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.     

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.     

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.     

Metallogeny of the Handagai skarn Fe–Cu deposit,northern Great Xing'an Range,NE China: Constraints on fluid inclusions and skarn genesis

The newly discovered Handagai skarn Fe–Cu deposit is located in the northern Great Xing'an Range of NE China and is hosted by the Ordovician Luohe Formation. The orebodies that form the deposit are generally concordant with the bedding within these sediments, and are spatially related to areas of skarn development. The Fe–Cu mineralization in this area records four stages of paragenesis, namely prograde skarn, retrograde skarn, quartz–sulfide, and quartz–carbonate stages. The Handagai deposit is a calcic skarn that is dominated by an andradite–diopside–epidote–actinolite assemblage. The mineralogy and geochemistry of the skarn indicate that it formed from a hydrothermal fluid that altered the carbonate units in this area to a garnet (And_42–95Grs_4–53) and pyroxene (Di_71–78Hd_22–29Jo_0–2) bearing skarn. The epidote within the skarn has an epidote end-member composition, with the chlorite in the skarn dominantly Fe-rich, indicating that these minerals formed in an Fe-rich environment. The petrographic, microthermometric, and Raman spectroscopic analysis of fluid inclusions within garnet, epidote, actinolite, quartz, and calcite precipitated at different stages of formation of the Handagai deposit indicate that mineralization-related fluid inclusions are either liquid-rich two-phase H₂O–NaCl (type I), gas-rich two-phase H₂O–NaCl (type II), three-phase (liquid + vapor + solid) H₂O–NaCl (type III), or CO₂–H₂O–NaCl inclusions (type IV). The early stages of mineralization are associated with all four types of inclusion, whereas the later stages of mineralization are only associated with type I and II inclusions. Inclusion homogenization temperatures vary between the four stages of mineralization (370 °C–530 °C and > 600 °C, 210 °C–290 °C, 190 °C–270 °C, and 150 °C–230 °C, from early to late, respectively), with salinities also varying between the earlier and later stages of mineralization (11–18 and > 45, 7–15, 6–9, and 3–7 wt.% NaCl equivalent (equiv.), respectively). The majority of the inclusions within the Handagai deposit have homogenization temperatures and salinities of 200 °C–350 °C and 4–14 wt.% NaCl equiv., respectively, indicating that this is a medium–high temperature and medium–low salinity type deposit. The fluid inclusions were trapped at pressures of 11 to 72 MPa, corresponding to depths of 0.4 to 2.9 km. The geology, mineralogy, geochemistry, and fluid inclusions microthermometry indicate that the Handagai deposit formed as a result of contact infiltration metasomatism, with the deposition of ore minerals resulting from a combination of factors that include boiling as a result of reduced pressure, cooling, and fluid mixing.     

Geology,mineralization, stable isotope,and fluid inclusion characteristics of the Vostok-2 reduced W-Cu skarn and Au-W-Bi-As stockwork deposit,Sikhote-Alin,Russia

The large (>180 Kt WO₃ and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH₄-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO₂-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ¹⁸O_H2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ³⁴S = −6.9 to −6.2‰) and carbon (δ¹³C_fluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ¹⁸O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ³⁴S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ¹³C_fluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ¹³C_fluid = −16.4 to −14.5‰) and late (δ¹³C_fluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO₂ removal due to boiling of CO₂-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.     

Geology,mineralization, and fluid inclusion characteristics of the Lermontovskoe reduced-type tungsten (±Cu,Au, Bi) skarn deposit,Sikhote-Alin,Russia

The Lermontovskoe deposit (∼48 Kt WO₃; average 2.6% WO₃, 0.24% Cu, 0.23 g/t Au) is situated in a W-Sn-Au metallogenic belt that formed in a collisional tectonic environment. This tungsten skarn deposit has a W-Au-As-Bi-Te-Sb signature that suggests an affinity with reduced intrusion-related Au deposits. The deposit is associated with an intrusion that is part of the ilmenite-series, high-K peraluminous granitoid (granodiorite to granite) suite. These rocks formed via mantle magma-induced melting of crustal sources.The deposit comprises reduced-type, pyroxene-dominated prograde and retrograde skarns followed by hydrosilicate (amphibole-chlorite-pyrrhotite-scheelite-quartz) and phyllic (muscovite/sericite-carbonate-albite-quartz-scheelite-sulfide, with abundant apatite) alteration assemblages. Fluid inclusions from the skarn assemblages indicate high-temperature (>500 °C), high-pressure (1400–1500 bars) and high-salinity (53–60 wt% NaCl-equiv.) magmatic-hydrothermal fluids. They were post-dated by high-carbonic, methane-dominate, low-salinity fluid at the hydrosilicate alteration stage. These fluids boiled at 360–380 °C and 1300–1400 bars. The subsequent phyllic alteration started again with a high-temperature (>450 °C), high-pressure (1000–1100 bars) and high-salinity (42–47 wt% NaCl-equiv.) fluid, with further incursion of high-carbonic, methane-dominated, low-salinity fluid that boiled at 390–420 °C and 1150–1200 bars. The latest phyllic alteration included the lower-temperature (340–360 °C), lower pressure (370–400 bars) high-carbonic, methane-dominated (but with higher CO₂ fraction), low-salinity fluid, and then the low-temperature (250–300 °C) H₂O-CO₂-CH₄-NaCl fluid, with both fluids boiled at the deposit level. The high-salinity aqueous fluids are interpreted to have come from crystallizing granitoid magma, whereas the reduced high-carbonic fluids probably came from a deeper mafic magma source. Both of these fluids potentially contributed to the W-Au-As-Bi-Te-Sb metal budget. Decreasing temperatures coupled with high aCa²⁺ and fluid boiling promoted scheelite deposition at all post-skarn hydrothermal stages.The deposit is characterized by limited downdip extent of mineralized zones and abundant coarse-grained muscovite-quartz (+apatite, scheelite) aggregates that formed at the phyllic alteration stage. Together with presence of high-temperature, high-pressure and high-salinity fluids directly exsolving from crystallizing magma, this suggests a root level of the mineralized magmatic-hydrothermal system of reduced W skarn deposits.     

Isotope and fluid inclusion geochemistry and genesis of the Qiangma gold deposit,Xiaoqinling gold field,Qinling Orogen,China

The Qiangma gold deposit is hosted in the > 1.9 Ga Taihua Supergroup metamorphic rocks in the Xiaoqinling terrane, Qinling Orogen, on the southern margin of the North China Craton. The mineralization can be divided as follows: quartz-pyrite veins early, quartz-polymetallic sulfide veinlets middle, and carbonate-quartz veinlets late stages, with gold being mainly introduced in the middle stage. Three types of fluid inclusions were identified based on petrography and laser Raman spectroscopy, i.e., pure carbonic, carbonic-aqueous (CO₂–H₂O) and aqueous inclusions.The early-stage quartz contains pure carbonic and CO₂–H₂O inclusions with salinities up to 12.7 wt.% NaCl equiv., bulk densities of 0.67 to 0.86 g/cm³, and homogenization temperatures of 280−365 °C. The early-stage is related to H₂O–CO₂ ± N₂ ± CH₄ fluids with isotopic signatures consistent with a metamorphic origin (δ¹⁸O_water = 3.1 to 5.2‰, δD = − 37 to − 73‰). The middle-stage quartz contains all three types of fluid inclusions, of which the CO₂–H₂O and aqueous inclusions yield homogenization temperatures of 249−346 °C and 230−345 °C, respectively. The CO₂–H₂O inclusions have salinities up to 10.9 wt.% NaCl equiv. and bulk densities of 0.70 to 0.98 g/cm³, with vapor bubbles composed of CO₂ and N₂. The isotopic ratios (δ¹⁸O_water = 2.2 to 3.6‰, δD = − 47 to − 79‰) suggest that the middle-stage fluids were mixed by metamorphic and meteoric fluids. In the late-stage quartz only the aqueous inclusions are observed, which have low salinities (0.9−9.9 wt.% NaCl equiv.) and low homogenization temperatures (145−223 °C). The isotopic composition (δ¹⁸O_water = − 1.9 to 0.5‰, δD = − 55 to − 66‰) indicates the late-stage fluids were mainly meteoric water.Trapping pressures estimated from CO₂–H₂O inclusions are 100−285 MPa for the middle stage, suggesting that gold mineralization mainly occurred at depths of 10 km. Fluid boiling and mixing caused rapid precipitation of sulfides and native Au. Through boiling and inflow of meteoric water, the ore-forming fluid system evolved from CO₂-rich to CO₂-poor in composition, and from metamorphic to meteoric, as indicated by decreasing δ¹⁸O_water values from early to late. The carbon, sulfur and lead isotope compositions suggest the hostrocks within the Taihua Supergroup to be a significant source of ore metals. Integrating the data obtained from the studies including regional geology, ore geology, and fluid inclusion and C–H–O–S–Pb isotope geochemistry, we conclude that the Qiangma gold deposit was an orogenic-type system formed in the tectonic transition from compression to extension during the Jurassic−Early Cretaceous continental collision between the North China and Yangtze cratons.     

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.     

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.     

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.     

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.     

Influence of crude oil on the genesis of the Lanjiagou porphyry molybdenum deposit,western Liaoning Province,China

The Lanjiagou porphyry molybdenum deposit in western Liaoning Province, China, is hosted in fine-grained Jurassic granites. LA-ICP-MS zircon U–Pb analyses indicate that the crystallization of the ore-hosting granites took place 185.0 ± 1.8 Ma (MSWD = 1.4). Molybdenum mineralization in the deposit can be divided into three stages: the stockwork quartz vein stage, the planar quartz vein stage, and the fissure-filling quartz vein stage. Re–Os isotopic ages for the molybdenite from the stockwork quartz vein-type ores yielded an isochron age of 188.8 ± 9.9 Ma (MSWD = 3.0), while six samples from the planar quartz vein-type ores yielded a similar isochron age of 185.6 ± 1.2 Ma (MSWD = 0.5). Re–Os isotopic ages for the molybdenite identical, within error, to zircon U–Pb isotopic ages indicate that the molybdenum mineralization is related to the host intrusions. Apart from primary inorganic fluid inclusions (IFIs), a large number of primary organic fluid inclusions (OFIs) are found in the latter two stages of vein quartz, and minors found in the first stage. The components and characteristics of OFIs in the three stages of vein quartz differ from each other, which is also true for the IFIs. OFIs in stockwork vein quartz are characterized by halite-bearing inclusions, and organic liquids in the inclusions are brown and do not fluoresce under ultraviolet (UV) light. Homogenization temperatures (T_h) for the primary IFIs coeval with OFIs of this stage ranges from 300 °C to > 450 °C, while the salinity varies from 10 to 53 wt.% NaCl equiv.. In planar vein quartz, OFIs are predominately two-phased (liquid and gas), and salt daughter minerals (halite) are absent. Organic liquids are light brown to colorless and show blue fluorescence under UV light; The T_h range for the IFIs of this stage is 250–360 °C, and the salinity range is 3–17 wt.% NaCl equiv. Finally, OFIs in fissure-filling vein quartz are marked by liquid–gas inclusions. Organic liquids are generally colorless and show yellow fluorescence under UV light. The T_h range for the primary IFIs is 180–240 °C and the salinity range is 4–11 wt.% NaCl equiv. Organic geochemical analyses indicate that organic matter in the Lanjiagou deposit was derived from mature crude oil. We suggest that large volumes of crude-oil-bearing non-magmatic fluids were flushed into the Lanjiagou porphyry hydrothermal system during all phases of ore formation and likely played important roles in mineralization.     

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.     

Silver-base metal epithermal vein and listwanite hosted deposit Crnac,Rogozna Mts., Kosovo,part II: A link between magmatic rocks and epithermal mineralization

Crnac is an intermediate sulfidation Pb–Zn–Ag epithermal deposit located within the Vardar suture zone of the Central Balkan Peninsula. The epithermal Pb–Zn–Ag mineralization consists of (i) a series of steeply-dipping veins hosted within the Jurassic amphibolites, and (ii) overlying hydrothermal-explosive breccia with angular (level IV) or rounded fragments of listwanite (surface) cemented by epithermal mineralization. The mineralization is related to the Oligocene quartz latite dykes that crosscut the Crnac antiform. Quartz latite rocks predominantly display a shoshonitic character. The obtained ⁴⁰Ar/³⁹Ar age of fresh quartz latite is 28.9 ± 0.3 Ma. Fine-grained sericite from altered quartz latite is dated at 28.6 ± 0.5 Ma. Early, alteration related fluid inclusions within quartz latite show coexistence of high-density brine and a low-density vapor-saturated phase that homogenized at 280–405 °C. Phase separation occurs at a paleodepth of 0.6 to 0.9 km.Epithermal mineralization developed in three stages: (i) early pyrite–arsenopyrite–pyrrhotite–quartz–kaolinite; (ii) main sphalerite–galena–tetrahedrite–chalcopyrite and (iii) late carbonate–pyrite–arsenopyrite assemblage. The onset of mineral deposition within epithermal veins was initiated by boiling of Na–Cl ± K ± Ca ± Mg fluid at a paleodepth of 0.6 to 0.9 km. Coexisting vapor and liquid-rich inclusions display salinities and trapping temperatures of 4 wt.% NaCl equiv., 280–370 °C and 2–27 wt.% NaCl equiv., 230–375 °C, respectively. Boiling continued throughout the deposition of the sphalerite-galena-tetrahedrite-chalcopyrite assemblage. Late stage carbonate was deposited from diluted, non-boiling, low-temperature Na–Ca–Mg–Cl ± CO₂ fluid (0.2 to 4.8 wt.% NaCl equiv., 115–280 °C).About 100–150 m higher in the system, precipitation of listwanite breccia cement began as a result of boiling Na–Cl ± Ca ± Mg ± K fluid of medium salinities (2.6 to 12.1 wt.% NaCl equiv.) at temperatures of 245–370 °C. Boiling and dilution of fluids continue throughout the precipitation of the main sphalerite-galena-tetrahedrite and late, mainly carbonate assemblage. Surface listwanite breccia contain quartz phenocrysts deposited from a homogeneous fluid with a medium salinity (8–10 wt.% NaCl equiv.) and high temperatures (T_h = 295–315 °C), whereas the early and main stage of a surface listwanite breccia cement precipitated from a boiling fluid of decreasing salinity and temperature. Aqueous ± CO₂, high salinity (16 to 18 wt.% NaCl equiv.), low temperature (120 °C), homogeneously trapped fluid that precipitated late stage carbonates, is most likely a remnant of boiled off fluid. The epithermal assemblage of the surface listwanites precipitated at a paleodepth of 0.4 to 0.6 km.The δ¹³C values of the late stage ankerite range from − 4.2 to 4.1‰, whereas δ¹⁸O range from 9.6 to 17.5‰. The calculated δ¹⁸O of fluid that precipitated carbonates within epithermal veins, and listwanite breccia cement range from 6.3 to 11.3‰, indicating a contribution of magmatic water.Deposition of all mineralization types was initiated by neutralization of primary acidic magmatic fluid by water-rock reactions that caused widespread propylitization and sericitization. Extensive and long-lasting boiling combined with dilution by meteoric water increased the pH towards the final stage of hydrothermal activity.     

Genesis of the Proterozoic Mangabeira tin–indium mineralization,Central Brazil: Evidence from geology,petrology, fluid inclusion and stable isotope data

The Mangabeira deposit is the only known Brazilian tin mineralization with indium. It is hosted in the Paleo- to Mesoproterozoic Mangabeira within-plate granitic massif, which has geochemical characteristics of NYF fertile granites. The granitic massif is hosted in Archean to Paleoproterozoic metasedimentary rocks (Ticunzal formation), Paleoproterozoic peraluminous granites (Aurumina suite) and a granite–gneiss complex. The mineralized area comprises evolved Li-siderophyllite granite, topaz–albite granite, Li–F-rich mica greisens and a quartz–topaz rock, similar to topazite. Two types of greisens are recognized in the mineralized area: zinnwaldite greisen and Li-rich muscovite greisen, formed by metasomatism of topaz–albite granite and Li-siderophyllite granite, respectively. Cassiterite occurs in the quartz–topaz rock and in the greisens. Indium minerals, such as roquesite (CuInS₂), yanomamite (InAsO₄·2H₂O) and dzhalindite (In(OH₃)), and In-rich cassiterite, sphalerite, stannite group minerals and scorodite are more abundant in the quartz–topaz rock, and are also recognized in albitized biotite granite and in Li-rich muscovite greisen. The host rocks and mineralized zones were subsequently overprinted by the Brasiliano orogenic event.Primary widespread two-phase aqueous and rare coeval aqueous-carbonic fluid inclusions are preserved in quartz from the topaz–albite granite, in quartz and topaz from the quartz–topaz rock and in cassiterite from the Li-rich muscovite greisen. Eutectic temperatures are − 25 °C to − 23 °C, allowing modeling of the aqueous fluids in the system H₂O–NaCl(–KCl). Rare three-phase H₂O–NaCl fluid inclusions (45–50 wt.% NaCl equiv.) are restricted to the topaz–albite granite. Salinities and homogenization temperatures of the aqueous and aqueous-carbonic fluid inclusions decrease from the topaz–albite granite (15–20 wt.% NaCl equiv.; 400 °C–450 °C), to the quartz–topaz rock (10–15 wt.% NaCl equiv.; 250 °C–350 °C) and to the greisen (0–5 wt.% NaCl equiv.; 200 °C–250 °C). Secondary fluid inclusions have the same range of salinities as the primary fluid inclusions, and homogenize between 150 and 210 °C.The estimated equilibrium temperatures based on δ¹⁸O of quartz–mica pairs are 610–680 °C for the topaz–albite granite and 285–370 °C for the Li-rich muscovite greisens. These data are coherent with measured fluid inclusion homogenization temperatures. Temperatures estimated using arsenopyrite geothermometry yield crystallization temperatures of 490–530 °C for the quartz–topaz rock and 415–505 °C for the zinnwaldite greisens. The fluids in equilibrium with the topaz–albite granite have calculated δ¹⁸O and δD values of 5.6–7.5‰ and − 67 to − 58‰, respectively. Estimated δ¹⁸O and δD values are mainly 4.8–7.9‰ and − 60 to − 30‰, respectively, for the fluids in equilibrium with the quartz–topaz rock and zinnwaldite greisen; and 3.4–3.9‰ and − 25 to − 17‰, respectively, for the Li-rich muscovite greisen fluid. δ³⁴S data on arsenopyrite from the quartz–topaz rock vary from − 1.74 to − 0.74‰, consistent with a magmatic origin for the sulfur. The integration of fluid inclusion with oxygen isotopic data allows for estimation of the minimum crystallization pressure at ca. 770 bar for the host topaz–albite granite, which is consistent with its evolved signature.Based on petrological, fluid inclusion and isotope data it is proposed that the greisens and related Mangabeira Sn–In mineralization had a similar hydrothermal genesis, which involved exsolution of F-rich, Sn–In-bearing magmatic fluids from the topaz–albite granite, early formation of the quartz–topaz rock and zinnwaldite greisen, progressive cooling and Li-rich muscovite greisen formation due to interaction with meteoric water. The quartz–topaz rock is considered to have formed in the magmatic-hydrothermal transition. The mineralizing saline and CO₂-bearing fluids are interpreted to be of magmatic origin, based on the isotopic data and paragenesis, which has been documented as characteristic of the tin mineralization genetically related to Proterozoic within-plate granitic magmatism in the Goias Tin Province, Central Brazil.     

Fluid inclusions and H–O–S–Pb isotope systematics of the Baishan porphyry Mo deposit in Eastern Tianshan,China

The Baishan porphyry Mo deposit formed in the Middle Triassic in Eastern Tianshan, Xinjiang, northwestern China. Mo mineralization is associated with the Baishan monzogranite and granite porphyry stocks, mainly presenting as various types of hydrothermal veinlets in alerted wall rocks, with potassic, phyllic, propylitic, and fluorite alteration. The ore-forming process can be divided into four stages: stage I K-feldspar–quartz–pyrite veinlets, stage II quartz–molybdenite ± pyrite veinlets, stage III quartz–polymetallic sulfide veinlets and stage IV barren quartz–calcite veins. Four types of fluid inclusions (FIs) can be distinguished in the Baishan deposit, namely, liquid-rich two-phase (L-type), vapor-rich two-phase (V-type), solid-bearing multi-phase (S-type) and mono-phase vapor (M-type) inclusions, but only the stage I quartz contains all types of FIs. The stages II and III quartz have three types of FIs, with exception of M-type. In stage IV quartz minerals, only the L-type inclusions can be observed. The FIs in quartz of stages I, II, III and IV are mainly homogenized at temperatures of 271–468 °C, 239–349 °C, 201–331 °C and 134–201 °C, with salinities of 2.2–11.6 wt.% NaCl equiv., 1.1–10.2 wt.% NaCl equiv., 0.5–8.9 wt.% NaCl equiv. and 0.2–5.7 wt.% NaCl equiv., respectively. The ore-forming fluids of the Baishan deposit are characterized by high temperature, moderate salinity and relatively reduced condition, belonging to a H₂O–NaCl ± CH₄ ± CO₂ system. Hydrogen and oxygen isotopic compositions of quartz indicate that the ore-forming fluids were gradually evolved from magmatic to meteoric in origin. Sulfur and lead isotopes suggest that the ore-forming materials came predominantly from a deep-seated magma source from the lower continental crust. The Mo mineralization in the Baishan deposit is estimated to have occurred at a depth of no less than 4.7 km, and the decrease in temperature and remarkable transition of the redox condition (from alkalinity to acidity) of ore-forming fluids were critical for the formation of the Baishan Mo 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.     

Geochronology and fluid inclusion study of the Yinjiagou porphyry–skarn Mo–Cu–pyrite deposit in the East Qinling orogenic belt,China

The Yinjiagou Mo–Cu–pyrite deposit of Henan Province is located in the Huaxiong block on the southern margin of the North China craton. It differs from other Mo deposits in the East Qingling area because of its large pyrite resource and complex associated elements. The deposit’s mineralization process can be divided into skarn, sulfide, and supergene episodes with five stages, marking formation of magnetite in the skarn episode, quartz–molybdenite, quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite, and calcite–galena–sphalerite in the sulfide episode, and chalcedony–limonite in the supergene episode. Re–Os and ⁴⁰Ar–³⁹Ar dating indicates that both the skarn-type and porphyry-type orebodies of the Yinjiagou deposit formed approximately 143 Ma ago during the Early Cretaceous. Four types of fluid inclusions (FIs) have been distinguished in quartz phenocryst, various quartz veins, and calcite vein. Based on petrographic observations and microthermometric criteria the FIs include liquid-rich, gas-rich, H₂O–CO₂, and daughter mineral-bearing inclusions. The homogenization temperature of FIs in quartz phenocrysts of K-feldspar granite porphyry ranges from 341 °C to >550 °C, and the salinity is 0.4–44.0 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite veins is 382–416 °C, and the salinity is 3.6–40.8 wt% NaCl eqv. The homogenization temperature of FIs in quartz–calcite–pyrite–chalcopyrite–bornite–sphalerite ranges from 318 °C to 436 °C, and the salinity is 5.6–42.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–molybdenite stockworks is in a range of 321–411 °C, and the salinity is 6.3–16.4 wt% NaCl eqv. The homogenization temperature of FIs in quartz–sericite–pyrite is in a range of 326–419 °C, and the salinity is 4.7–49.4 wt% NaCl eqv. The ore-forming fluids of the Yinjiagou deposit are mainly high-temperature, high-salinity fluids, generally with affinities to an H₂O–NaCl–KCl ± CO₂ system. The δ¹⁸O_H2O values of ore-forming hydrothermal fluids are 4.0–8.6‰, and the δD_V-SMOW values are between −64‰ and −52‰, indicating that the ore-forming fluids were primarily magmatic. The δ³⁴S_V-CDT values of sulfides range between −0.2‰ and 6.3‰ with a mean of 1.6‰, sharing similar features with deeply sourced sulfur, implying that the sulfur mainly came from the lower crust composed of poorly differentiated igneous materials, but part of the heavy sulfur came from the Guandaokou Group dolostone. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb, and ²⁰⁸Pb/²⁰⁴Pb values of sulfides are in the range of 17.331–18.043, 15.444–15.575, and 37.783–38.236, respectively, which is generally consistent with the Pb isotopic signature of the Yinjiagou intrusion, suggesting that the Pb chiefly originated from the felsic–intermediate intrusive rocks in the mine area, with a small amount of lead from strata. The Yinjiagou deposit is a porphyry–skarn deposit formed during the Mesozoic transition of a tectonic regime that is EW-trending to NNE-trending, and the multiepisode boiling of ore-forming fluids was the primary mechanism for mineral deposition.     

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.     

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

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