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 and Genesis of the Ta'ergou Skarn - Quartz Vein Tungsten Deposit in the North Qilian Caledonian Orogenic Belt, Northwest China

Abstract. The Ta'ergou tungsten deposit in Gansu province, northwestern China, is located in the western part of the North Qilian Caledonian orogen, and consists of scheelite skarn bodies and wolframite quartz veins. The tungsten‐bearing skarn developed by the replacement of carbonate layers intercalated in the Precambrian schist and amphibolite whereas wolframite‐quartz ore veins developed along a group of fractures that cut through horizontal skarns. The Ta'ergou tungsten deposit is genetically related to the Caledonian Yeniutan granodiorite intrusion and occurs ca. 500 m wide in the exo‐contact zone 300 ～ 500 m apart from the intrusion. The granodiorite displays a lower grade of differentiation, low content of SiO₂ and high contents of mafic components. There are three types of fluid inclusions in the wolframite‐quartz vein systems, i. e. aqueous, CO₂‐H₂O and CO₂‐rich. The homogenization temperature of aqueous inclusion ranges from 140 to 380d?C and their salinities from 6.4 to 17.4 equivalent wt% NaCl. Laser Raman spectroscopy shows that the inclusions contain a relatively high content of CO₂. The δ³⁴S values of skarn type sulfides range from +8.1 to +12.7 per mil and those of quartz vein sulfides from +9.3 to +14.9 per mil, similar to sulfides of the granodiorite with from +6.0 to +11.7 per mil. The δ¹⁸O values of quartz are between +10.5 and +13.3 per mil and those of wolframite between +3.4 and +5.1 per mil. The δ¹⁸O water values of ore forming fluids range from +0.6 to +6.4 per mil and suggest the mixture of magmatic fluids with meteoric water formed the ore‐forming fluids. It has been proved that Precambrian strata in the west sector of North Qilian region are enriched in tungsten. We propose the strata were remelted to be tungsten‐granitoid during subduction. The polymetallic tungsten was gradually accumulated into the roof pendants of the granite intrusion by fractional crystallization and then was deposited by hydrothermal fluids during metasomatism and infilling along fractures. On the other hand, the granite intrusion also acted as “heating machine” to make hydrothermal fluids leach out the metals from Precambrian strata and these metals joined the ore‐forming hydrothermal system.     

Geology and Geochemistry of the Dashuigou Tellurium Deposit,Western Sichuan,China

The Dashuigou tellurium deposit, located on the western margin of the Yangtze platform, is unique. The deposit is hosted by Triassic metabasalt 50 to 80 meters thick. The orebodies occur as a group of NNE-striking parallel veins. Mineralization developed in three stages: Stage I— pyrrhotite-pyrite, Stage II—tetradymite, and Stage III—chalcopyrite-pyrite. Stage II is the principal tellurium mineralization stage and the tellurium-bearing minerals are mainly tetradymite, tsumoite, tellurbismuth, joseite, calaverite, stuetzite, and native tellurium. The general ore grade of the tellurium in Stage II ranges from 0.2 to 5 wt%, and it reaches 15 to 25 wt% for the massive ores. The dominant gangue minerals are calcite and dolomite, with minor biotite, muscovite, albite, quartz, and chlorite.

Fluid-inclusion studies of calcite, dolomite, and quartz from Stages I, II, and III yield homogenization temperatures of 356° to 260° C (mean = 320° C), 295° to 198° C (mean = 240°), and 235° to 152° C (mean = 170° C), respectively. Salinities of primary fluid inclusions in all three stages are 1.5 to 5.8 wt% NaCl equivalent, 9 to 15.2 wt% NaCl equivalent, and 2.8 to 3.0 wt% NaCl equivalent, respectively.

Isotopic studies show that δ34 values of sulfides range from -2.2 to +2.8 per mil. δ¹³C values of calcites and dolomites in the ore veins range from -5.3 to -7.42 per mil, and δ¹⁸O values range from +10.9 to +13.1 per mil, which are quite different from the δ¹³C values of+1.0 to +2.8 per mil and δ¹⁸O values of +16.8 to +28.5 per mil for the calcites from the Triassic carbonates in the deposit. The δD and δ¹⁸O values of muscovite and quartz were measured to be -61 to -54 per mil and +9.9 to +13.0 per mil, respectively. Values of δ¹⁸O_water computed from fluid-inclusion trapping temperatures are +3.9 and +7 per mil.

A date of 93 Ma was obtained through measurement of muscovite from the No. 12 ore vein. Sulfur-, oxygen-, carbon-, and hydrogenisotope data indicate that the ore-forming substances of the Dashuigou tellurium deposit were derived from deep-seated sources, and the mineralizations probably are associated with Late Mesozoic alkaline or alkaline granitic magmatism. The estimated sulfur fugacities (fs₂) are 10^?16.7 for Stage I and 10^?14 to 10^15.5 for Stage II, whereas the tellurium fugacities (f_Te2) are 10^?15 to 10^?14 and 10^?11.2 to 10^?10.5, respectively.     

The alteration, mineralogy and geochronology (SHRIMP U–Pb and 40Ar/39Ar) of copper-bearing Anjerd skarn, north of the Shayvar Mountain, NW Iran

A Cu-bearing skarn zone occurs north of the Shayvar Mountain in northwestern Iran. Skarn-type metasomatic alteration and mineralization occur along the contact between Upper Cretaceous impure carbonates and a Miocene Cu-bearing granitic stock. Both endoskarn and exoskarn developed in the rocks. Exoskarn is the principal skarn zone and is enclosed by a skarnoid–hornfelsic zone. Skarn formation occured during stages: (1) prograde, (2) middle stage and (3) late stage. In the prograde stage, there were two main processes: (a) metamorphic–bimetasomatic and (b) prograde metasomatic. The metamorphic process began immediately after intrusion of the pluton into the enclosing impure carbonates. The prograde metasomatic stage commenced with segregation and evolution of a fluid phase in the pluton and movement into fractures and micro-fractures in the skarnoid–hornfelsic rocks developed in a metamorphic zone. The introduction of considerable amounts of Fe, Si and Mg led to the development of voluminous medium- to coarse-grained anhydrous calc-silicates. During the middle stage, the previously formed skarn zones were affected by intense multiple hydrofracturing in the Cu-bearing stock. In addition to Fe, Si and Mg, substantial amounts of Cu, Pb and Zn, along with volatile components such as H₂S and CO₂ were added to the skarn system. Consequently, substantial amounts of hydrous calc-silicates (epidote, tremolite–actinolite), sulfides (pyrite, chalcopyrite and molybdenite), oxides (magnetite, hematite) and carbonates (calcite) replaced the anhydrous calc-silicates. The retrograde stage was synchronous with the incursion of relatively low-temperature, more oxidized fluids into skarn system, resulting in partial alteration of the early-formed calc-silicates and development of a series of very fine-grained aggregates of chlorite, clay, hematite and calcite. Zircon grains from the endoskarn zone provide constraints on the timing of solidification of the granite stock (9.91 ± 0.31 Ma) that caused mineralization in the Anjerd area. One sample of primary hornblende from the monzogranitic Shayvar batholith has an ⁴⁰Ar/³⁹Ar age of 26.54 ± 0.65 Ma and indicates that intrusion of the Miocene stock and associated Cu skarn formation occurred a considerable time after intrusion of the batholith.     

The Gumeshevo skarn-porphyry copper deposits in the Central Urals,Russia: Evolution of the ore-magmatic system as deduced from isotope geochemistry (Sr,Nd, C,O, H)

The Early Devonian Gumeshevo deposit is one of the largest ore objects pertaining to the dioritic model of the porphyry copper system paragenetically related to the low-K quartz diorite island-arc complex. The (⁸⁷Sr/⁸⁶Sr)_t and (ɛ_Nd)_t of quartz diorite calculated for t = 390 Ma are 0.7038–0.7045 and 5.0–5.1, respectively, testifying to a large contribution of the mantle component to the composition of this rock. The contents of typomorphic trace elements (ppm) are as follows: 30–48 REE sum, 5–10 Rb, 9–15 Y, and 1–2 Nb. The REE pattern is devoid of Eu anomaly. Endoskarn of low-temperature and highly oxidized amphibole-epidote-garnet facies is surrounded by the outer epidosite zone. Widespread retrograde metasomatism is expressed in replacement of exoskarn and marble with silicate (chlorite, talc, tremolite)-magnetite-quartz-carbonate mineral assemblage. The ⁸⁷Sr/⁸⁶Sr ratios of epidote in endoskarn and carbonate in retrograde metasomatic rocks (0.7054–0.7058 and 0.7053–0.7065, respectively) are intermediate between the Sr isotope ratios of quartz dioritic rocks and marble (⁸⁷Sr/⁸⁶Sr = 0.70784 ± 2). Isotopic parameters of the fluid equilibrated with silicates of skarn and retrograde metasomatic rocks replacing exoskarn at 400°C are δ¹⁸O = +7.4 to +8.5‰ and δD = −49 to −61‰ (relative to SMOW). The δ¹³C and δ¹⁸O of carbonates in retrograde metasomatic rocks after marble are −5.3 to +0.6 (relative to PDB) and +13.0 to +20.2% (relative to SMOW), respectively. Sulfidation completes metasomatism, nonuniformly superimposed on all metasomatic rocks and marbles with formation of orebodies, including massive sulfide ore. The δ³⁴S of sulfides is 0 to 2‰ (relative to CDT);⁸⁷Sr/⁸⁶Sr of calcite from the late calcite-pyrite assemblage replacing marble is 0.704134 ± 6. The δ¹³C and ⁸⁷Sr/⁸⁶Sr of postore veined carbonates correlate positively (r = 0.98; n = 6). The regression line extends to the marble field. Its opposite end corresponds to magmatic (in terms of Bowman, 1998b) calcite with minimal δ¹³C, δ¹⁸O, and ⁸⁷Sr/⁸⁶Sr values (−6.9 ‰, +6.7‰, and 0.70378 ± 4, respectively). The aforementioned isotopic data show that magmatic fluid was supplied during all stages of mineral formation and interacted with marble and other rocks, changing its Sr, C, and O isotopic compositions. This confirms the earlier established redistribution of major elements and REE in the process of metasomatism. A contribution of meteoric and metamorphic water is often established in quartz from postore veins.     

Multi-stage metasomatism in the lithosphere beneath the Veneto Volcanic Province (VVP, Northern Italy)

Mantle peridotites from the Veneto Volcanic Province (VPP) have been investigated in order to constrain P-T conditions of mantle events, determine the style of the metasomatic reactions, and the compositions of the metasomatic agents. Studied rocks show dominant protogranular and transitional textures; only one sample shows effect of pyrometamorphism. Clinopyroxenes in protogranular lherzolites show depleted LREE patterns, while those of transitional rocks are characterised by spoon-shaped REE patterns (La up to 60 times chondrite), and variable enrichments in LILE. Two generations of fluid inclusions are recognised: 1) Type I (CO₂ ± CO ± C fluid) found only in orthopyroxene of transitional xenoliths which may contain very small amphibole; 2) Type II (CO₂-rich fluid) found in all minerals of all xenoliths. Most of inclusions homogenize to liquid, with Th_L ranging between ?44 and 31°C. The densest CO₂ fluid inclusions (d?=?1.13?g/cm³), indicates a trapping pressure of ~10?kbar at 800°C. We propose that the mantle beneath the VVP equilibrated at pressures of 10?kbar, at about 800°C. Traces of an aqueous fluid preserved as fluid inclusions in orthopyroxene suggest the existence of an older subduction related metasomatic event and the occurrence of two stages metasomatism in the lithosphere beneath the SE Alps.     

Fluid composition and origin in the hydrothermal system of the Nezhdaninsky gold deposit,Sakha (Yakutia), Russia

Petrochemical characteristics of igneous, sedimentary, and metasomatic rocks; chemical and isotopic compositions of minerals and fluids; and PT parameters of mineral formation at the Nezhdaninsky deposit are reported. A model of hydrothermal system formation is developed on this basis. In addition to decreasing Ba/Rb and Li/Mg ratios in the course of the hydrothermal process, resulting in the formation of ore-bearing metasomatic rocks, increasing K/Ba and diminishing K/Cs ratios indicate the probable participation of magmatic fluid in the ore deposition. The agreement of the K/Rb and K/Ba ratios with the values typical of the main trend of igneous rocks (MT) implies that the K, Rb, and Ba contents were distributed in the ore-forming hydrothermal fluid according to the ratios in the source magmatic chamber. The K/Rb ratios in metasomatic rocks correspond to the MT and approach the pegmatitic-hydrothermal trend and the composition of orthomagmatic fluid of Mo-W greisen. Similar REE patterns of igneous and terrigenous rocks do not allow the REE source to be constrained unequivocally. The lithological control of lithophile element distribution testifies to the supply of host rock components to the hydrothermal system. All studied rocks and minerals are enriched in LREE. The REE total and the contribution of HREE decrease from preore to synore metasomatic rocks, from preore to regenerated carbonates, and from older to younger scheelite. A similar tendency is noted in granitoids of the Kurum pluton. The δ¹⁸O values of quartz range from +10.3 to +12.6‰ in Au-Mo-W zones, from +15.9 to +16.4‰ in metasomatic rocks, from +14.8 to +16.6‰ in gold-ore veins, and from +13.5 to +16.9‰ in silver-base-metal ore mineralization. The estimates of \(\delta ^{18} O_{H_2 O} \) suggest that water was supplied from a magmatic source (δ¹⁸O = +(5.5?9.0‰)) and as a product of sedimentary rock dehydration. High-temperature (up to 390°C) and highly concentrated (up to 31 wt % NaCl equiv) fluids participated in the mineral formation. The phase separation of the fluid into H₂O-CO₂ liquid and predominantly carbon dioxide gas was combined with mixing of a high-temperature and relatively highly concentrated chloride solution with a low-temperature and poorly mineralized fluid. The redox conditions varied from equilibrium with CH₄-bearing fluid at the gold-molybdenum-tungsten stage to equilibrium with CO₂-bearing fluid during the gold-ore stage.     

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.     

Mineralogy and metasomatic evolution of the Mianeh iron skarn deposit,Norduz-Agarak border,NW Iran

The Mianeh iron skarn deposit lies in the Arasbaran region within the Qaradagh metallogenic district, NW Iran. This high-grade massive magnetite skarn originated by the interaction of Upper Cretaceous limestone with metasomatic ore-bearing fluids associated with hypabyssal Oligo-Miocene quartz diorite. Mineral chemistry of the primary clinopyroxenes demonstrates the sub-alkaline, volcanic arc setting of magmatism. Two general stages of skarnification are recognized: (1) silicate skarn (stage I) is composed essentially of grossular and low-Fe diopside formed before the main mineralization and (2) magnetite-garnet skarn (stage II) composed of strongly anisotropic coarse-grained garnets with a narrow compositional zoning radially formed by addictive infiltrating of silica and iron-rich metasomatic fluids which overprint and/or crosscut the early stage silicate skarn. Anhydrous prograde calc-silicate assemblages were replaced by a series of hydrous calc-silicates (epidote, tremolite-actinolite) and/or quartz, calcite, magnetite, hematite, and pyrite. Magnetite (±hematite) is the dominant hypogene ore mineral that initially precipitated coincident with the late prograde to the early retrograde metasomatic stages. Mineralogical studies suggest that silicate skarn formation commenced at temperatures about 560 °C, X(CO₂)_fluid ≤ 0.15, αSiO₂～?1.0, and fluid pressure 1.0 kbar. The magnetite-garnet skarn formed from H₂O-rich fluids [X(CO₂)_fluid < 0.1] at a temperature of 525 to 450 °C and maximum log ?O₂ between ?20.2 and ?23. During the late stages of prograde skarn development, the stability field of andradite shifted to low ?O₂ and ?S₂ conditions resulting in main iron ore deposition (as magnetite). The andradite replacement temperature and presence of pyrite (instead of pyrrhotite) suggest that log?S₂ remained constant at about ?6 to ?7 during cooling of the system.     

The world-class Natalka gold deposit, northeast Russia: REE patterns, fluid inclusions, stable oxygen isotopes, and formation conditions of ore

REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)^2? complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by $ \delta ^{18} O_{H_2 O} REE patterns of hydrothermally altered rocks, fluid inclusions, and stable oxygen isotopes of quartz were studied at the Natalka gold deposit. Metasomatic rocks formed under decompression reveal gradual depletion in LREE and HREE relative to siltstone of the protolith. The HREE patterns of metasomatic rocks formed under decompression are uniform; an insignificant removal of LREE can be noted. The progressive extraction of REE with increasing alteration of rocks could have been due to the effect of magmatogenic or meteoric fluid. Because a Ce anomaly is absent, the participation of oxidized meteoric water was limited. The inverse correlation between the total REE content and the Eu anomaly value in altered rocks indicates a substantial role of magmatogenic fluid. The REE patterns of altered rocks formed under compression show that the role of metamorphic fluid was not great. All metasomatic rocks are enriched in LREE, so that the enrichment of fluid in LREE as well may be suggested. Three fluid compositions were captured as fluid inclusions: (1) H₂O-CO₂-NaCl-MgCl₂ with a salinity of 1.0–4.9 wt % NaCl equiv, (2) CO₂-CH₄, and (3) H₂O-NaCl-MgCl₂ with a salinity of 7.0–5.6 wt % NaCl equiv. Compositions (1) and (2) coexisted in the mineral-forming system at 250–350°C and 1.1–2.4 kbar as products of phase separation under conditions of decreasing P and T. The interaction of this fluid with host rocks resulted in the formation of extensive halos of beresitized rocks with sulfide disseminations. The precipitation of arsenopyrite and pyrite led to the substantial depletion of mineral-forming fluid in H₂S and destabilization of the Au(HS)²⁻ complex. The fluid with the third composition arose due to the boiling of the H₂O-CO₂-CH₄-NaCl-MgCl₂ liquid and was responsible for metasomatic alteration of host rocks. The late mineral assemblages were deposited from this fluid at the initial stage of ore formation. The high methane concentrations in the ore-forming fluid were likely caused by interaction of hydrothermal ore-bearing solutions with carbonaceous host rocks. The δ¹⁸O values of quartz from quartz-scheelite-pyrite-arsenopyrite and sulfide-sulfosalt mineral assemblages vary from +11.6 to +14.1‰ and +11.2 to +13.5‰, respectively. The parental fluids of the early and late mineral assemblages probably were derived from a magmatic source and were characterized by = +6.3 to +8.8‰ at 350°C and +3.6 to +5.9‰ at 280°C, respectively. The narrow interval of oxygen isotopic compositions shows that this source was homogeneous. The data obtained allow us to suggest that the deposit formation was related to magmatic activity, including the direct supply of ore components from a magma chamber and mobilization of these components in the processes of dehydration and decarbonation during contact and regional metamorphism. Original Russian Text ? N.A. Goryachev, O.V. Vikent’eva, N.S. Bortnikov, V.Yu. Prokof’ev, V.A. Alpatov, V.V. Golub, 2008, published in Geologiya Rudnykh Mestorozhdenii, 2008, Vol. 50, No. 5, pp. 414–444.     

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.     

Metasomatism of continental crust during subduction: the UHP whiteschists from the Southern Dora-Maira Massif (Italian Western Alps)

The ultrahigh‐pressure pyrope whiteschists from the Brossasco‐Isasca Unit of the Southern Dora‐Maira Massif represent metasomatic rocks originated at the expense of post‐Variscan granitoids by the influx of fluids along shear zones. In this study, geochemical, petrological and fluid‐inclusion data, correlated with different generations of pyrope‐rich garnet (from medium, to very‐coarse‐grained in size) allow constraints to be placed on the relative timing of metasomatism and sources of the metasomatic fluid. Geochemical investigations reveal that whiteschists are strongly enriched in Mg and depleted in Na, K, Ca and LILE (Cs, Pb, Rb, Sr, Ba) with respect to the metagranite. Three generations of pyrope, with different composition and mineral inclusions, have been distinguished: (i) the prograde Prp I, which constitutes the large core of megablasts and the small core of porphyroblasts; (ii) the peak Prp II, which constitutes the inner rim of megablasts and porphyroblasts and the core of small neoblasts; and (iii) the early retrograde Prp III, which locally constitutes an outer rim. Two generations of fluid inclusions have been recognized: (i) primary fluid inclusions in prograde kyanite that represent a NaCl‐MgCl₂‐rich brine (6–28 wt% NaCl_eq with Si and Al as other dissolved cations) trapped during growth of Prp I (type‐I fluid); (ii) primary multiphase‐solid inclusions in Prp II that are remnants of an alumino‐silicate aqueous solution, containing Mg, Fe, alkalies, Ca and subordinate P, Cl, S, CO₃^2‐, LILE (Pb, Cs, Sr, Rb, K, LREE, Ba), U and Th (type‐II fluid), at the peak pressure stage. We propose a model that illustrates the prograde metasomatic and metamorphic evolution of the whiteschists and that could also explain the genesis of other Mg‐rich, alkali‐poor schists of the Alps. During Alpine metamorphism, the post‐Variscan metagranite of the Brossasco‐Isasca Unit experienced a prograde metamorphism at HP conditions (stage A: ～1.6 GPa and ≤ 600 °C), as indicated by the growth of an almandine‐rich garnet in some xenoliths. At stage B (1.7–2.1 GPa and 560–590 °C), the influx of external fluids, originated from antigorite breakdown in subducting oceanic serpentinites, promoted the increase in Mg and the decrease of alkalies and Ca in the orthogneiss toward a whiteschist composition. During stage C (2.1 < P < 2.8 GPa and 590 < T < 650 °C), the metasomatic fluid influx coupled with internal dehydration reactions involving Mg‐chlorite promoted the growth of Prp I in the presence of the type‐I MgCl₂‐brine. At the metamorphic peak (stage D: 4.0–4.3 GPa and 730 °C), Prp II growth occurred in the presence of a type–II alumino‐silicate aqueous solution, mostly generated by internal dehydration reactions involving phlogopite and talc. The contribution of metasomatic external brines at the metamorphic climax appears negligible. This fluid, showing enrichment in LILE and depletion in HFSE, could represent a metasomatic agent for the supra‐subduction mantle wedge.     

Geochemistry and mineralization age of magnesian skarn-type iron deposits of the Janggun mine, Republic of Korea

The Janggun iron deposits, Republic of␣Korea, occur as lens-shaped magnesian skarn, magnetite and base-metal sulfide orebodies developed in the Cambrian Janggun Limestone Formation. Mineralization stage of the deposits can be divided into two separate events. The skarn stage (107 Ma) consists of magnetite, pyrrhotite, base-metal sulfides, carbonates and magnesian skarn minerals. The hydrothermal stage (70 Ma) consists of base-metal sulfides, native bismuth, bismuthinite, tetrahedrite, boulangerite, bournonite and stannite. Mineral assemblages, chemical compositions and thermodynamic considerations indicate that formation temperatures, −log fs₂ and −log fo₂ values of ore fluids from the skarn stage were 433 to 345 °C, 8.1 to 9.7 bar and 29.4 to 31.6 bar, and the hydrothermal stage was 245 to 315 °C, 10.4 to 13.2 bar and 33.6 to 35.4 bar, respectively. Thermochemical considerations indicate that the XCO₂ during magnesian skarnization ranged from 0.06 to 0.09, and the activity of H⁺ presumably decreased when the fluids equilibrated with host dolomitic limestone which resulted in a pH change from about 6.1 to 7.8, and decreases in fo₂ and fs₂. The δ³⁴S values of ore sulfides have a wide range from 3.2 to 11.6 ‰ (CDT). Calculated ³⁴SH_{2 S} values of ore fluids are 2.9 to 5.4 ‰ (skarn stage) and 8.7 to 13.5 ‰ (hydrothermal stage). These are interpreted to represent an initial deep-seated, igneous source of sulfur which gave way to influence of oxidized sedimentary sulfur to hydrothermal stage. The δ¹³C values of carbonates in ores range from −4.6 to −2.5 ‰ (PDB). It is likely that carbon in the ore fluids was a mixture of deep-seated magmatic carbon and dissolved carbon of dolomitic limestone. The δ¹⁸OH_{2 O} and δD values (SMOW) of water in the ore fluids were 14.7 to 1.8 and −85 to −73 ‰ during the skarn stage and 11.1 to −0.2 and −87 to −80 ‰ in the hydrothermal stage. Received: 5 March 1997 / Accepted: 28 August 1997     

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.     

Implication of Apatite and Anhydrite for Formation of an Iron‐Oxide‐Apatite (IOA) Rare Earth Element Prospect,Benjamin River,Canada

The Benjamin River apatite prospect in northern New Brunswick, Canada, is hosted by the Late Silurian Dickie Brook plutonic complex, which is made up of intrusive units represented by monzogranite, diorite and gabbro. The IOA ores, composed mainly of apatite, augite, and magnetite at Benjamin River form pegmatitic pods and lenses in the host igneous rocks, the largest of which is 100 m long and 10–20 m wide in the diorite and gabbro units. In this study, 28 IOA ore and rock samples were collected from the diorite and gabbro units. Mineralogical observations show that the apatite–augite–magnetite ores are variable in the amounts of apatite, augite, and magnetite and are associated with minor amounts of epidote‐group minerals (allanite, REE‐rich epidote and epidte) and trace amounts of albite, titanite, ilmenite, titanomagnetite, pyrite, chlorite, calcite, and quartz. Apatite and augite grains contain small anhydrite inclusions. This suggests that the magma that crystallized apatite and augite had high oxygen fugacity. In back scattered electron (BSE) images, apatite grains in the ores have two zones of different appearance: (i) primary REE‐rich zone; and (ii) porous REE‐poor zone. The porous REE‐poor zones mainly appear in rims and/or inside of the apatite grains, in addition to the presence of apatite grains which totally consist of a porous REE‐poor apatite. This porous REE‐poor apatite is characterized by low REE (<0.84 wt%), Si (<0.28 wt%), and Cl (<0.17 wt%) contents. Epidote‐group minerals mainly occur in grain boundary between the porous REE‐poor apatite and augite. These indicate that REE leached from primary REE‐rich apatite crystallized as allanite and REE‐rich epidote. Magnetite in the ores often occurs as veinlets that cut apatite grains or as anhedral grains that replace a part of augite. These textures suggest that magnetite crystallized in the late stage. Pyrite veins occur in the ores, including a large amount of quartz and calcite veins. Pyrite veins mainly occur with quartz veins in augite. These textures indicate pyrite veins are the latest phase. Apatite–augite–magnetite ore, gabbro–quartz diorite and feldspar dike collected from the Benjamin River prospect contain dirty pure albite (Ab₉₈Or₂–Ab₁₀₀) under the microscope. The feldspar dikes mainly consist of dirty pure albite. Occurrences of the dirty pure albite suggest remarkable albitization (sodic alteration) of original plagioclase (An_25.3–An₆₀ in Pilote et al., 2012) associating with intrusion of monzogranite into gabbro and diorite. SO₄^2? bearing magma crystallized primary REE‐rich apatite, augite and anhydrite reacted with Fe in the sodic fluids, which result in oxidation of Fe²⁺ and release of S^2? into the sodic fluids. REE, Ca and Fe from primary REE‐rich apatite, augite and plagioclase altered by the sodic fluids were released into the fluids. Then Fe³⁺ in the sodic fluids precipitated as Fe oxides and epidote‐group minerals in apatite–augite–magnetite ores. Finally, residual S^2? in sodic fluids crystallized as latest pyrite veins. In conclusion, mineralization in Benjamin River IOA prospect are divided into four stages: (1) oxidized magmatic stage that crystallized apatite, augite and anhydrite; (2) sodic metasomatic stage accompanying alteration of magmatic minerals; (3) oxidized fluid stage (magnetite–epidote group minerals mineralization); and (4) reduced fluid stage (pyrite mineralization).     

Ore geochemistry,zircon mineralogy,and genesis of the Sakharjok Y-Zr deposit,Kola Peninsula,Russia

The Sakharjok Y-Zr deposit in Kola Peninsula is related to the fissure alkaline intrusion of the same name. The intrusion ∼7 km in extent and 4–5 km² in area of its exposed part is composed of Neoarchean (2.68–2.61 Ma) alkali and nepheline syenites, which cut through the Archean alkali granite and gneissic granodiorite. Mineralization is localized in the nepheline syenite body as linear zones 200–1350 m in extent and 3–30 m in thickness, which strike conformably to primary magmatic banding and trachytoid texture of nepheline syenite. The ore is similar to the host rocks in petrography and chemistry and only differs from them in enrichment in zircon, britholite-(Y), and pyrochlore. Judging from geochemical attributes (high HSFE and some incompatible element contents (1000–5000 ppm Zr, 200–600 ppm Nb, 100–500 ppm Y, 0.1–0.3 wt % REE, 400–900 ppm Rb), REE pattern, Th/U, Y/Nb, and Yb/Ta ratios), nepheline syenite was derived from an enriched mantle source similar to that of contemporary OIB and was formed as an evolved product of long-term fractional crystallization of primary alkali basaltic melt. The ore concentrations are caused by unique composition of nepheline syenite magma (high Zr, Y, REE, Nb contents), which underwent subsequent intrachamber fractionation. Mineralogical features of zircon-the main ore mineral—demonstrate its long multistage crystallization. The inner zones of prismatic crystals with high ZrO₂/HfO₂ ratio (90, on average) grew during early magmatic stage at a temperature of 900–850°C. The inner zones of dipyramidal crystals with average ZrO₂/HfO₂ = 63 formed during late magmatic stage at a temperature of ∼500°C. The zircon pertaining to the postmagmatic hydrothermal stage is distinguished by the lowest ZrO₂/HfO₂ ratio (29, on average), porous fabric, abundant inclusions, and crystallization temperature below 500°C. The progressive decrease in ZrO₂/HfO₂ ratio was caused by evolution of melt and postmagmatic solution. The metamorphic zircon rims relics of earlier crystals and occurs as individual rhythmically zoned grains with an averaged ZrO₂/HfO₂ ratio (45, on average) similar to that of the bulk ore composition. The metamorphic zircon is depleted in uranium in comparison with magmatic zircon, owing to selective removal of U by aqueous metamorphic solutions. Zircon from the Sakharjok deposit is characterized by low concentrations of detrimental impurities, in particular, contains only 10–90 ppm U and 10–80 ppm Th, and thus can be used in various fields of application.     

Zinc and sulfur isotope variation in sphalerite from carbonate-hosted zinc deposits,Cantabria, Spain

We studied zinc and sulfur isotopes and the chemical composition of sphalerite samples from Picos de Europa (Aliva mine) and sphalerite and hydrozincite samples from La Florida mine, two carbonate-hosted Mississippi Valley-type (MVT) deposits located in northern Spain; despite being close, they are hosted in carbonatic rocks of different ages, Lower Carboniferous and Lower Cretaceous, respectively. The two generations of sphalerite at Picos de Europa show different δ⁶⁶Zn values (stage 1 sphalerite +0.24 per mil and stage 2 sphalerite from ?0.75 to +0.08 per mil). Both generations also differ in the sulfur isotope composition (stage 1 has δ³⁴S?=?+6.6 and stage 2 has δ³⁴S?=??0.9 to +2.9 per mil) and the chemical composition (stage 1 sphalerite, compared to stage 2 sphalerite, is significantly enriched in Pb, As, Mn, Sb, slightly enriched in Ag, Ni, and Cu and depleted in Co, Ga, Tl, Te, Ge, and Sn). We suggest that Zn isotope fractionation was controlled predominantly by pH and T changes. High Zn isotope values reflect rapid precipitation of sphalerite from higher-temperature acidic fluids that carried Zn mostly as chloride species after interaction with carbonate rocks while lower Zn isotope values most likely resulted from a longer precipitation process from fluid at higher pH and decreasing T that carried dominantly Zn sulfide species. At La Florida, sphalerite samples show light ⁶⁶Zn-depleted signatures with δ⁶⁶Zn values from ?0.80 to ?0.01 per mil (mostly between ?0.80 and ?0.24 per mil) and δ³⁴S values from +10.7 to +15.7 per mil without any relationship between the δ⁶⁶Zn and δ³⁴S values. Here, the variation in Zn isotope values is interpreted as related to mixing of fluids from two reservoirs. The Zn was carried by a single deep-seated and higher T (~250–320 °C) fluid, and precipitation took place after mixing with a connate S-rich fluid in a system with mH₂S?>?mZn²⁺ as a result of change in pH, T, and Zn predominant species. The light δ⁶⁶Zn accompanied by heavy δ³⁴S values resulted from fractionation of Zn aqueous sulfides at near-neutral pH and decreasing T. Hydrozincite samples show much heavier δ⁶⁶Zn values (+0.21 to +0.33 per mil), consistent with fractionation during supergene processes.     

Geochemistry and petrogenesis of placer nephrite from Hetian, Xinjiang, Northwest China

The Yurungkash and Karakash rivers, also known respectively as the White Jade and Black Jade rivers, located in Hetian, Xinjiang Province, Northwest China, are the two main sources in China of white, green, and black placer nephrite, with a long history (~ 5000 years) of exploration and mining. The twenty-nine placer nephrite samples collected from both rivers and analyzed in the present study possess fine-grained and compact microstructures. The mineral assemblages in the samples provide clues to the metamorphic/metasomatic processes that formed the nephrite, which was the result of one of the following reactions: dolomitic marble → tremolite, or dolomitic marble → diopside → tremolite. White nephrite from the Yurungkash River and green nephrite from the Karakash River are predominantly tremolite. Based on electron probe microanalytical data, backscattered electron images, and Raman spectra, two kinds of black nephrite from the Karakash River are identified: one dominated by actinolite aggregates, and another consisting of tremolite aggregates with graphite crystals up to 2 mm in length. Compared with black nephrite, white and green nephrites contain fewer mineral inclusions and have lower FeO and MnO contents. All the amphiboles in the nephrites have very low contents of Cr₂O₃ (0.00–0.07 wt.%) and NiO (0.00–0.05 wt.%) relative to serpentinite-related nephrite (0.07–0.43 wt.% Cr₂O₃, 0.08–0.36 wt.% NiO). Most of the nephrite samples have low total rare earth element (ΣREE) contents, ranging from 12.22 to 49.40 ppm. In two nephrite samples, relatively high ΣREE concentrations (161 and 190 ppm) are related to the presence of REE-bearing minerals. Whole-rock REE chondrite-normalized patterns of all samples are characterized by strong negative Eu anomalies (0.16–0.48), moderate light-REE enrichment (La/Nd_N = 1.8–5.0), and nearly flat heavy-REE distributions (Gd/Yb_N = 0.3–1.7). Nephrite samples from both river locations have δ¹⁸O and δD isotope compositions ranging from 1.1‰ to 5.6‰ and − 55.7‰ to − 72.4‰, respectively. These values are closer to those recorded in dolomite-related nephrites than those in serpentinite-related deposits. Importantly, δ¹⁸O and δD values correspond to fluid isotope compositions of δ¹⁸O = 1.6‰ to 6.1‰ (330 °C), 1.8‰ to 6.3‰ (350 °C), and 2.5‰ to 7.0‰ (430 °C), and δD = − 34.9‰ to − 52.5‰ (350 °C to 650 °C). These values are close to or within the field of magmatic water. Geochemical and petrographic characteristics point to a dolomite-related metamorphic/metasomatic origin for nephrite at both locations. The placer nephrite is likely to have been derived from primary nephrite deposits in the Kunlun Mountains around Hetian, based on the geological occurrence of the deposits.     

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.     

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.