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

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

Evolution of palaeofluids at the Variscan thrust front in eastern Belgium

The geochemical evolution of the fluids migra- ting at the Variscan thrust front in eastern Belgium has been investigated by a petrographic, mineralogical and geoche-mical study of ankerite, quartz and ferroan calcite veins hosted by lower Devonian rocks. Three vein generations have been recognized. The first generation consists of quartz, chlorite and ankerite filling pre- to early Variscan extensional fractures. The second generation is present as shear veins of Variscan age, and contains quartz, chlorite and ferroan calcite. The third generation consists of ankerite filling post-Variscan fractures. The oxygen and carbon isotopic composition of the two ankerite phases and of the ferroan calcites are respectively between –16.4 and –11.4‰ PDB between –17.8 and –1.7‰ PDB. This range is greater than that of calcite nodules in the lower Devonian siliciclastic sediments (δ¹⁸O= –15.6 to –11.1‰ PDB and δ¹³C= –13.4 to –10.2‰ PDB). This suggests precipitation of the carbonate veins from a fluid which was at most only partly isotopically buffered by the calcite nodules in the host rock. The calculated oxygen isotopic composition of the ambient fluid from which the calcite veins formed is between +7.8 and +10.0‰ SMOW. Two main fluid types have been recognized in fluid inclusions in the quartz and carbonates. The first fluid type is present as secondary fluid inclusions in the first and second vein generations. The fluid has a salinity of 0.5–7.2 eq. wt.% NaCl and a high, but variable, homogenization temperature (Th=124–188°C). Two origins can be proposed for this fluid. It could have been expelled from the lower Devonian or could have been derived from the metamorphic zone to the south of the area studied. Taking into account the microthermometric and stable-isotope data, and the regional geological setting, the fluid most likely originated from metamorphic rocks and interacted with the lower Devonian along its migration path. This is in agreement with numerical simulations of the palaeofluid and especially the palaeotempera-ture field, which is based on chlorite geothermometry and vitrinite reflectance data. The second fluid type occurs as secondary inclusions in the shear veins and as fluid inclusions of unknown origin in post-Variscan ankerite veins. Therefore, it has a post-Variscan age. The inclusions are characterized by a high salinity (18.6–22.9 eq. wt.% CaCl₂). The composition of the fluid is similar to that which caused the development of Mississippi Valley-type Pb–Zn deposits in Belgium.     

Fluid infiltration effects on stable isotope systematics of the Susurluk skarn deposit,NW Turkey

A calcic skarn deposit occurs along the contact zone between Oligo-Miocene Çatalda? Granitoid and Mesozoic limestones in Susurluk, northwestern Turkey. The skarn zone with little or no retrograde stage is represented by fluid inclusions with high homogenization temperatures (up to >600 °C) and a wide range of salinity (12 to >70 wt.% NaCl). Pluton-derived fluids facilitated occurrence of continuous prograde reactions in the country rocks (particularly in the proximal zone) and oxygen isotopic depletion in calc-silicate and calcite minerals. δ¹⁸O of anhydrous minerals within proximal and distal zones indicate that skarn-forming fluids had a magmatic origin. The δ¹⁸O values are 5.93–9.08‰ (mean 6.8‰) for garnet, 4.08–9.94‰ (mean 6.4‰) for pyroxene, 4.89–7.92‰ (mean 6.4‰) for wollastonite and 6.65–8.28‰ (mean 7.5‰) for vesuvianite. Temperatures estimated by isotopic compositions of mineral pairs are significantly lower than those measured from the fluid inclusions, indicating that isotopic equilibrium is not preserved between the skarn minerals. δ¹⁸O and δ¹³C values are systematically depleted from marbles to skarn carbonates. Calc-silicate forming reactions and permeability increase triggered by volatilization and consequent strong infiltration of H₂O-rich siliceous fluids into the system promoted fluid–rock interaction causing isotopic resetting and isotopic depletion of silicates (e.g. pyroxene and wollastonite) and skarn calcites.     

Evolution of carbon dioxide-bearing saline fluids in the mantle wedge beneath the Northeast Japan arc

Lherzolite xenoliths containing fluid inclusions from the Ichinomegata volcano, located on the rear-arc side of the Northeast Japan arc, may be considered as samples of the uppermost mantle above the melting region in the mantle wedge. Thus, these fluid inclusions provide valuable information on the nature of fluids present in the sub-arc mantle. The inclusions in the Ichinomegata amphibole-bearing spinel–plagioclase lherzolite xenoliths were found to be composed mainly of CO₂–H₂O–Cl–S fluids. At equilibrium temperature of 920 °C, the fluid inclusions preserve pressures of 0.66–0.78 GPa, which correspond to depths of 23–28 km. The molar fraction of H₂O and the salinity of fluid inclusions are 0.18–0.35 and 3.71 ± 0.78 wt% NaCl equivalent, respectively. These fluid inclusions are not believed to be fluids derived directly from the subducting slab, but rather fluids exsolved from sub-arc basaltic magmas that are formed through partial melting of mantle wedge triggered by slab-derived fluids.     

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

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

A Study of Ore-forming Fluids in the Shimensi Tungsten Deposit, Dahutang Tungsten Polymetallic Ore Field, Jiangxi Province, China

The Dahutang tungsten polymetallic ore field is located north of the Nanling W-Sn polymetallic metallogenic belt and south of the Middle—Lower Yangtze River Valley Cu-Mo-Au-Fe porphyry-skarn belt.It is a newly discovered ore field,and probably represents the largest tungsten mineralization district in the world.The Shimensi deposit is one of the mineral deposits in the Dahutang ore field,and is associated with Yanshanian granites intruding into a Neoproterozoic granodiorite batholith.On the basis of geologic studies,this paper presents new petrographic,microthermometric,laser Raman spectroscopic and hydrogen and oxygen isotopic studies of fluid inclusions from the Shimensi deposit.The results show that there are three types of fluid inclusions in quartz from various mineralization stages:liquid-rich two-phase fluid inclusions,vapor-rich two-phase fluid inclusions,and three-phase fluid inclusions containing a solid crystal,with the vast majority being liquid-rich two-phase fluid inclusions.In addition,melt and melt-fluid inclusions were also found in quartz from pegmatoid bodies in the margin of the Yanshanian intrusion.The homogenization temperatures of liquid-rich two-phase fluid inclusions in quartz range from 162 to 363℃ and salinities are 0.5wt%-9.5wt%NaCI equivalent.From the early to late mineralization stages,with the decreasing of the homogenization temperature,the salinity also shows a decreasing trend.The ore-forming fluids can be approximated by a NaCl-H_2O fluid system,with small amounts of volatile components including CO_2,CH_4 and N_2,as suggested by Laser Raman spectroscopic analyses.The hydrogen and oxygen isotope data show that δ5D_(V-smow) values of bulk fluid inclusions in quartz from various mineralization stages vary from-63.8‰ to-108.4‰,and the δ~(18)O_(H2O) values calculated from the δ~(18)O_(V-)smow values of quartz vary from-2.28‰ to 7.21‰.These H-O isotopic data are interpreted to indicate that the ore-forming fluids are mainly composed of magmatic water in the early stage,and meteoric water was added and participated in mineralization in the late stage.Integrating the geological characteristics and analytical data,we propose that the ore-forming fluids of the Shimensi deposit were mainly derived from Yanshanian granitic magma,the evolution of which resulted in highly differentiated melt,as recorded by melt and melt-fluid inclusions in pegmatoid quartz,and high concentrations of metals in the fluids.Cooling of the ore-forming fluids and mixing with meteoric water may be the key factors that led to mineralization in the Dahutang tungsten polymetallic ore field.     

Reconciling fluid inclusion types,fluid processes,and fluid sources in skarns: an example from the Bismark Deposit,Mexico

The Bismark deposit (8.5 Mt at 8% Zn, 0.5% Pb, 0.2% Cu, and 50 g/t Ag) located in northern Mexico is an example of a stock-contact skarn end member of a continuum of deposit types collectively called high-temperature, carbonate-replacement deposits. The deposit is hosted by massive sulfide within altered limestone adjacent to the Bismark quartz monzonite stock (~42 Ma) and the Bismark fault. Alteration concurrently developed in both the intrusion and limestone. The former contains early potassic alteration comprising K-feldspar and biotite, which was overprinted by kaolinite-rich veins and alteration and later quartz, sericite, and pyrite with minor sphalerite and chalcopyrite. Prograde exoskarn alteration in the limestone consists of green andradite and diopside, and transitional skarn comprising red-brown andradite, green hedenbergite and minor vesuvinite, calcite, fluorite, and quartz. The main ore stage post-dates calc-silicate minerals and comprises sphalerite and galena with gangue pyrite, pyrrhotite, calcite, fluorite, and quartz. The entire hydrothermal system developed synchronously with faulting. Fluid inclusion studies reveal several distinct temporal, compositional, and thermal populations in pre-, syn- and post-ore quartz, fluorite, and calcite. The earliest primary fluid inclusions are coexisting vapor-rich (type 2A) and halite-bearing (type 3A; type 3B contain sylvite) brine inclusions (32 to >60 total wt% salts) that occur in pre-ore fluorite. Trapping temperatures are estimated to have been in excess of 400 °C under lithostatic pressures of ~450 bar (~1.5 km depth). Primary fluid inclusions trapped in syn-ore quartz display critical to near critical behavior (type 1C), have moderate salinity (8.4 to 10.9 wt% NaCl equiv.) and homogenization temperatures (Th) ranging from 351 to 438 °C. Liquid-rich type 1A and 1B (calcite-bearing) inclusions occur as primary to secondary inclusions predominantly in fluorite and show a range in Th (104–336 °C) and salinity (2.7–11.8 wt% NaCl equiv.), which at the higher Th and salinity ranges overlap with type 1C inclusions. Oxygen isotope analysis was carried out on garnet, quartz, and calcite (plus carbon isotopes) in pre-, syn-, post-ore, and peripheral veins. Pre-ore skarn related garnets have a δ¹⁸O_mineral range between 3.9 and 8.4‰. Quartz from the main ore stage range between 13.6 and 16.0‰. Calcite from the main ore stage has δ¹³C values of –2.9 to –5.1‰ and δ¹⁸O values of 12.3 to 14.1‰, which are clearly distinct from post-ore veins and peripheral prospects that have much higher δ¹⁸O (16.6–27.3‰) and δ¹³C (1.3–3.1‰) values. Despite the numerous fluid inclusion types, only two fluid sources can be inferred, namely a magmatic fluid and an external fluid that equilibrated with limestone. Furthermore, isotopic data does not indicate any significant mixing between the two fluids, although fluid inclusion data may be interpreted otherwise. Thus, the various fluid types were likely to have formed from varying pressure–temperature conditions through faulting during exsolution of magmatic fluids. Late-stage hydrothermal fluid activity was dominated by the non-magmatic fluids and was post-ore.     

Origin and migration of palaeofluids in the Upper Visean of the Campine Basin, northern Belgium

Upper Visean limestones in the Campine Basin of northern Belgium are intensively fractured. The largest and most common fractures are cemented by non-ferroan, dull brown-orange luminescent blocky calcite. First melting temperatures of fluid inclusions in these calcites are around -57°C, suggesting that precipitation of the cements occurred from NaCl-CaCl₂-MgCl₂ fluids. The final melting temperatures (T_m^ice) are between -5 and -33°C. The broad range in the T_m^ice data can be explained by the mixing of high salinity fluids with meteoric waters, but other hypotheses may also be valid. Homogenization temperatures from blocky calcite cements in the shelf limestones are interpreted to have formed between 45 and 75°C. In carbonates which were deposited close to and at the shelf margin, precipitation temperatures were possibly in the range 70-85°C and 72-93°C, respectively. On the shelf, the calcites have a δ¹⁸O around -9.3‰ PDB and they are interpreted to have grown in a fluid with a δ¹⁸O between −3.5 and +1.0‰ SMOW. At the shelf margin, blocky calcites (δ¹⁸O∼ - 13.5‰ PDB) could have precipitated from a fluid with a δ¹⁸O betweenn -4.0 and -1.1‰ SMOW. The highest oxygen isotopic compositions are comparable to those of Late Carboniferous marine fluids (δ¹⁸O= - 1‰ SMOW). The lowest values are more positive than a previously reported composition for Carboniferous meteoric waters (δ¹⁸O= -7‰ SMOW). Precipitation is likely to have occurred in marine-derived fluids, which mixed with meteoric waters sourced from near the Brabant Massif. Fluids with a similar negative oxygen isotopic composition and high salinity are actually present in Palaeozoic formations. The higher temperature range in the limestones near the shelf margin is explained by the upward migration of fluids from the ‘basinal’ area along fractures and faults into the shelf.     

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

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

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

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

Activity of Silica-Rich Hydrothermal Fluid and Its Impact on Deep Dolomite Reservoirs in the Sichuan Basin, Southern China

Well-developed dissolution pores occur in the dolomites of the Sinian Dengying Formation, which is an important oil and gas reservoir layer in the Sichuan Basin and adjacent areas in southern China. The pores are often filled with quartz, and some dolomites have been metasomatically altered to siliceous chert. Few studies have documented the characteristics, source or origin of silica-rich fluids and their effects on the dolomite reservoir. The peak homogenisation temperatures(T_h) of fluid inclusions in pore-filling quartz are between 150℃ and 190℃, with an average of 173.7℃. Gases in the inclusions are mainly composed of CO_2, CH_4 and N_2. Compared with host dolomite, pore-filling quartz and metasomatic chert contain higher amounts of Cr, Co, Mo, W and Fe, with average concentrations of 461.58, 3.99, 5.05, 31.43 and 6666.83 ppm in quartz and 308.98, 0.99, 1.04, 13.81 and 4703.50 ppm in chert, respectively. Strontium levels are lower than that in the host dolomite, with average concentrations in quartz and chert of 4.81 and 11.06 ppm, respectively. Rare earth element compositions in quartz and chert display positive Eu anomalies with a maximum δEu of 5.72. The δD_(SMOW) values of hydrogen isotopes in water from quartz inclusions vary from-85.1‰ to-53.1‰ with an average of-64.3‰, whereas the δ~(18)O_(SMOW) values range from 7.2‰ to 8.5‰ with an average of 8.2‰. The average ~(87)Sr/~(86)Sr ratios in quartz and chert are 0.711586 and 0.709917, respectively, which are higher than that in the host dolomite. The fluid inclusions, elemental and isotopic compositions demonstrate that the formation of quartz and chert was related to silica-rich hydrothermal fluid and that the fluid was the deep circulation of meteoric water along basement faults. Interactions with silica-rich hydrothermal fluids resulted in densification of dolomite reservoirs in the Dengying Formation through quartz precipitation and siliceous metasomatism. However, it increased the resistance of the host dolomite to compaction, improving the ability to maintain reservoir spaces during deep burial. Evidence for silica-rich hydrothermal activity is common in the Yangtze Platform and Tarim Basin and its influence on deep dolomite reservoirs should be thoroughly considered.     

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

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

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

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

The mangazeya Ag–Pb–Zn vein deposit hosted in sedimentary rocks,Sakha-Yakutia,Russia: Mineral assemblages,fluid inclusions,stable isotopes (C,O, S), and origin

The succession of mineral assemblages, chemistry of gangue and ore minerals, fluid inclusions, and stable isotopes (C, O, S) in minerals have been studied in the Mangazeya silver–base-metal deposit hosted in terrigenous rocks of the Verkhoyansk Fold–Thrust Belt. The deposit is localized in the junction zone of the Kuranakh Anticlinorium and the Sartanga Synclinorium at the steep eastern limb of the Endybal Anticline. The deposit is situated at the intersection of the regional Nyuektame and North Tirekhtyakh faults. Igneous rocks are represented by the Endybal massif of granodiorite porphyry 97.8 ± 0.9 Ma in age and dikes varying in composition. One preore and three types of ore mineralization separated in space are distinguished: quartz–pyrite–arsenopyrite (I), quartz–carbonate–sulfide (II), and silver–base-metal (III). Quartz and carbonate (siderite) are predominant in ore veins. Ore minerals are represented by arsenopyrite, pyrite, sphalerite, galena, fahlore, and less frequent sulfosalts. Three types of fluid inclusions in quartz differ in phase compositions: two- or three-phase aqueous–carbon dioxide (FI I), carbon dioxide gas (FI II), and two-phase (FI III) containing liquid and a gas bubble. The homogenization temperature and salinity fall within the ranges of 367–217°C and 13.8–2.6 wt % NaCl equiv in FI I; 336–126°C and 15.4–0.8 wt % NaCl equiv in FI III. Carbon dioxide in FI II was homogenized in gas at +30.2 to +15.3°C and at +27.2 to 29.0°C in liquid. The δ³⁴S values for minerals of type I range from–1.8 to +4.7‰ (V-CDT); of type II, from–7.4 to +6.6‰; and of type III, from–5.6 to +7.1‰. δ¹³C and δ¹⁸O vary from–7.0 to–6.7‰ (V-PDB) and from +16.6 to +17.1 (V-SMOW) in siderite-I; from–9.1 to–6.9‰ (V-PDB) and from +14.6 to +18.9 (V-SMOW) in siderite-II; from–5.4 to–3.1‰ (V-PDB) and from +14.6 to +19.5 (V-SMOW) in ankerite; and from–4.2 to–2.9‰ (V-PDB) and from +13.5 to +16.8 (V-SMOW) in calcite. The data on mineral assemblages, fluid inclusions, and ratios of stable isotopes allow us to speak about the formation of the Mangazeya deposit in relation to the activity of the hydrothermal–magmatic system. The latter combines emplacement of subvolcanic granitic stocks and involvement of fluids variable in salinity and temperature in ore deposition zone. The fluids released from crystallizing felsic magma and were formed in a convective cell by heating of meteoric and marine waters. The mechanism of ore deposition is related to phase separation (boiling) and mixing of fluids.     

Fluid Inclusions and Stable Isotopic Characteristics of the Yaoling Tungsten Deposit in South China: Metallogenetic Constraints

The Yaoling tungsten deposit is a typical wolframite quartz vein‐type tungsten deposit in the South China metallogenic province. The wolframite‐bearing quartz veins mainly occur in Cambrian to Ordovician host rocks or in Mesozoic granitic rocks and are controlled by the west‐north‐west trending extensional faults. The ore mineralization mainly comprises wolframite and variable amounts of molybdenite, chalcopyrite, pyrite, fluorite, and tourmaline. Hydrothermal alteration is well developed at the Yaoling tungsten deposit, including greisenization, silicification, fluoritization, and tourmalinization. Three types of primary/pseudosecondary fluid inclusions have been identified in vein quartz, which is intimately intergrown with wolframite. These include two‐phase liquid‐rich aqueous inclusions (type I), two‐ or three‐phase CO₂‐rich inclusions (type II), and type III daughter mineral‐bearing multiphase high‐salinity aqueous inclusions. Microthermometric measurements reveal consistent moderate homogenization temperatures (peak values from 200 to 280°C), and low to high salinities (1.3–39 wt % NaCl equiv.) for the type I, type II, and type III inclusions, where the CO₂‐rich type II inclusions display trace amounts of CH₄ and N₂. The ore‐forming fluids are far more saline than those of other tungsten deposits reported in South China. The estimated maximum trapping pressure of the ore‐forming fluids is about 1230–1760 bar, corresponding to a lithostatic depth of 4.0–5.8 km. The δD_H2O isotopic compositions of the inclusion fluid ranges from ?66.7 to ?47.8‰, with δ¹⁸O_H2O values between 1.63 and 4.17‰, δ¹³C values of ?6.5–0.8‰, and δ³⁴S values between ?1.98 and 1.92‰, with an average of ?0.07‰. The stable isotope data imply that the ore‐forming fluids of the Yaoling tungsten deposit were mainly derived from crustal magmatic fluids with some involvement of meteoric water. Fluid immiscibility and fluid–rock interaction are thought to have been the main mechanisms for tungsten precipitation at Yaoling.     

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

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

Dawsonite fixation of mantle CO2 in the cretaceous Songliao Basin,Northeast China: a natural analogue for CO2 mineral trapping in oilfields

Abundant crude oil and CO₂ gas coexist in the fourth member of the Upper Cretaceous Quantou reservoir in the Huazijing Step of the southern Songliao Basin, China. Here, we present results of a petrographic characterization of this reservoir based on polarizing microscope, X-ray diffraction, fluid inclusion, and carbon–oxygen isotopic data. These data were used to identify whether CO₂ might be trapped in minerals after the termination of a CO₂-enhanced oil recovery (EOR) project, and to determine what effects might the presence of CO₂ have on the properties of crude oil in the reservoir. The crude oil reservoir in the study area, which coexists with mantle-derived CO₂, is hosted by dawsonite-bearing lithic arkoses and feldspathic litharenites. These sediments are characterized by a paragenetic sequence of clay, quartz overgrowth, first-generation calcite, dawsonite, second-generation calcite, and ankerite. The dawsonite analysed during this study exhibits δ¹³ C (Peedee Belemnite, PDB) values of ?4.97‰ to 0.67‰, which is indicative for the formation of magmatic–mantle CO₂. The paragenesis and compositions of fluid inclusions in the dawsonite-bearing sandstones record a sequence of two separate filling events, the first involving crude oil and the second involving magmatic–mantle CO₂. The presence of prolate primary hydrocarbon inclusions within the dawsonite indicates that these minerals precipitated from oil-bearing pore fluids at temperatures of 94–97°C, in turn suggesting that CO₂ could be stored as carbonate minerals after the termination of a CO₂-EOR project. In addition, the crude oil in the basin would become less dense after deposition of bitumen by deasphalting the injection of CO₂ gas into the oil pool.     

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

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

Rare earth elements and yttrium geochemistry of dolomite from post-Variscan vein-type mineralization of the Nízký Jeseník and Upper Silesian Basins, Czech Republic

Rare earth elements and yttrium geochemistry of dolomite from post-Variscan vein-type Zn–Pb–Cu mineralization was studied in the Nízký Jeseník and Upper Silesian Basins. Combined with crush–leach analyses of fluid inclusions, the study provided important information on fluid–rock interaction, physico-chemical and redox conditions during crystallization of the dolomite. The mineralization is hosted by Carboniferous siliciclastic rocks, representing Variscan flysch and molasse sedimentation. Dolomite samples contain highly variable contents of REE (between 18 and 295 ppm) and Y (between 17 and 95 ppm). REY patterns are divided into four different groups which differ in regional provenance, LREE vs. HREE enrichment/depletion and significance of Eu, Gd and Y anomalies. These patterns can be the result of 1) precipitation of dolomite from near neutral fluids with important concentrations of complexing ligands as a main factor for the REY partitioning, 2) interaction of migrating fluids with host or basement rocks, or, most probably, 3) a combination of both.Regarding the importance of complexing ligands, it is proposed that in all samples fluoride and chloride complexes prevailed over sulphate, bicarbonate and hydroxide complexes. Interaction of fluids with rocks was strongly affected by the fluid temperature. Dolomites which precipitated from fluids with homogenization temperature higher than 110 °C are mostly REY-enriched while fluids colder than 110 °C produced REY-depleted dolomite. The REY-enrichment may indicate higher effectiveness of leaching of REE-bearing minerals (probably monazite, allanite and biotite) at higher temperatures. The preferential loss of LREE can be caused by the recrystallization or remobilization of dolomite. Generally, an increase in salinity and contents of Cl and F in the fluids is mostly accompanied by a higher REY content in dolomite. Positive Eu anomalies and small negative Gd and Y anomalies are typical for most of the chondrite-normalized patterns. Positive Eu_CN anomalies in dolomites are most probably the result of an increase of Eh in the parent fluid. Distribution of Y is expected to be predominantly controlled by solution complexation.     

Fluid evolution of the Hub Stock, Horní Slavkov–Krásno Sn–W ore district, Bohemian Massif, Czech Republic

The Horní Slavkov–Krásno Sn–W ore district is hosted by strongly altered Variscan topaz–albite granite (Krudum granite body) on the northwestern margin of the Bohemian Massif. We studied the fluid inclusions on greisens, ore pockets, and ore veins from the Hub Stock, an apical expression of the Krudum granite. Fluid inclusions record almost continuously the post-magmatic cooling history of the granite body from ～500 to <50°C. Rarely observed highest-temperature (～500°C) highest-salinity (～30?wt.% NaCl eq.) fluid inclusions are probably the result of secondary boiling of fluids exsolved from the crystallizing magma during pressure release which followed hydraulic brecciation of the gneissic mantle above the granite cupola. The greisenization was related to near-critical low-salinity (0–7?wt.% NaCl eq.) aqueous fluids with low amount of CO₂, CH₄, and N₂ (≤10?mol% in total) at temperatures of ～350–400°C and pressures of 300–530 bar. Crush-leach data display highly variable and negatively correlated I/Cl and Br/Cl values which are incompatible with both orthomagmatic and/or metamorphic origin of the fluid phase, but can be explained by infiltration of surficial and/or sedimentary fluids. Low fluid salinity indicates a substantial portion of meteoric waters in the fluid mixture that is in accordance with previous stable isotope data. The post-greisenization fluid activity associated with vein formation and argillitization is characterized by decreasing temperature (<350 to <50°C), decreasing pressure (down to ～50–100 bar), and mostly also decreasing salinity.