), which also suggests that the ore-forming fluid is of magmatic origin.     

Genesis of the Saishitang skarn type copper deposit,West Qinling,Qinghai Province: Evidence from fluid inclusions and stable isotopes

The Saishitang skarn type copper deposit, located in the southeast part of the Dulan–Ela Mountain Triassic volcanic–magmatic arc and forearc accretionary wedge, belongs to the Tongyugou–Saishitang tin–copper polymetallic ore field in West Qinling, Qinghai province. Based on the contact/crosscutting relationships, mineral associations and mineralization characteristics, hydrothermal fluid evolution can be divided into three stages: skarn (I), quartz sulfide (II) and polymetallic sulfide-bearing quartz–calcite vein (III). The quartz sulfide stage (II) can be further divided into a massive sulfide stage (II-1) and a layered sulfide stage (II-2). This paper presents detailed analysis of fluid inclusions, H–O, S and Pb isotope compositions of rock samples from each of the above three stages as well as analysis of fluid inclusions from quartz diorite. The homogenization temperature, salinity, density and pressure of fluid inclusions in quartz diorite and typical transparent minerals showed a tendency of gradual decline in these evolutionary stages. The ore-forming fluid can be classified as a Na⁺–Ca^2 +–SO₄^2 − Cl⁻ system with a minor proportion of a Na⁺–Ca^2 +–NO₃⁻ SO₄^2 − system, which likely resulted from mixing of magmatic and formation water. The H–O isotope composition indicates that the proportion of formation water increased during the ore-forming process, and meteoric water was mixed in the late quartz–calcite vein stage. The δ³⁴S (CDT) values (− 6.45–5.57‰) and Pb isotope compositions show that the ore-forming materials were mainly derived from magmatic fluid. Ore-forming fluid was boiling during the main ore-forming stage (II-1) due to pressure decrease. Consequently, the physical and chemical conditions (i.e., pH, Eh, f_O2, f_S2) changed, and metallic elements (including Cu) in the fluid could no longer exist in the form of complexes and precipitated from the fluid. According to the integrated analysis of ore features, mineral associations, alteration characteristics, ore-forming environment and fluid evolutionary process, it is concluded that the Saishitang deposit is a typical skarn deposit.     

Origin of fluids in the Hetaoping Pb–Zn deposit,Baoshan–Narong–Dongzhi block metallogenic belt,Yunnan Province,SW China

The Hetaoping skarn type Pb–Zn deposit is located in the Baoshan–Narong–Dongzhi block metallogenic belt (BND belt), a belt between the Tengchong terrane and the Lanping basin. The deposit is hosted by marble of the upper Cambrian Hetaoping Formation and there are no outcrops of plutonic rocks present. This deposit is one of two large Pb–Zn deposits recently discovered in the BND belt. The Hetaoping deposit is a high Mn skarn. Four types of fluid inclusions were recognized in quartz from the deposit: vapor-rich inclusions (Type I), liquid-rich inclusions (Type II), pure vapor inclusions (Type III), and pure fluid inclusions (Type IV). The coexistence of Type I and Type III inclusions in Stage I (pre-ore stage) and Stage II (main ore stage) shows evidence of fluid boiling. Quartz-hosted fluid inclusions (Stage I and Stage II) display high homogenization temperatures and salinities (134–315 °C; 3.7–18.6 wt% NaCl equivalent) but calcite-hosted fluid inclusions in Stage III (post-ore stage) record lower homogenization temperatures and salinities (85–214 °C; 0.5–5.4 wt% NaCl equivalent). These data suggest a possible mixing between primary magmatic water and meteoric water. Based on chromatography data, the fluid inclusions in quartz contain abundant CO₂ and O₂ and subordinate CO, CH₄ and C₂H₂ + C₂H₄, suggesting an oxidizing environment. Based on their Na/K and Cl/SO₄ ratios, fluids contained in fluid inclusions are similar to volcanic spring waters. The low Na/K ratios (0.40–1.34) of the ore-forming fluids may have resulted from interaction with a deep alkaline intermediate-acid intrusion. Hydrogen and oxygen isotope determinations on quartz from different ore stages show low δ¹⁸O and δD values relative to VSMOW (−4.3‰ to 2.3‰; −109‰ to −91‰), indicating that the ore-forming fluids were diluted by external fluid sources as the skarn system cooled. Overall, geological and geochemical interpretations suggest that the Hetaoping deposit is a distal manganese skarn Pb–Zn deposit related to concealed intrusions.     

Mineralogy,fluid inclusions,and isotopes of the Cihai iron deposit,eastern Tianshan,NW China: Implication for hydrothermal evolution and genesis of subvolcanic rocks-hosted skarn-type deposits

Most skarn deposits are closely related to granitoids that intruded into carbonate rocks. The Cihai (>100 Mt at 45% Fe) is a deposit with mineral assemblages and hydrothermal features similar to many other typical skarn deposits of the world. However, the iron orebodies of Cihai are mainly hosted within the diabase and not in contact with carbonate rocks. In addition, some magnetite grains exhibit unusual relatively high TiO₂ content. These features are not consistent with the typical skarn iron deposit. Different hydrothermal and/or magmatic processes are being actively investigated for its origin. Because of a lack of systematic studies of geology, mineral compositions, fluid inclusions, and isotopes, the genetic type, ore genesis, and hydrothermal evolution of this deposit are still poorly understood and remain controversial.The skarn mineral assemblages are the alteration products of diabase. Three main paragenetic stages of skarn formation and ore deposition have been recognized based on petrographic observations, which show a prograde skarn stage (garnet-clinopyroxene-disseminated magnetite), a retrograde skarn stage (main iron ore stage, massive magnetite-amphibole-epidote ± ilvaite), and a quartz-sulfide stage (quartz-calcite-pyrite-pyrrhotite-cobaltite).Overall, the compositions of garnet, clinpyroxene, and amphibole are consistent with those of typical skarn Fe deposits worldwide. In the disseminated ores, some magnetite grains exhibit relatively high TiO₂ content (>1 wt.%), which may be inherited from the diabase protoliths. Some distinct chemical zoning in magnetite grains were observed in this study, wherein cores are enriched in Ti, and magnetite rims show a pronounced depletion in Ti. The textural and compositional data of magnetite confirm that the Cihai Fe deposit is of hydrothermal origin, rather than associated with iron rich melts as previously suggested.Fluid inclusions study reveal that, the prograde skarn (garnet and pyroxene) formed from high temperature (520–600 °C), moderate- to high-salinity (8.1–23.1 wt.% NaCl equiv, and >46 wt.% NaCl equiv) fluids. Massive iron ore and retrograde skarn assemblages (amphibole-epidote ± ilvaite) formed under hydrostatic condition after the fracturing of early skarn. Fluids in this stage had lower temperature (220°–456 °C) and salinity (8.4–16.3 wt.% NaCl equiv). Fluid inclusions in quartz-sulfide stage quartz and calcite also record similar conditions, with temperature range from 128° to 367 °C and salinity range from 0.2 to 22.9 wt.% NaCl equiv. Oxygen and hydrogen isotopic data of garnet and quartz suggest that mixing and dilution of early magmatic fluids with external fluids (e.g., meteoric waters) caused a decrease in fluid temperature and salinity in the later stages of the skarn formation and massive iron precipitation. The δ¹⁸O values of magnetite from iron ores vary between 4.1 and 8.5‰, which are similar to values reported in other skarn Fe deposits. Such values are distinct from those of other iron ore deposits such as Kiruna-type and magmatic Fe-Ti-V deposits worldwide. Taken together, these geologic, geochemical, and isotopic data confirm that Cihai is a diabase-hosted skarn deposit related to the granitoids at depth.     

Isotope and fluid inclusion geochemistry of the Cangyuan Pb-Zn-Ag polymetallic deposit in Yunnan,SW China

The Cangyuan Pb-Zn-Ag polymetallic deposit is located in the Baoshan Block, southern Sanjiang Orogen. The orebodies are hosted in low-grade metamorphic rocks and skarn in contact with Cenozoic granitic rocks. Studies on fluid inclusions (FIs) of the deposit indicate that the ore-forming fluids are CO₂-bearing, NaCl-H₂O. The initial fluids evolved from high temperatures (462–498 °C) and high salinities (54.5–58.4 wt% NaCl equiv) during the skarn stage into mesothermal (260–397 °C) and low salinities (1.2–9.5 wt% NaCl equiv) during the sulfide stage. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O: 2.7–8.8‰; δD: −82 to −120‰) suggest that the ore-forming fluids are mixture of magmatic fluids and meteoric water. Sulfur isotopic compositions of the sulfides yield δ³⁴S values of −2.3 to 3.2‰; lead isotopic compositions of ore sulfides are similar to those of granitic rocks, indicating that the sulfur and ore-metals are derived from the granitic magma. We propose that the Cangyuan Pb-Zn-Ag deposit formed from magmatic hydrothermal fluids. These Cenozoic deposits situated in the west of Lanping-Changdu Basin share many similarities with the Cangyuan in isotopic compositions, including the Laochang, Lanuoma and Jinman deposits. This reveals that the Cenozoic granites could have contributed to Pb-Zn-Cu mineralization in the Sanjiang region despite the abundance of Cenozoic Pb-Zn deposits in the region, such as the Jingding Pb-Zn deposit, that is thought to be of basin brine origin.     

Inhomogeneous lithospheric thinning in the central North China Craton: Zircon U–Pb and S–He–Ar isotopic record from magmatism and metallogeny in the Taihang Mountains

The large scale Mesozoic magmatism and related metallogeny in the Taihang Mountains (TM) provide important clues for the lithospheric thinning of the North China Craton (NCC). Among the ore deposits, the vein gold mineralization of Shihu in the Fuping region and the skarn ore deposit of Xishimen in the Wu'an region represent typical Mesozoic metallogeny in the TM. In the Shihu gold mine, the Mapeng batholith is dominantly composed of monzogranite and granodiorite, whereas, the Wu'an pluton in the Xishimen iron mine mainly comprises monzonite and diorite. Here we present zircon LA–ICP-MS U–Pb data from 8 samples which reveal the timing of magmatism in the TM as ca. 130 Ma, which is contemporaneous with the large-scale metallogeny in the margins of the NCC. The δ³⁴S values recorded in the sulfide minerals from the Shihu gold deposit and the Xishimen skarn iron deposit show a range of 2.2‰–5.0‰, and 11.6‰–18.7‰, respectively. Helium isotopic compositions of fluid inclusions in pyrite from the Shihu gold deposit vary from 0.12 to 1.98 Ra (where Ra is the ³He/⁴He ratio of air = 1.39 × 10^? 6), with calculated mantle helium values of 1.4%–25%, whereas, those of the Xishimen skarn iron deposit range from 0.06 to 0.19 Ra, with calculated mantle helium of 0.7%–2.2%. The S–He–Ar isotopic data suggest a lower crustal origin for the ore-forming components, with variable inputs of mantle source. The large population of inherited zircons in our samples, with ²⁰⁷Pb/²⁰⁶Pb ages ranging between 2500 Ma and 1800 Ma, also supports crustal participation. Our data reveal that the Shihu gold deposit witnessed greater mantle input than the Xishimen skarn iron deposit, suggesting that the continental lithosphere is markedly thinner under the Fuping region than that under the Wu'an region. Our interpretation is also supported by published data from two ultra-broadband high-precision magnetotelluric sounding profiles across the TM region showing a variation in the lithosphere thickness from 155 km to 70 km while moving from the south (Wu'an region) to the north (Fuping region). Our study suggests that inhomogeneous lithospheric thinning in the central NCC occurred at least as early as ca. 130 Ma ago.     

Geology,geochronology, fluid inclusion and H–O isotope geochemistry of the Luoboling Porphyry Cu–Mo deposit,Zijinshan Orefield,Fujian Province,China

The Luoboling Cu–Mo deposit in the Zijinshan Orefield, Fujian province, southeastern China, is a large porphyry deposit hosted by the Sifang granodiorite and the Luoboling granodiorite porphyry. The largest Cu–Mo orebody is saddle-shaped with various types of hydrothermal veinlets. Intensive hydrothermal alteration in the deposit is characterized by outward zoning from potassic, overprinted by phyllic alteration, to phyllic and alunite–dickite alteration. Based on the mineral assemblages and crosscutting relationships of veins, the ore-forming process can be divided into three stages, namely: an early-stage K-feldspar + quartz ± magnetite ± molybdenite veins associated with potassic alteration; a middle-stage quartz + molybdenite + chalcopyrite + pyrite veins in phyllic zone; and a late-stage quartz ± gypsum veins in the phyllic and alunite–dickite alteration zones. Six molybdenite separates yield a Re−Os isochron age 104.6 ± 1.0 Ma, which is identical to the age of emplacement of the Sifang and Luoboling granodiorite porphyries. Three types of fluid inclusions (FIs) were observed at the Luoboling deposit: 1) NaCl–H₂O (aqueous), 2) daughter mineral-bearing and 3) CO₂–H₂O fluid inclusions. FIs of the early and middle stages are predominantly vapor-rich aqueous and daughter mineral-bearing inclusions, together with minor CO₂-rich and liquid-rich aqueous inclusions; whereas the late-stage minerals only contain liquid-rich aqueous inclusions. Homogenization temperatures and salinities of FIs trapped in the early-stage minerals range from 420 to 540 °C and 0.4 to 62.9 wt.% NaCl equiv., respectively. FIs of the middle-stage yield homogenization temperatures of 340 to 480 °C and salinities of 0.5 to 56.0 wt.% NaCl equiv. CO₂ content and the oxygen fugacity (indicated by daughter minerals) of FIs trapped in middle-stage minerals are lower than those in the early stage. The liquid-rich aqueous inclusions of the late-stage homogenize at temperatures of 140 to 280 °C, yielding salinities of 0.4 to 8.4 wt.% NaCl equiv. The minimum estimated pressures of the three stages are 30–70 MPa, 10–40 MPa and 1–10 MPa, respectively, corresponding to minimum ore-forming depths of 1–2.8 km. Fluids trapped in early, middle and late stages yield δD values of − 67‰ to − 54‰, − 54‰ to − 70‰, and − 62‰, and δ¹⁸O values of 5.4‰ to 6.7‰, 2.8‰ to 4.2‰, and − 2.1‰, respectively. Fluid boiling, which resulted in the formation of stockworks and the precipitation of sulfides, occurred in the early and middle stages. The fluids subsequently evolved into a low temperature, low salinity system in the late stage, along with an input of meteoric water. The Luoboling porphyry Cu–Mo system was developed in a transition from continental arc to back-arc extension region, which was related to the westward subduction of the paleo-Pacific plate beneath the Huanan Orogen.     

Isotopic (C–O–S) geochemistry and Re–Os geochronology of the Haobugao Zn–Fe deposit in Inner Mongolia,NE China

The Haobugao Zn–Fe deposit is a typical skarn deposit located in the southern part of the Great Xing’an Range that hosts polymetallic mineralization over a large region. The main ore minerals at the deposit include sphalerite, magnetite, galena, chalcopyrite and pyrite, and the main gangue minerals include andradite, grossular garnet, hedenbergite, diopside, ilvaite, calcite and quartz. There are broadly two mineralizing periods represented by the relatively older skarn and younger quartz–sulfide veins. In detail, there are five metallogenic stages consisting of an early skarn, late skarn, oxide, early quartz–sulfide, and late quartz–sulfide–calcite stages. Electron microprobe analyses show that the garnet at the deposit varies in composition from And_97.95Gro_0.41Pyr_1.64 to And_30.69Gro_66.69Pyr_2.63, and pyroxene is compositionally in the diopside–hedenbergite range (i.e. Di_90.63Hd_8.00Jo_1.37–Hd_88.98Di_4.53Jo_6.49). Petrographic observations and electron microprobe analyses indicate that the sphalerite has three generations ([Zn_0.93Fe_0.08]S–[Zn_0.75Fe_0.24]S). The Zn associated with the first generation sphalerite replaced Cu and Fe of early xenomorphic granular chalcopyrite (i.e. [Cu_1.01Fe_1.03]S₂–[Cu_0.99Fe_0.99]S₂), and part of the first generation sphalerite is coeval with late chalcopyrite (i.e. [Cu_0.96Fe_0.99Zn_0.03]S₂–[Cu_1.00Fe_1.03Zn_0.01]S₂). Magnetite has a noticeable negative Ce anomaly (δCe = ∼0.17 to 0.54), which might be a result of the oxidized ore-fluid. Thirty δ³⁴S_V-PDB analyses of sulfides from the ore range from −2.3 to −0.1‰ in value, which are indicative of a magmatic source. The δ¹³C‰ and δ¹⁸O‰ values for calcite from the ore formed at quartz–sulfide–calcite stage vary from −9.9 to −5.5‰ and from −4.2 to 1.1‰, respectively, contrasting with δ¹³C‰ (2.9–4.8‰) and δ¹⁸O‰ (9.8–13.9‰) values for calcite from marble. It is suggested that the ore-forming fluid associated with late stage of mineralization was predominantly magmatic in origin with some input of local meteoric water.Molybdenite from the Haobugao deposit defines an isochron age of 142 ± 1 Ma, which is interpreted as the mineralization age being synchronous, within error, with the zircon U–Pb ages of 140 ± 1, 141 ± 2, and 141 ± 1 Ma for granite at the deposit. These data and characteristics of lithology and mineralization further show that the Zn–Fe mineralization is temporally and spatially related to the emplacement of granite in an extensional tectonic setting during the Mesozoic.     

The origin and evolution of skarn-forming fluids from the Phu Lon deposit,northern Loei Fold Belt,Thailand: Evidence from fluid inclusion and sulfur isotope studies

The Phu Lon skarn Cu–Au deposit is located in the northern Loei Fold Belt (LFB), Thailand. It is hosted by Devonian volcano-sedimentary sequences intercalated with limestone and marble units, intruded by diorite and quartz monzonite porphyries. Phu Lon is a calcic skarn with both endoskarn and exoskarn facies. In both skarn facies, andradite and diopside comprise the main prograde skarn minerals, whereas epidote, chlorite, tremolite, actinolite and calcite are the principal retrograde skarn minerals.Four types of fluid inclusions in garnet were distinguished: (1) liquid-rich inclusions; (2) daughter mineral-bearing inclusions; (3) salt-saturated inclusions; and (4) vapor-rich inclusions. Epidote contains only one type of fluid inclusion: liquid-rich inclusions. Fluid inclusions associated with garnet (prograde skarn stage) display high homogenization temperatures and moderate salinities (421.6–468.5 °C; 17.4–23.1 wt% NaCl equiv.). By contrast, fluid inclusions associated with epidote (retrograde skarn stage) record lower homogenization temperatures and salinities (350.9–399.8 °C; 0.5–8 wt% NaCl equiv.). These data suggest a possible mixing of saline magmatic fluids with external, dilute fluid sources (e.g., meteoric fluids), as the system cooled. Some fluid inclusions in garnet contain hematite daughters, suggesting an oxidizing magmatic environment. Sulfur isotope determinations on sulfide minerals from both the prograde and retrograde stages show a uniform and narrow range of δ³⁴S values (?2.6 to ?1.1 ‰ δ³⁴S), suggesting that the ore-forming fluid contained sulfur of orthomagmatic origin. Overall, the Phu Lon deposit is interpreted as an oxidized Cu–Au skarn based on the mineralogy and fluid inclusion characteristics.     

Copper isotopes trace the evolution of skarn ores: A case study from the Hongshan-Hongniu Cu deposit,southwest China

Transition metal isotopes are sensitive geochemical tracers of ore genesis. Here we present MC-ICP-MS analytical data of Cu isotope compositions from the Hongshan-Hongniu Cu deposit in Yunnan province. The δ⁶⁵Cu values (δ⁶⁵Cu = [(⁶⁵Cu/⁶³Cu)_sample/(⁶⁵Cu/⁶³Cu)_NIST976 − 1] × 1000) of seven whole-rock quartz monzonite porphyries and twenty-two chalcopyrite samples from the skarn ore-bodies display relatively narrow ranges from −0.15‰ to 0.38‰ and from −0.02‰ to 0.77‰, respectively. The overlap of δ⁶⁵Cu values indicates a genetic relationship between the quartz monzonite porphyry and skarn ore-bodies. We also evaluate the spatial and temporal variations of Cu isotope compositions in the skarn ore-bodies by comparison with some well-documented porphyry deposits in the world. The quartz monzonite porphyry shows compositional zoning with the inner domain enriched in heavy Cu isotope and the skarn related to the porphyry depleted in heavy Cu isotope. The chalcopyrites that formed during the late stage of mineralization tend to be enriched in heavy Cu isotope, and this feature is analogous to porphyry deposits. The δ⁶⁵Cu values of the quartz monzonite porphyry show typical features of hypogene mineralization, suggesting a potential scope for deep exploration and development in this deposit.     

Some new data on the genesis of the Linghou Cu–Pb–Zn polymetallic deposit—Based on the study of fluid inclusions and C–H–O–S–Pb isotopes

The Linghou deposit, located near Hangzhou City of Zhejiang Province, eastern China, is a medium-sized polymetallic sulfide deposit associated with granitic intrusion. This deposit is structurally and lithologically controlled and commonly characterized by ore veins or irregular ore lenses. In this deposit, two mineralization events were identified, of which the former produced the Cu–Au–Ag orebodies, while the latter formed Pb–Zn–Cu orebodies. Silicification and calc-silicate (skarn type), phyllic, and carbonate alternation are four principal types of hydrothermal alteration. The early Cu–Au–Ag and late Pb–Zn–Cu mineralizations are characterized by quartz ± sericite + pyrite + chalcopyrite + bornite ± Au–Ag minerals ± magnetite ± molybdenite and calcite + dolomite + sphalerite + pyrite + chalcopyrite + galena, respectively. Calcite clusters and calcite ± quartz vein are formed during the late hydrothermal stage.The NaCl–H₂O–CO₂ system fluid, coexisting with NaCl–H₂O system fluid and showing the similar homogenization temperatures (385 °C and 356 °C, respectively) and different salinities (16.89–21.68 wt.% NaCl eqv. and 7.70–15.53 wt.% NaCl eqv.), suggests that fluid immiscibility occurred during the Cu–Au–Ag mineralization stage and might have given rise to the ore-metal precipitation. The ore-forming fluid of the Pb–Zn–Cu mineralization mainly belongs to the NaCl–H₂O–CO₂ system of high temperature (~ 401 °C) and mid-high salinity (10.79 wt.% NaCl eqv.).Fluids trapped in the quartz-chalcopyrite vein, Cu–Au–Ag ores, Pb–Zn–Cu ores and calcite clusters yielded δ¹⁸O_H2O and δD values varying from 5.54‰ to 13.11‰ and from − 71.8‰ to − 105.1‰, respectively, indicating that magmatic fluids may have played an important role in two mineralization events. The δ¹³C_PDB values of the calcite change from − 2.78‰ to − 4.63‰, indicating that the CO₃^2 − or CO₂ in the ore-forming fluid of the Pb–Zn–Cu mineralization was mainly sourced from the magmatic system, although dissolution of minor marine carbonate may have also occurred during the ore-forming processes. The sulfide minerals have homogeneous lead isotopic compositions with ²⁰⁶Pb/²⁰⁴Pb ranging from 17.958 to 18.587, ²⁰⁷Pb/²⁰⁴Pb ranging from 15.549 to 15.701, and ²⁰⁸Pb/²⁰⁴Pb ranging from 37.976 to 39.052, indicating that metallic elements of the Linghou deposit came from a mixed source involving mantle and crustal components.Based on geological evidence, fluid inclusions, and H–O–C–S–Pb isotopic data, the Linghou polymetallic deposit is interpreted as a high-temperature, skarn-carbonate replacement type. Two types of mineralization are both related to the magmatic–hydrothermal system, with the Cu–Au–Ag mineralization having a close relationship with granodiorite.     

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

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

The Nadun Cu–Au mineralization,central Tibet: Root of a high sulfidation epithermal deposit

A new high sulfidation epithermal Cu–Au occurrence (Nadun) has been discovered adjacent to the Cretaceous Duolong porphyry Cu–Au deposit within the Bangong–Nujiang metallogenic belt, central Tibet. The Nadun Cu–Au mineralization is hosted in a tectonic–hydrothermal breccia with advanced argillic alteration, which occurs above sandstone, associated with quartz–pyrite veins. The granodiorite porphyry with strong argillic alteration yields a zircon U–Pb age of 119.1 ± 1.3 Ma, whereas the weakly argillic granodiorite porphyry intruded into the breccia has a younger age of 116.1 ± 1.3 Ma. This indicates that Cu–Au epithermal mineralization likely occurred between ~ 116 Ma and ~ 119 Ma, consistent with the duration of magmatic–hydrothermal activity at Duolong (~ 115–118 Ma), and providing evidence that Nadun and Duolong were formed during the same event. Moreover, the Nadun and Duolong porphyries have similar Hf isotopic compositions (εHf(t) values ranging from − 8.8 to 8.1; mean = 5.0 ± 1.1, n = 32), likely indicating that the deposits are comagmatic. In addition, boiling assemblages in vapor-rich inclusions coexisting with brines occur in early stage quartz–pyrite veins, and likely record phase separation at a temperature of > 550–300 °C and pressure of 700–110 bars. Most liquid-rich fluid inclusions formed at the breccia stage show similar salinity (1.7–19.3 wt.% NaCl equiv) to vapor-rich inclusions from the underlying quartz–pyrite veins, likely indicating vapor contraction during cooling at elevated presssure. This suggests that quartz–pyrite veins may act as conduits for ore-forming fluid traveling from the porphyry to the epithermal hydrothermal system. O and H isotopic compositions (δ¹⁸O_fluid = 0.42–9.71‰ and δD = − 102 to − 66‰) suggest that ore-forming fluids are dominantly from a magmatic source with a minor addition of meteoric water at a later stage. The S and Fe isotope compositions of sulfides (δ³⁴S = − 5.9 to 0.5‰ and δ⁵⁷Fe = − 2.15 to 0.17‰) decrease from the quartz–pyrite vein to breccia ore, indicating that ore-forming fluids gradually become SO₄²-enriched and relatively oxidized. This body of evidence suggests that the Nadun Cu–Au mineralization may represent the root of a high sulfidation epithermal deposit.