Fluid evolution of the Chalukou giant Mo deposit in the northern Great Xing'an Range,NE China

The Chalukou giant Mo deposit in the Heilongjiang Province, northeastern China, is a porphyry deposit hosted in an intermediate‐felsic complex surrounded by Mesozoic volcano–sedimentary rocks. The mineralization process is composed of four stages, including quartz + K‐feldspar (Stage I), quartz + molybdenite (Stage II), pyrite + chalcopyrite + quartz ± other sulphides (Stage III) and carbonate ± fluorite ± quartz (Stage IV). The mineralization is generally associated with intense K‐feldspar‐, fluorite‐, phyllic‐ and propylitic alteration. Primary fluid inclusions (FIs) in quartz include four compositional types, i.e. pure carbonic (PC‐type), aqueous‐carbonic (C‐type), daughter mineral‐bearing (S‐type) and aqueous (W‐type) inclusions. Halite, sylvite and hematite are recognized as the daughter minerals in Stage I S‐type FIs, whereas molybdenite and chalcopyrite occur as daughter minerals in Stage II S‐type FIs. High‐salinity and high pressure (>220 MPa) FIs exist in Stage I quartz veins, characterized by homogenization through halite dissolution at temperatures of 324 to 517 °C. The paucity of coexisting vapour‐rich FIs with similar homogenization temperatures at this stage indicates that the initial S‐type inclusions have directly exsolved from the magma rather than boiling off of a low‐salinity vapour. Stage I quartz has captured the C‐ and W‐type FIs, which have totally homogenized at 270–530 °C with salinities of 1.6–17.0 wt.% NaCl equiv. At Stage II, the coexistence of all FI types were only observed at pressures of 150–218 MPa and temperatures of 352–375 °C, with two salinity clusters of 0.9–16.6 wt.% NaCl equiv. and 37–56 wt.% NaCl equiv. Stage III quartz contains W‐type FIs with homogenization temperatures of 158–365 °C, salinities of 0.5–9.0 wt.% NaCl equiv., and minimum pressures of 12–116 MPa; whilst Stage IV fluorite or calcite only contains W‐type FIs with homogenization temperatures of 121–287 °C, salinities of 0.5–5.3 wt.% NaCl equiv., and minimum pressures of 10–98 MPa. The estimated trapping pressure from Stages II to III suggests an alternating lithostatic–hydrostatic fluid‐system caused by fluid boiling. Ore fluids at the Chalukou Mo deposit may have been evolved from a CO₂‐rich, high‐salinity, and high‐oxygen fugacity (fO₂) magma system, to a CO₂‐poor, low‐salinity, and low‐fO₂ epithermal system. Two key points may have contributed to the formation of the Chalukou giant Mo deposit: The magmatic origin and fluid boiling that has resulted in decompression and rapid precipitation of metals. Copyright © 2014 John Wiley & Sons, Ltd.     

Orientation,composition, and entrapment conditions of fluid inclusions in the footwall of the northern Snake Range detachment,Nevada

Footwall rocks of the northern Snake Range detachment fault (Hampton and Hendry's Creeks) offer exposures of quartzite mylonites (sub-horizontal foliation) that were permeated by surface fluids. An S–C–C′ mylonitic fabric is defined by dynamically recrystallized quartz and mica. Electron backscatter diffraction analyses indicate a strong preferred orientation of quartz that is overprinted by two sets of sub-vertical, ESE and NNE striking fractures. Analyses of sets of three perpendicular thin sections indicate that fluid inclusions (FIs) are arranged according to macroscopic fracture patterns. FIs associated with NNE and ESE-striking fractures coevally trapped unmixed CO₂ and H₂O-rich fluids at conditions near the critical CO₂–H₂O solvus, giving minimum trapping conditions of T = 175–200 °C and ∼100 MPa H₂O-rich FIs trapped along ESE-trending microcracks in single crystals of quartz may have been trapped at conditions as low as 150 °C and 50 MPa indicating the latest microfracturing and annealing of quartz in an overall extensional system. Results suggest that the upper crust was thin (4–8 km) during FI trapping and had an elevated geotherm (>50 °C/km). Footwall rocks that have been exhumed through the brittle-ductile transition in such extensional systems experience both brittle and crystal-plastic deformation that may allow for circulation of meteoric fluids and grain-scale fluid–rock interactions.     

Fluid evolution of rare-element and muscovite granitic pegmatites from central Galicia, NW Spain

Fluid inclusions have been studied in three pegmatite fields in Galicia, NW Iberian Peninsula. Based on microthermometry and Raman spectroscopy, eight fluid systems have been recognized. The first fluid may be considered to be a pegmatitic fluid which is represented by daughter mineral (silicates)-rich aqueous inclusions. These inclusions are primary and formed above 500 °C (dissolution of daughter minerals). During pegmatite crystallization, this fluid evolved to a low-density, volatile-rich aqueous fluid with low salinity (93% H₂O; 5% CO₂; 0.5% CH₄; 0.2% N₂; 1.3% NaCl) at minimum P–T conditions around 3 ± 0.5 kbar and 420 °C. This fluid is related to rare-metal mineralization. The volatile enrichment may be due to mixing of magmatic fluids and fluids equilibrated with the host rock. A drop in pressure from 3 ± 0.5 to 1 kbar at a temperature above 420 °C, which may be due to the transition from predominantly lithostatic to hydrostatic pressure, is recorded by two-phase, water-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂). Another inclusion type is represented by two-phase, vapour-rich inclusions with a low-density vapour phase (CO₂, CH₄ and N₂), indicating a last stage of decreasing temperature (360 °C) and pressure (around 0.5 kbar), probably due to progressive exhumation. Finally, volatile (CO₂)-rich aqueous inclusions, aqueous inclusions (H₂O-NaCl) and mixed-salt aqueous inclusions with low Th, are secondary in charac- ter and represent independent episodes of hydrothermal fluid circulation below 310 °C and 0.5 kbar. Received: 14 October 1999 / Accepted: 5 October 1999     

Fluid evolution in the Kolar Gold Field: evidence from fluid inclusion studies

Gold mineralization in the Kolar schist belt of the Dharwar craton occurs dominantly in the form of a sulfide-poor Au-quartz lode (the Champion lode exposed in the Mysore and other mines) and sulfide-rich auriferous lodes (from the Nundydroog mine). Fluid inclusion microthermometric experiments were conducted on primary inclusions in quartz intimately associated with Au-mineralization. Homogenization studies on aqueous-biphase (L + V), aqueous polyphase (L + V+ halite) and aqueous-carbonic (L_CO2± V_CO2 + L_aq) inclusions from the Champion lode furnish a temperature range of 120 to 420 °C. Freezing of aqueous biphase inclusions and dissolution of halite in the aqueous polyphase inclusions provide salinity of 5 to 50 wt.% NaCl equivalent. Fluid inclusion thermobarometry from the total homogenization of aqueous-carbonic inclusions and from intersecting isochores of coeval pure-carbonic (L_CO2± V_CO2) and pure-aqueous inclusions constrain the P-T path of evolution of the fluid in the Champion lode. Gold precipitation was likely to have been brought about in response to a sharp fall in pressure with attendant unmixing of liquid-CO₂ from the parent H₂O-CO₂ fluid of possible metamorphic origin. This would imply transportation of gold by some pressure-sensitive complex such as the Au-carbonyl. Fluid characteristics are different in the sulfide-rich auriferous lodes, as indicated by the virtual absence of the CO₂-bearing and the halite-bearing inclusions. The fluid evolution path, as evident from the crude positive colinearity of temperature and salinity, is due to mixing of a low (≤200 °C) temperature-low saline (≤7 wt.% NaCl equivalent) fluid with a high temperature (≥400 °C)-high saline (≥50 wt.% NaCl equivalent) fluid. The lack of CO₂ and association of Au with sulfides indicate a different mode of gold transport, as chloride or bisulfide complexing, deposition of which was possibly brought about by fluid mixing. Received: 17 April 1997 / Accepted: 30 June 1998     

Geology, Geochemistry, and Genesis of the Tongcun Reduced Porphyry Mo (Cu) Deposit, NW Zhejiang Province, China

The Tongcun Mo(Cu) deposit in Kaihua city of Zhejiang Province,eastern China,occurs in and adjacent to the Songjiazhuang granodiorite porphyry and is a medium-sized and important porphyry type ore deposit.Two irregular Mo(Cu) orebodies consist of various types of hydrothermal veinlets.Intensive hydrothermal alteration contains skarnization,chloritization,carbonatization,silicification and sericitization.Based on mineral assemblages and crosscutting relationships,the oreforming processes are divided into five stages,i.e.,the early stage of garnet + epidote ± chlorite associated with skarnization and K-feldspar + quartz ± molybdenite veins associated with potassicsilicic alteration,the quartz-sulfides stage of quartz + molybdenite ± chalcopyrite ± pyrite veins,the carbonatization stage of calcite veinlets or stockworks,the sericite + chalcopyrite ± pyrite stage,and the late calcite + quartz stage.Only the quartz-bearing samples in the early stage and in the quartzsulfides stage are suitable for fluid inclusions(FIs) study.Four types of FIs were observed,including1) CO_2-CH_4 single phase FIs,2) CO_2-bearing two- or three-phase FIs,3) Aqueous two-phase FIs,and4) Aqueous single phase FIs.FIs of the early stages are predominantly CO_2- and CH_4-rich FIs of the CO_2-CH4-H_2O-NaCl system,whereas minerals in the quartz-sulfides stage contain CO_2-rich FIs of the CO_2-H_2O-NaCl system and liquid-rich FIs of the H_2O-NaCl system.For the CO_2-CH_4 single phase FIs of the early mineralization stage,the homogenization temperatures of the CO_2 phase range from 15.4 ℃ to 25.3 ℃(to liquid),and the fluid density varies from 0.7 g/cm~3 to 0.8 g/cm~3;for two- or three-phase FIs of the CO_2-CH_4-H_2O-NaCl system,the homogenization temperatures,salinities and densities range from 312℃ to 412℃,7.7 wt%NaCl eqv.to 10.9 wt%NaCl eqv.,and 0.9 g/cm~3 to 1.0 g/cm~3,respectively.For CO_2-H_2O-NaCI two- or threephase FIs of the quartz-sulfides stage,the homogenization temperatures and salinities range from255℃ to 418℃,4.8 wt%NaCl eqv.to 12.4 wt%NaCl eqv.,respectively;for H_2O-NaCl two-phase FIs,the homogenization temperatures range from 230 ℃ to 368 ℃,salinities from 11.7 wt%NaCl eqv.to16.9 wt%NaCl eqv.,and densities from 0.7 g/cm~3 to 1.0 g/cm~3.Microthermometric measurements and Laser Raman spectroscopy analyses indicate that CO_2 and CH_4 contents and reducibility(indicated by the presence of CH_4) of the fluid inclusions trapped in quartz-sulfides stage minerals are lower than those in the early stage.Twelve molybdenite separates yield a Re-Os isochron age of 163 ± 2.4 Ma,which is consistent with the emplacement age of the Tongcun,Songjiazhuang,Dayutang and Huangbaikeng granodiorite porphyries.The S18OSMow values of fluids calculated from quartz of the quartz-sulfides stage range from 5.6‰ to 8.6‰,and the JDSMOw values of fluid inclusions in quartz of this stage range from-71.8‰ to-88.9‰,indicating a primary magmatic fluid source.534SV-cdt values of sulfides range from+1.6‰ to +3.8‰,which indicate that the sulfur in the ores was sourced from magmatic origins.Phase separation is inferred to have occurred from the early stage to the quartz-sulfides stage and resulted in ore mineral precipitation.The characteristics of alteration and mineralization,fluid inclusion,sulfur and hydrogen-oxygen isotope data,and molybdenite Re-Os ages all suggest that the Tongcun Mo(Cu) deposit is likely to be a reduced porphyry Mo(Cu) deposit associated with the granodiorite porphyry in the Tongcun area.     

Geological and Fluid Inclusion Constraints on Gold Deposition Processes of the Dayingezhuang Gold Deposit,Jiaodong Peninsula,China

The Dayingezhuang gold deposit, hosted mainly by Late Jurassic granitoids on Jiaodong Peninsula in eastern China, contains an estimated 170 t of gold and is one of the largest deposits within the Zhaoping fracture zone. The orebodies consist of auriferous altered pyrite–sericite–quartz granites that show Jiaojia-type (i.e., disseminated and veinlet) mineralization. Mineralization and alteration are structurally controlled by the NE- to NNE-striking Linglong detachment fault. The mineralization can be divided into four stages: (K-feldspar)–pyrite–sericite–quartz, quartz–gold–pyrite, quartz–gold–polymetallic sulfide, and quartz–carbonate, with the majority of the gold being produced in the second and third stages. Based on a combination of petrography, microthermometry, and laser Raman spectroscopy, three types of fluid inclusion were identified in the vein minerals: NaCl–H2O (A-type), CO2–H2O–NaCl (AC-type), and pure CO2 (PC-type). Quartz crystals in veinlets that formed during the first stage contain mainly AC-type fluid inclusions, with rare PC-type inclusions. These fluid inclusions homogenize at temperatures of 251°C–403°C and have low salinities of 2.2–9.4 wt% NaCl equivalent. Quartz crystals that formed in the second and third stages contain all three types of fluid inclusions, with total homogenization temperatures of 216°C–339°C and salinities of 1.8–13.8 wt% NaCl equivalent for the second stage and homogenization temperatures of 195°C–321°C and salinities of 1.4–13.3 wt% NaCl equivalent for the third stage. In contrast, quartz crystals that formed in the fourth stage contains mainly A-type fluid inclusions, with minor occurrences of AC-type inclusions; these inclusions have homogenization temperatures of 106°C–287°C and salinities of 0.5–7.7 wt% NaCl equivalent. Gold in the ore-forming fluids may have changed from Au(HS)0 as the dominant species under acidic conditions and at relatively high temperatures and fO2 in the early stages, to Au(HS)2– under neutral-pH conditions at lower temperatures and fO2 in the later stages. The precipitation of gold and other metals is inferred to be caused by a combination of fluid immiscibility and water–rock interaction.     

Fluid evolution in quartz vein-hosted tungsten mineralization in Chhendapathar, Bankura District, West Bengal: Evidence from fluid inclusion study

Tungsten mineralization in Chhendapathar area is hosted by quartz veins that traverse mostly the metasediments in and around Jikhu Nala. Fluid inclusion microthermometric experiments reveal the presence of four distinct types of inclusions. These are: aqueous biphase, monophase carbonic, aqueouscarbonic and halite-bearing polyphase inclusions. Salinity-temperature variation points towards the presence of two fluids of contrasting salinities and both independently followed simple cooling paths without any indication of fluid mixing. The P-T of mineralization was calculated from the intersection of coexisting and coeval aqueous biphase, carbonic and halite-bearing inclusions. The deduced values range from 1.63kb/361°C to 2.30kb/385°C. However, the initial temperature must have been much higher as indicated from the high dissolution temperature (> 450°C) of halite. Transportation of tungsten in the high saline fluid was facilitated by cation-tungstate ion pairing, i.e., with the help of Na₂WO₄ and/or NaHWO₄ complexes. A rapid fall in solubility in such fluid with falling temperature (in the range of 300–400°C), and by occasional fluid-rock interaction triggered precipitation of wolframite.     

The nature, origin and physicochemical controls of hydrothermal Mo-Bi mineralization in the Cadillac deposit, Quebec, Canada

Mo-Bi mineralization occurs in subvertical and subhorizontal quartz-muscovite-± K-feldspar veins surrounded by early albitic and later K-feldspathic alteration halos in monzogranite of the Archean Preissac pluton, Abitibi region, Québec, Canada. Molybdenite is intergrown with muscovite in the veins or associated with K-feldspar in the alteration halos. Mineralized veins contain five main types of fluid inclusions: aqueous liquid and liquid-vapor inclusions, aqueous carbonic liquid-liquid-vapor inclusions, carbonic liquid and vapor inclusions, halite-bearing aqueous liquid and liquid-vapor inclusions, trapped mineral-bearing aqueous liquid and liquid-vapor inclusions. The carbonic solid in frozen carbonic and aqueous-carbonic inclusions melts in most cases at −56.7 ± 0.1 °C indicating that the carbonic fluid consists largely of CO₂. All aqueous inclusion types and the aqueous phase in carbonic inclusions have low initial melting temperatures (≥70 °C), requiring the presence of salts other than NaCl. Leachate analyses show that the bulk fluid contains variable proportions of Na, K, Ca, Cl, and traces of Mg and Li. The following solids were identified in the fluid inclusions by SEM-EDS analysis: halite, calcite, muscovite, millerite (NiS), barite and antarcticite (CaCl₂ · 6H₂O). All are interpreted to be trapped phases except halite which is a daughter mineral, and antarcticite which formed during sample preparation (freezing). Aqueous inclusions homogenize to liquid at temperatures between 75 °C and 400 °C; the mode is 375 °C. Aqueous-carbonic inclusions homogenize to liquid or vapor between 210 °C and 400 °C. Halite-bearing aqueous inclusions homogenize by halite dissolution at approximately 170 °C. Aqueous inclusions containing trapped solids exhibit liquid-vapor homogenization at temperatures similar to those of halite-bearing aqueous inclusions. Temperatures of vein formation, based on oxygen isotopic fractionation between quartz and muscovite, range from 342 °C to 584 °C. The corresponding oxygen isotope composition of the aqueous fluid in equilibrium with these minerals ranges from 1.2 to 5.5 per mil with a mean of 3.9 per mil, suggesting that the liquid had a significant meteoric component. Isochores for aqueous fluid inclusions intersect the modal isotopic isotherm of 425 °C at pressures between 590 and 1900 bar. A model is proposed in which molybdenite was deposited owing to decreasing temperature and/or pressure from CO₂-bearing, moderate to high salinity fluids of mixed magmatic-meteoric origin that were in equilibrium with K-feldspar and muscovite. These fluids resulted from the degassing of a monzogranitic magma and evolved through interaction with volcanic (komatiitic) and sedimentary country rocks. Received: 6 February 1997 / Accepted: 28 January 1998     

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.     

Immiscibility of high salinity fluids in volcanic rocks and the mechanism of magma degassing in the Dongying sag, eastern China

Fluid inclusions that bear halite daughter minerals were discovered in volcanic rocks at Pingnan area in the Dongying sag. The samples of the fluid inclusions collected from the BGX-15 well drill cores are hosted in quartz of diorite-porphyrite. The daughter minerals are identified as NaCl crystals after being observed under a microscope and analyzed by in situ Raman spectroscopy at −185°C. The results of micro-thermal analysis show that the homogenization temperatures of primary fluid inclusions are between 359 and 496°C, and the salinities of fluid inclusions are from 43.26 to 54.51 wt-%. All fluid inclusions in the studied samples can be divided into five types including primary fluid inclusions and secondary fluid inclusions. The fact that five types of fluid inclusions were symbiotic in the same quartz grain implies that immiscibility happened in magma. Due to the decrease in temperature and pressure during the ascent of magma, the fluids became intensively immiscible. This process accelerates the degassing of CO₂ from magma, but the remnant fluids with high salinity are preserved in fluid inclusions. Thus, the primary fluid inclusions are mainly in NaCl-H₂O fluids and poor in CO₂. The results of our study indicate that the degassing of magma and accumulation of CO₂ gas at the Pingnan area are relative to the immiscibility of high salinity fluids. This discovery is important because it can help us have a further understanding of the mechanism of magma degassing and accumulation of the inorganic CO₂ in eastern China. Translated from Acta Geologica Sinica, 2006, 80(11): 1699–1705 [译自: 地质学报]     

Geological,fluid inclusion,and O–C–S–Pb–He–Ar isotopic constraints on the genesis of the Honghuagou lode gold deposit,northern North China Craton

The Honghuagou Au deposit is located in the Chifeng-Chaoyang region within the northern margin of the North China Craton. The auriferous quartz veins are mainly hosted in the mafic gneiss and migmatite of the Neoarchean Xiaotazigou Formation along NNW- and NE-striking faults, with pyrite as the predominant ore mineral. The gold mineralization process can be divided into two stages, involving stage I quartz-pyrite and stage II quartz-calcite-polymetallic sulfide. Three types of fluid inclusions (FIs) have been identified in the Honghuagou deposit, namely, carbonic inclusions, aqueous‑carbonic inclusions, and aqueous inclusions. Quartz of stage I contains all types of FIs, whereas only aqueous inclusions are evident in stage II veins. The FIs of stages I and II yield homogenization temperatures of 275–340 °C and 240–290 °C with salinities of 3.4–10.7 wt% and 1.4–9.7 wt% NaCl eqv., respectively. The ore-forming fluids are characterized by medium temperature and low salinity, belonging to the H₂O–NaCl–CO₂ system. The δ¹⁸O_H2O values of the ore fluids are between 2.1‰ and 5.9‰, within the range of enriched mantle-derived fluids in the North China Craton. The carbon isotope compositions of calcite (δ¹³C_PDB = −4.4‰ to −4‰) are also similar to mantle carbon. He-Ar isotope data (³He/⁴He = 0.38–0.44 Ra; ⁴⁰Ar/³⁶Ar = 330–477) of fluid inclusions in pyrite indicate a mixed crustal and mantle source for the ore-forming fluids. Whereas, S-Pb isotope compositions of sulfides reveal that ore metals are principally derived from crustal rocks. On the basis of available geological and geochemical evidence, we suggest that the Honghuagou deposit is an orogenic gold deposit.     

Fluid inclusions and H–O–S–Pb isotope systematics of the Chalukou giant porphyry Mo deposit,Heilongjiang Province,China

The Chalukou giant porphyry Mo deposit, located in the northern Great Xing'an Range, is the largest Mo deposit in the Xing'an–Mongolia orogenic belt. This deposit's ore bodies are mainly hosted in an intermediate–felsic complex and Jurassic volcanic sedimentary rocks, of which Late Jurassic granite porphyry, quartz porphyry and fine grained granite are closely associated with the Mo mineralization. Three types of fluid inclusions (FIs) are present in the quartz associated with oxide and sulphide minerals, i.e., liquid-rich two-phase, gas-rich two-phase and daughter mineral-bearing multiphase FIs. The FIs in the quartz phenocrysts of the granite porphyry contain liquid-rich two-phase, gas-rich two-phase and daughter mineral-bearing multiphase FIs. The homogenization temperatures vary from 230 °C to 440 °C and 470 °C to 510 °C, and their salinities vary from 0.7% to 53.7% NaCl eq. and 6.2% to 61.3% NaCl eq., respectively. The FIs of K-feldspar–quartz–magnetite veins of the early stage are composed of liquid-rich two-phase, gas-rich two-phase and daughter mineral-bearing multiphase FIs with homogenization temperatures and salinities of 320 °C to 440 °C and 4.2% to 52.3% NaCl eq., respectively. The FIs of quartz–molybdenite veins and breccia of the middle stage are composed of liquid-rich two-phase, gas-rich two-phase and daughter mineral-bearing multiphase FIs with homogenization temperatures and salinities of 260 °C to 410 °C and 0.4% to 52.3% NaCl eq., respectively. FIs of quartz–fluorite–galena–sphalerite veins of the late stage are liquid-rich two-phase FIs with homogenization temperatures and salinities of 170 °C to 320 °C and 0.5% to 11.1% NaCl eq., respectively. The ore-forming fluids of the Chalukou deposit are characterised by high temperature, high salinity and high oxygen fugacity, belonging to an F-rich H₂O–NaCl ± CO₂ system. The δ¹⁸O_W values vary from − 4.5‰ to 3.2‰, and the δD_W values vary from − 138‰ to − 122‰, indicating that the ore-forming fluids were a mixture of magmatic and meteoric water. The δ³⁴S values range from − 1.9‰ to + 3.6‰ with an average of + 1.6‰. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of the metallic minerals are in the ranges of 18.269–18.501, 15.524–15.567 and 38.079–38.264, respectively. Both the S and Pb isotopic systems indicate that the ore metals and fluids came primarily from a deep-seated magma source from the juvenile lower crust. The Mo mineralization in the Chalukou deposit occurred at a depth of 0.5 to 1.3 km, and multiple stages of phase separation or immiscibility of ore-forming fluid was critical for the formation of the Chalukou deposit.     

Re-equilibration of CO2 fluid inclusions at controlled hydrogen fugacities

Abstract Natural, pure CO₂ inclusions in quartz and olivine (c. Fo₉₀) were exposed to controlled f_H2 conditions at T= 718–728°C and P_total= 2 kbar; their compositions were monitored (before and after exposures) by microsampling Raman spectroscopy (MRS) and microthermometry. In both minerals exposed at the graphite–methane buffer (f_H2= 73 bar), fluid speciations record the diffusion of hydrogen into the inclusions. In quartz, room-temperature products in euhedral isolated (EI type) inclusions are carbonic phases with molar compositions of c. CO₂(60) + CH₄(40) plus graphite (Gr) and H₂O, whereas anhedral inclusions along secondary fractures (AS type) are Gr-free and contain H₂O plus carbonic phases with compositions in the range c. CO₂(60) + CH₄(40) to CO₂(10) + CH₄(90). EI type inclusions in olivine evolved to c. CO₂(90–95) + CH₄(5–10) without Gr, whereas AS type inclusions have a range of compositions from CO₂(90) + CH₄(10) ± Gr to CH₄(50) + H₂(50) ± Gr; neither H₂O nor any hydrous species was detected by optical microscopy or MRS in the olivine-hosted products. Differences in composition between and among the texturally distinct populations of inclusions in both minerals probably arise from variations in initial fluid densities, as all inclusions apparently equilibrated with the ambient f_H2. These relations suggest that compositional variability among inclusions in a given natural sample does not require the entrapment of multiple generations of fluids. In addition, the absence of H₂O in the olivine-hosted inclusions would require the extraction of oxygen from the fluids, in which case re-equilibration mechanisms may be dependent on the composition and structure of the host mineral. Many of the same samples were re-exposed to identical P–T conditions using Ar as the pressure medium, yielding ambient f_H2= 0.06 bar. In most inclusions, the carbonic fluids returned to pure CO₂ and graphite persisted in the products. Reversal of the mechanisms from the prior exposure at f_H2= 73 bar did not occur in any inclusions but the AS types in olivine, in which minor CO₂ was produced at the expense of CH₄ and/or graphite. The observed non-reversibility of previous mechanisms may be attributed to: (1) slower fluid–solid reactions compared to reactions in the homogeneous fluid phase; (2) depressed activities of graphite due to poor ordering; and/or (3) low ambient f_O2 at the conditions of the second run.     

Fluid inclusion and stable isotopic constraints on fluid sources and evolution of the Luojiahe Cu deposit in the southern margin of the North China Craton

The Luojiahe Cu deposit in the Zhongtiaoshan region is located in the southern margin of the North China Craton. The orebodies are hosted in the mafic volcanic-sedimentary sequences of the metamorphosed (greenschist-facies) Neoarchean Songjiashan Group. The Luojiahe Cu mineralization can be divided into the primary volcanogenic massive sulfide (VMS) mineralization stage (Stage I, banded or stockwork ores) and the subsequent metamorphic remobilization stage (Stage II, coarse-vein ores).Three types of quartz selected for fluid inclusion (FI) studies were collected from the Stage I banded (Q1) and stockwork (Q2) ores and Stage II coarse-vein (Q3) ores. Four types of FIs were identified: (1) liquid-rich FIs (L-type), (2) pure vapor and vapor-rich FIs (V-type), (3) daughter mineral-bearing FIs (S-type), and (4) CH₄-H₂O FIs (C-type). Systematical microthermometric and H-O isotopic studies show that the Stage I ore-forming fluids consist predominantly of high salinity evolved seawater (125–220 °C; 23.9–27.9 wt.% NaCl equiv.) and some magmatic-hydrothermal fluids (249–339 °C; 34.5–42.2 wt.% NaCl equiv.). The two fluid end-members are represented by the L-type FIs in Q1 and the S- and V-type FIs in Q2. The temperature- and salinity variation trends of the L-type FIs in Q1 indicate a mixing process between the hot evolved seawater and cold seawater at Stage I. Furthermore, the V- and S-type FI coexistence in Q2 and their microthermometric data suggest that fluid unmixing has occurred in original magmatic fluids at Stage I. In contrast, the Stage II ore-forming fluids consist of CH₄-rich metamorphic fluids (192–350 °C; 10.6–43.2 wt.% NaCl equiv.). Carbon isotopic analysis of the Stage II calcite (− 4.58 to − 10.83‰) and graphite (− 32.01 to − 39.16‰) in the ore-hosting chlorite schist indicates that the metamorphic ore-forming fluids had exchanged carbon isotope with graphite. The generation of CH₄ may have resulted from the interaction between H₂O (released by metamorphic devolatilization) and graphite. The continuous consumption of H₂O in the hydrothermal fluid system may have increased the fluid salinity and triggered fluid unmixing in the CH₄-NaCl-H₂O system. In addition, the VMS metallogenic environment is generally favorable for microbial communities. It is considered that the graphite at Luojiahe may have been derived from sedimentary organic matter formed in seafloor hydrothermal vent systems, as also supported by carbon isotopic data.We propose that at Stage I, the main mineralization may have been resulted from 1) fluid mixing of hot evolved seawater and cold seawater in the near-surface environment; and 2) fluid unmixing caused by the percolation of magmatic fluids into syn-volcanic faults, forming the stockwork ores. At Stage II, the interaction between H₂O and graphite may have resulted in the reduction of ore-forming fluids and Cu precipitation, and fluid unmixing in the CH₄-NaCl-H₂O system may have further promoted the Cu mineralization.     

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.     

Primary Ore Mineral Assemblage and Fluid Inclusion Study of the Batu Hijau Porphyry Cu-Au Deposit, Sumbawa, Indonesia

Abstract. The Batu Hijau porphyry Cu‐Au deposit, Sumbawa Island, Indonesia, is associated with a tonalitic intrusive complex. The temperature‐pressure condition of mineralization at the Batu Hijau deposit is discussed on the basis of fluid inclusion microthermometry. Then, the initial Cu‐Fe sulfide mineral assemblage is discussed. Bornite and chalcopyrite are major copper ore minerals associated with quartz veinlets. The quartz veinlets have been classified into ‘A’ veinlets associated with bornite, digenite, chalcocite and chalcopyrite, ‘B’ veinlets having chalcopyrite bornite along vuggy center‐line, rare ‘C’ chalcopyrite‐quartz veinlets, and late ‘D’ veinlets consisting of massive pyrite and quartz (Clode et al., 1999). Copper and gold mineralization is associated with abundant ‘A’ quartz veinlets. Abundant fluid inclusions are found in veinlet quartz consisting mainly of gas‐rich inclusions and polyphase inclusions throughout the veinlet types. The hydrothermal activity occurred in temperature‐pressure conditions of aqueous fluid immiscibility into hypersaline brine and dilute vapor. The halite dissolution (Tm[halite]) and liquid‐vapor homogenization (Th) temperatures of the polyphase inclusions in veinlet quartz range from 270 to 472d?C and from 280 to 454d?C, respectively. The estimated salinity ranges from 36 to 47 wt% (NaCl equiv.). The apparent pressures lower than 300 bars are estimated to have been along the liquid‐vapor‐halite curve for the fluid inclusions having the Th lower than the Tm that trapped the brine saturated with halite, or at slightly higher pressure relative to liquid‐vapor‐halite curve for the fluid inclusions having the Th higher than the Tm that trapped the brine unsaturated with halite. The actual temperature and pressure during the hydrothermal activity at the Batu Hijau deposit are estimated to have been around 300d?C and 50 bars. At such temperature‐pressure conditions, the principal and initial Cu‐Fe sulfide mineral assemblages are thought to be chalcopyrite + bornite solid solution (bnss) for the chalcopyrite‐bearing assemblage, and chalcocite‐digenite solid solution and bnss for the chalcopyrite‐free assemblage.     

Fluid evolution and ore genesis of the A'gui Cu deposit in southern Great Xing'an Range,Northeast China: Evidence from fluid inclusion and C–H–O–S–Pb isotopes

The A'gui Cu deposit is located in the eastern slope of the southern Great Xing'an Range (SGXR), and it is a vein-type Cu deposit spatially and temporally related to the Cretaceous monzogranite which intruded Pingshan Formation. Vein-type Cu orebodies are mainly hosted in the NE and nearly EW faults. Previous studies on the A'gui deposit mainly focused on geological exploration, and there was no study on its fluid evolution and genesis. Therefore, we carried out conducted fluid inclusion and stable isotope (C–H–O–S–Pb) analysis to study the fluid evolution, fluid and ore-forming material sources and genesis of the A'gui deposit. According to the field investigations and mineral crosscutting relationships, four paragenetic stages were identified: quartz–pyrite–chalcopyrite–pyrrhotite–arsenopyrite ± magnetite (Stage I), quartz–pyrite–chalcopyrite (Stage II), quartz–chalcopyrite ± pyrite–sphalerite–galena (Stage III) and carbonate ± quartz (Stage IV). From Stage I to Stage II, the assemblage of fluid inclusions (FIs) in quartz is characterized by the development of daughter mineral–bearing three–phase FIs (SL–type), vapour FIs (V–type), vapour–rich two–phase aqueous FIs (LV–type) and liquid–rich two–phase aqueous FIs (VL–type). Only VL–type FIs appeared in the Stage III quartz and Stage IV calcite. The homogenization temperatures of FIs in stages I, II, III and IV are 329–390 °C, 255–336 °C, 166–244 °C and 120–157 °C, with salinities of 3.37–45.33 wt%, 3.53–39.76 wt%, 4.17–7.86 wt% and 3.37–7.15 wt% NaCl eqv., respectively. The fluid inclusion type assemblage suggested that obvious fluid boiling occurred in the Stage I and Stage II. Fluid boiling may be the reason for the precipitation of useful minerals. According to the HO isotope analysis of stages I–II quartz (δ¹⁸O_H2O = −2.1 to 3.2 ‰, δD_V–SMOW = −128.4 ‰ to −110.6 ‰), the fluid was originally magmatic water. From Stage III to Stage IV (δ¹⁸O_H2O = −12.3 to −2.3 ‰, δD_V–SMOW = −129.6 ‰ to −104.2 ‰), the HO isotope value is obviously close to the meteoric water line, indicating that meteoric water is mixed with evolved magmatic solutions. The ore–forming fluid of the A'gui deposit represents a medium–high temperature NaCl-H₂O magmatic hydrothermal system. The C isotope compositions (δC_V–PDB = −5.74 ‰ to −4.76 ‰) in stage IV indicate that the C in the fluid was derived from a magmatic source and was affected by meteoric water. In addition, the measured S isotope compositions in stages I–III of the hydrothermal fluids (δ³⁴S_V–CDT = 2.2 to 3.7 ‰) indicate that S mainly comes from granitic magma. Further, the Pb isotope (²⁰⁶Pb/²⁰⁴Pb = 18.276–18.367, ²⁰⁷Pb/²⁰⁴Pb = 15.52–15.556, ²⁰⁸Pb/²⁰⁴Pb = 38.157–38.193) in stages I–III indicate that the ore-forming materials are derived from the mixture of mantle and orogenic material. In summary, this study showed the A'gui is a typical magmatic hydrothermal vein-type Cu deposit that related to Cretaceous monzogranite formed under the joint constraints of Mongolia-Okhotsk Ocean and Paleo-Pacific Ocean tectonic system. Fluid boiling and mixing are the main ore-forming mechanism.     

A magmatic-hydrothermal transition in Arkaroola (northern Flinders Ranges, South Australia): from diopside–titanite pegmatites to hematite–quartz growth

A set of Palaeozoic diopside–titanite veins are present in Mesoproterozoic metagranites and metasediments that constitute the basement (Mt Painter Inlier) of the Adelaide Fold Belt (South Australia). These massive veins (up to 1 m) of pegmatitic nature contain large crystals of diopside, LREE–Y-enriched titanite (up to 40 cm in length) and minor amounts of quartz. They can be used to trace the system’s development from a high-temperature magmatic stage through to a massive hydrothermal event. The pegmatitic origin of these veins is evident from a complex fluid-melt inclusion assemblage, consisting of a highly saline inhomogeneous fluid and relicts of melt. Immiscibility of melt and heterogeneous highly saline fluids (exceeding 61 eq. mass% NaCl) is preserved in primary inclusions in diopside and secondary inclusions in titanite, indicating relatively shallow conditions of formation (510 ± 20°C and 130 ± 10 MPa). Graphic intergrowth of diopside and albite occurs at the contact with granitic pegmatites. The system evolved into hydrothermal conditions, which can be deduced from a later population of only fluid inclusions (homogeneous and less saline, ≈ 40 eq. mass% NaCl), trapped around 350 ± 20°C and 80 ± 10 MPa. During quartz crystallization, the conditions moved across the halite liquidus resulting in a heterogeneous mixture of brine and halite crystals, which were trapped at 200 ± 20°C and 50 ± 10 MPa. Brecciation and a palaeo-geothermal system overprinted the pegmatitic veins with an epithermal hematite–quartz assemblage and lesser amounts of bladed calcite and fluorite, in an intermittently boiling hydrothermal system of fairly pure H₂O at 100–140°C and 1–5 MPa. Remobilization of LREEs and Y from titanite and/or the granitic host rock is evidenced by precipitation of apatite, allanite and wakefieldite in an intermediate stage. Occasional incorporation of radioactive elements or minerals, presumably U-rich, in the fluorite is responsible for radiolysis of H₂O to H₂.     

Fluid Inclusions in Surface‐temperature Halite: Sample Preparation and Application

Paleo-temperature and paleo-environment can be interpreted from measuring homogenization temperatures of fluid inclusions within halite. In order to conduct such measurements, vapor bubbles within low-temperature fluid inclusion often need to be created through cooling process by using cooling stage or freezer. Proper cooling is critical for interpreting measured temperature data. We tested two common cooling methods, using heating/freezing stage and freezer, for studying fluid inclusions in halite precipitated in laboratory at conrtolled temperature of 25℃. While using the heating/freezing stage, halite samples were kept at-18℃ for 40–50 min; whereas for freezer, samples were stored at-18℃ for 1, 10, 20 and 40 days, respectively. By comparing the homogenization temperatures of the two cooling processes, we explored the detailed experimental processes and developed an optimal cooling nucleation procedure for homogenization temperature analyses of fluid inclusions within surface-temperature halite. The results show that the maximum homogenization temperatures from both methods approximate the actual brine temperature of 25℃. However, extended refrigeration time has noticeable influence on the results. The refrigeration time of the experiment can be shortened to meet requirements.     

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.