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.     

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.     

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

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

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

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

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.     

Geochemistry,fluid inclusion and stable isotope constraints (C and O) of the Sivrikaya Fe-skarn mineralization (Rize,NE Turkey)

The Sivrikaya Fe-skarn mineralization is hosted by dolomitic limestone layers of Late Cretaceous volcano-sedimentary unit, comprised of andesite, basalt and their pyroclastites, including, sandstone, shale and dolomitic limestone layers. Intrusion of the Late Cretaceous–Eocene İkizdere Granitoid in the volcano–sedimentary unit resulted in skarn mineralization along the granitoid–dolomitic limestone contact. The ore is associated with exoskarns, and mineralization is characterized by early anhydrous garnet and pyroxene with late hydrous minerals, such as epidote, tremolite, actinolite and chlorite. The ore minerals are mainly magnetite and hematite, with minor amounts of pyrite and chalcopyrite. The composition of garnet and pyroxene in the exoskarn is Adr_{79.45−99.03}Grs_0−17.9Prs_0.97−2.65 and Di_69.1−77.1Hd_22.2−29.8Jhn_0.6−1.4, respectively, and abundances of magnetite in the ore suggest that the Fe-skarn mineralization formed under relatively oxidized conditions.Homogenization temperatures (T_h) of all fluid inclusions and calculated salinity content are in the range of 166 °C–462 °C and 0.35–14.3 wt% NaCl equ., respectively. Well-defined positive correlation between Th and salinity values indicates that meteoric water was involved in the hydrothermal solutions. Eutectic temperatures (Te) between −40.8 °C and −53.6 °C correspond to the presence of CaCl₂ in the early stage of fluid inclusions. On the other hand, the Te temperatures of later-stage fluid inclusions, in the range of −38 °C and −21.2 °C, correspond to the presence of MgCl₂, FeCl₂, KCl and NaCl type salt combinations. None of the fluid inclusions were found to contain separated gas phases in microscopy observations. However, a limited amount of dissolved CH₄ was identified in the early stage, high temperature fluid inclusions using Raman spectroscopic studies.Δ¹⁸O values in both dolomitic limestone (10.8–12.5‰) and skarn calcite (7.6–9.8‰) were highly depleted compared to the typical δ¹⁸O values of marine limestones. Decreases in δ¹⁸O values are accepted as an indication of dilution by meteoric water because retrograde brecciation of garnet, magnetite and breccia filling epidote and quartz in volcanic host rocks are an indication of increasing permeability, allowing infiltration of meteoric water. Highly depleted δ¹³C isotopes (up to −6.5‰) of dolomitic limestone, indicate that organic matter in carbonates had an effect on the decreasing isotopic ratios. The presence of CH₄ and CH₂ in fluid inclusions can be explained by the thermal degradation of these organic materials.     

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

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

Ore genesis of Badi copper deposit,northwest Yunnan Province,China: evidence from geology,fluid inclusions,and sulfur,hydrogen and oxygen isotopes

The Badi copper deposit is located in Shangjiang town, Shangri-La County, Yunnan Province. Tectonically, it belongs to the Sanjiang Block. Vapor–liquid two-phase fluid inclusions, CO₂-bearing fluid inclusions, and daughter-bearing inclusions were identified in sulfide-rich quartz veins. Microthermometric and Raman spectroscopy studies revealed their types of ore-forming fluids: (1) low-temperature, low-salinity fluid; (2) medium-temperature, low salinity CO₂-bearing; and (3) high-temperature, Fe-rich, high sulfur fugacity. The δ¹⁸O values of chalcopyrite-bearing quartz ranged from 4.96‰ to 5.86‰, with an average of 5.40‰. The δD values of ore-forming fluid in equilibrium with the sulfide-bearing quartz were from ? 87‰ to ? 107‰, with an average of ? 97.86‰. These isotopic features indicate that the ore-forming fluid is a mixing fluid between magmatic fluid and meteoric water. The δ³⁴S values of chalcopyrite ranged from 13.3‰ to 15.5‰, with an average of 14.3‰. Sulfur isotope values suggest that the sulfur in the deposit most likely derived from seawater. Various fluid inclusions coexisted in the samples; similar homogenization temperature to different phases suggests that the Badi fluid inclusions might have been captured under a boiling system. Fluid boiling caused by fault activity could be the main reason for the mineral precipitation in the Badi 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.     

Geochemical Characteristics,Origin, and Evolution of Ore‐Forming Fluids of the Khut Copper Skarn Deposit,West of Yazd in Central Iran

The Khut copper skarn deposit is located at about 50 km northwest of Taft City in Yazd province in the middle part of the Urumieh‐Dokhtar magmatic arc. Intrusion of granitoid of Oligocene–Miocene age into carbonate rocks of the Triassic Nayband Formation led to the formation of marble and a calcic skarn. The marble contains high grade Cu mineralization that occurs mainly as open space filling and replacement. Cu‐rich sulfide samples from the mineralized marble are also anomalous in Au, Zn, and Pb. In contrast, the calcic skarn is only weakly anomalous in Cu and W. The calcic skarn is divided into garnet skarn and garnet–pyroxene skarn zones. Paragenetic relationships and microthermometric data from fluid inclusions in garnet and calcite indicate that the compositional evolution of skarn minerals occurred in three main stages as follows. (i) The early prograde stage, which is characterized by Mg‐rich hedenbergite (Hd_53.7Di_42.3–Hd_86.1Di_9.5) with Al‐bearing andradite (69.8–99.5 mol% andradite). The temperature in the early prograde skarn varies from 400 to 500°C at 500 bar. (ii) The late prograde stage is manifested by almost pure andradite (96.2–98.4 mol% andradite). Based on the fluid inclusion data from garnet, fluid temperature and salinity in this stage is estimated to vary from 267 to 361°C and from 10.1 to 21.1 wt% NaCl equivalent, respectively. Pyrrhotite precipitation started during this stage. (iii) The retrograde stage occurs in an exoskarn, which consists of an assemblage of ferro‐actinolite, quartz, calcite, epidote, chlorite, sphalerite, pyrite, and chalcopyrite that partially replaces earlier mineral assemblages under hydrostatic conditions during fracturing of the early skarn. Fluids in calcite yielded lower temperatures (T < 260°C) and fluid salinity declined to ～8 wt% NaCl equivalent. The last stage mineralization in the deposit is supergene weathering/alteration represented by the formation of iron hydroxide, Cu‐carbonate, clay minerals, and calcite. Sulfur isotope data of chalcopyrite (δ³⁴S of +1.4 to +5.2‰) show an igneous sulfur source. Mineralogy and mineral compositions of the prograde assemblage of the Khut skarn are consistent with deposition under intermediately oxidized and slightly lower fS₂ conditions at shallow crustal levels compared with those of other typical Fe‐bearing Cu–Au skarn systems.     

Mineralisation of amethyst-bearing geodes in Ametista do Sul (Brazil) from low-temperature sedimentary brines: evidence from monophase liquid inclusions and stable isotopes

Fluid inclusion studies in combination with hydrogen, oxygen and sulphur isotope data provide novel insights into the genesis of giant amethyst-bearing geodes in Early Cretaceous Paraná continental flood basalts at Amestita do Sul, Brazil. Monophase liquid inclusions in colourless quartz, amethyst, calcite, barite and gypsum were analysed by microthermometry after stimulating bubble nucleation using single femtosecond laser pulses. The salinity of the fluid inclusions was determined from ice-melting temperatures and a combination of prograde and retrograde homogenisation temperatures via the density maximum of the aqueous solutions. Four mineralisation stages are distinguished. In stage I, celadonite, chalcedony and pyrite formed under reducing conditions in a thermally stable environment. Low δ³⁴S_V-CDT values of pyrite (?25 to ?32?‰) suggest biogenic sulphate reduction by organotrophic bacteria. During the subsequent stages II (amethyst, goethite and anhydrite), III (early subhedral calcite) and IV (barite, late subhedral calcite and gypsum), the oxidation state of the fluid changed towards more oxidising conditions and microbial sulphate reduction ceased. Three distinct modes of fluid salinities around 5.3, 3.4 and 0.3 wt% NaCl-equivalent characterise the mineralisation stages II, III and IV, respectively. The salinity of the stage I fluid is unknown due to lack of fluid inclusions. Variation in homogenisation temperatures and in δ¹⁸O values of amethyst show evidence of repeated pulses of ascending hydrothermal fluids of up to 80–90 °C infiltrating a basaltic host rock of less than 45 °C. Colourless quartz and amethyst formed at temperatures between 40 and 80 °C, while the different calcite generations and late gypsum precipitated at temperatures below 45 °C. Calculated oxygen isotope composition of the amethyst-precipitating fluid in combination with δD values of amethyst-hosted fluid inclusions (?59 to ?51?‰) show a significant ¹⁸O-shift from the meteoric water line. This ¹⁸O-shift, high salinities of the fluid inclusions with chloride-sulphate composition, and high δ³⁴S values of anhydrite and barite (7.5 to 9.9?‰) suggest that sedimentary brines from deeper parts of the Guaraní aquifer system must have been responsible for the amethyst mineralisation.     

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

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

Mineral compositions and fluid evolution of the Tonglushan skarn Cu–Fe deposit,SE Hubei,east-central China

The Tonglushan Cu–Fe deposit (1.12 Mt at 1.61% Cu, 5.68 Mt at 41% Fe) is located in the westernmost district of the Middle–Lower Yangtze River metallogenic belt. As a typical polymetal skarn metallogenic region, it consists of 13 skarn orebodies, mainly hosted in the contact zone between the Tonglushan quartz-diorite pluton (140 Ma) and Lower Triassic marine carbonate rocks of the Daye Formation. Four stages of mineralization and alterations can be identified: i.e. prograde skarn formation, retrograde hydrothermal alteration, quartz-sulphide followed by carbonate vein formation. Electron microprobe analysis (EMPA) indicates garnets vary from grossular (Ad_20.2–41.6Gr_49.7–74.1) to pure andradite (Ad_47.4–70.7Gr_23.9–45.9) in composition, and pyroxenes are represented by diopsides. Fluid inclusions identify three major types of fluids involved during formation of the deposit within the H₂O–NaCl system, i.e. liquid-rich inclusions (Type I), halite-bearing inclusions (Type II), and vapour-rich inclusions (Type III). Measurements of fluid inclusions reveal that the prograde skarn minerals formed at high temperatures (>550°C) in equilibrium with high-saline fluids (>66.57 wt.% NaCl equivalent). Oxygen and hydrogen stable isotopes of fluid inclusions from garnets and pyroxenes indicate that ore-formation fluids are mainly of magmatic-hydrothermal origin (δ¹⁸O = 6.68‰ to 9.67‰, δD = –67‰ to –92‰), whereas some meteoric water was incorporated into fluids of the retrograde alteration stage judging from compositions of epidote (δ¹⁸O = 2.26‰ to 3.74‰, δD= –31‰ to –73‰). Continuing depressurization and cooling to 405–567°C may have resulted in both a decrease in salinity (to 48.43–55.36 wt.% NaCl equivalent) and the deposition of abundant magnetite. During the quartz-sulphide stage, boiling produced sulphide assemblage precipitated from primary magmatic-hydrothermal fluids (δ¹⁸O = 4.98‰, δD = –66‰, δ³⁴S values of sulphides: 0.71–3.8‰) with an extensive range of salinities (4.96–50.75 wt.% NaCl equivalent), temperatures (240–350°C), and pressures (11.6–22.2 MPa). Carbonate veins formed at relatively low temperatures (174–284°C) from fluids of low salinity (1.57–4.03 wt.% NaCl equivalent), possibly reflecting the mixing of early magmatic fluids with abundant meteoric water. Boiling and fluid mixing played important roles for Cu precipitation in the Tonglushan deposit.     

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

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

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

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

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

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

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.     

Late Hercynian polymetallic vein-type base-metal mineralization in the Iberian Pyrite Belt: fluid-inclusion and stable-isotope geochemistry (S–O–H–Cl)

Late Variscan vein-type mineralization in the Iberian Pyrite Belt, related to the rejuvenation of pre-existing fractures during late Variscan extensional tectonism, comprises pyrite–chalcopyrite, quartz–galena–sphalerite, quartz–stibnite–arsenopyrite, quartz–pyrite, quartz–cassiterite–scheelite, fluorite–galena–sphalerite–chalcopyrite, and quartz–manganese oxide mineral assemblages. Studies of fluid inclusions in quartz, stibnite, and barite as well as the sulfur isotopic compositions of stibnite, galena, and barite from three occurrences in the central part of the Iberian Pyrite Belt reveal compelling evidence for there having been different sources of sulfur and depositional conditions. Quartz–stibnite mineralization formed at temperatures of about 200 °C from fluids which had undergone two-phase separation during ascent. Antimony and sulfide are most probably derived by alteration of a deeper lying, volcanic-hosted massive sulfide mineralization, as indicated by δ³⁴S signatures from ?1.45 to ?2.74‰. Sub-critical phase separation of the fluid caused extreme fractionation of chlorine isotopes (δ³⁷Cl between ?1.8 and 3.2‰), which correlates with a fractionation of the Cl/Br ratios. The source of another high-salinity fluid trapped in inclusions in late-stage quartz from quartz–stibnite veins remains unclear. By contrast, quartz–galena veins derived sulfide (and metals?) by alteration of a sedimentary source, most likely shale-hosted massive sulfides. The δ³⁴S values in galena from the two study sites vary between ?15.42 and ?19.04‰. Barite which is associated with galena has significantly different δ³⁴S values (?0.2 to 6.44‰) and is assumed to have formed by mixing of the ascending fluids with meteoric water.     

Genesis of the Maanqiao gold deposit in the western Qinling orogen,central China: Constraints from fluid inclusions and in-situ sulfur isotopes

The western Qinling orogen (WQO) is one of the most important prospective gold provinces in China. The Maanqiao gold deposit, located on the southern margin of the Shangdan suture, is a representative gold deposit in the WQO. The Maanqiao deposit is hosted by the metasedimentary rocks of the Upper Devonian Tongyusi Formation. The EW-trending brittle-ductile shear zone controls the orebodies; they occur as disseminated, and auriferous quartz–sulfide vein. The ore-related hydrothermal alteration comprises silicification, sulfidation, sericitization, chloritization, and carbonatization. Native gold is visible and mainly associated with pyrite and pyrrhotite. Mineralization can be classified into the following three stages: bedding-parallel barren quartz–pyrite–(pyrrhotite) (early-stage), auriferous quartz–polymetallic (middle-stage), and carbonate–(quartz)–sulfide (late-stage).Detailed fluid inclusion (FI) studies revealed three types of inclusions in quartz and calcite: aqueous (W-type), CO₂–H₂O (C-type), and pure carbonic (PC-type) FIs. The primary FIs in the early-stage quartz are C- and PC-type, in the middle-stage quartz are mainly W- and C-type, and in the late-stage calcite are only W-type. During gold mineralization, the total FI homogeneous temperatures evolved from 189–375 °C (mostly 260–300 °C) to 132–295 °C (mostly 180–240 °C) to 123–231 °C (mostly 130–150 °C), and the salinities varied among 2.2–9.1 wt.% NaCl equiv. (mostly 5–8 wt.%) to 0.2–9.0 wt.% NaCl equiv. (mostly 3–6 wt.%) to 0.3–3.6 wt.% NaCl equiv. (mostly 2–4 wt.%). The ore-forming fluid was characterized as an H₂O–NaCl−CO₂−CH₄–(N₂) system with medium-low temperature and low salinity. The fluid immiscibility and fluid-rock interaction may be responsible for the precipitation of the sulfides and gold at the Maanqiao gold deposit. Three types of pyrite corresponding to the three mineralization stages, as well as pyrrhotite and arsenopyrite in the middle stage, are micro-analyzed for in-situ sulfur isotopic composition by LA-ICP-MS. Py1 yield near-zero δ³⁴S values of −2.5‰ to 3.0‰, which are somewhat lower than that of the granite hosted pyrites (Py-g, 4.8‰ to 6.6‰). The result suggests a mixed sulfur source from magmatic-hydrothermal fluids and the metamorphism of diagenetic pyrite. Pyrite + pyrrhotite + arsenopyrite assemblages in the middle-stage have relatively higher δ³⁴S values (6.6‰ to 12.3‰) and are mainly developed due to the metamorphism of the ore-host and underlying Devonian sedimentary sequences. The low δ³⁴S values of the late-stage fracture-filled Py3 (−21.9‰ to −17.0‰) resulted from an increasing oxygen fugacity, which was caused by the inflow of oxidized meteoric waters.Based on our studies, the Maanqiao gold deposit is considered to be an orogenic type and closely related to the Indosinian Qinling orogeny.     

Fluid Inclusion Study of Skarns in the Maruyama Deposit, the Kamioka Mine, Central Japan

Abstract: Fluid inclusions in skarn minerals in the Maruyama deposit, the Kamioka mine, central Japan were studied. Homogenization temperatures (Th) of fluid inclusions in 48 skarn minerals (hedenbergite, andradite, epidote and quartz) were measured, and gas composition of fluid inclusions in 12 skarn minerals was measured with a quadrupole mass spectrometer. The maximum Th value of primary inclusions in hedenbergite is 380C with peaks around 360C. Primary inclusions in hedenbergite near contact between skarn and limestone have slightly lower Th values and their distribution has a tendency of long trail skirt toward low temperature, which indicates ceasing of skarnization coincides with temperature decrease. Fluid inclusions in andradite and quartz in the hedenbergite skarn have lower Th values, in this order, than those in hedenbergite. CH4–detected fluid inclusions are localized around the Maruyama fault. Gas composition of the fluid inclusions indicates that fluid trapped in the hedenbergite has CO2 content less than 1 mole % and is not in equilibrium with graphite.