Contrasting fluid inclusion characteristics of staniferous and non-staniferous pegmatites of Southeast Bastar, Central India

Tin and rare metal-bearing granitic pegmatites in the Bastar–Malkangiri pegmatite belt of Central India are hosted by metabasic and metasedimentary country rocks. Fluid inclusion studies were conducted in spatially associated two-mica granite and the staniferous and non-staniferous pegmatites to characterize the physicochemical environment of mineralization, to distinguish different pegmatites in terms of their fluid characteristics and to envisage a possible genetic link between the pegmatites and spatially associated granite. Three different types of primary inclusions were identified. The type-I, aqueous bi-phase (L+V) inclusions are the most abundant and ubiquitous. Type-II polyphase (L+V+S) inclusions are rare. Type-III, monophase (L) and metastable aqueous inclusions, though less abundant than type-I inclusions, are ubiquitous. The fluid evolution trends indicate that mixing of two different fluids of contrasting salinities, one of high salinity (20–30 wt% NaCl equivalent) and another of low salinity (0–10 wt% NaCl equivalent), was responsible for precipitation of the bulk of the cassiterite. This mixing is the single most important characteristic that distinguishes the staniferous pegmatites from their non-staniferous counterparts. The non-staniferous pegmatites, on the other hand, are typified by the presence either of a high saline or a low saline fluid that evolved through simple cooling. The minimum pressure–temperature of entrapment, estimated from the intersections of the halide liquidus with the corresponding inclusion isochores of type-II inclusions, range between 2.1–2.2 kb and 300–325 °C. The similar P–T range of fluid entrapment of the staniferous and non-staniferous pegmatites indicates that they were possibly emplaced within a similar physical environment. Type-I inclusions from granite recorded only the high salinity fluid, the salinity of which compares well with that of the highly saline fluid component of type-I inclusions in the pegmatites. This is a possible indication of a genetic link between the pegmatites and spatially associated granite.     

Fluid inclusion studies on the Koraput Alkaline Complex,Eastern Ghats Province,India: Implications for mid-Neoproterozoic granulite facies metamorphism and exhumation

Following ultrahigh temperature granulite metamorphism at ∼1 Ga, the Eastern Ghats Province of India was intruded by the Koraput Alkaline Complex, and was subsequently re-metamorphosed in the granulite facies in the mid-Neoproterozoic time. Fluid inclusion studies were conducted on silica undersaturated alkali gabbro and syenites in the complex, and a pre-metamorphic pegmatitic granite dyke that intrudes it. High density (1.02–1.05 g/cc), pseudo-secondary pure CO₂ inclusions are restricted to metamorphic garnets within the gabbro and quartz within the granite, whereas moderate (∼0.92–0.95 g/cc) and low density (∼0.75 g/cc) secondary inclusions occur in garnet, magmatic clinopyroxene, plagioclase, hornblende and quartz. The isochores calculated for high density pseudo-secondary inclusions pass very close to the peak metamorphic window (∼8 kbar, 750 °C), and are interpreted to represent the fluid present during peak metamorphism that was entrapped by the growing garnet. Microscopic round inclusions of undigested, relict calcite in garnet suggest that the CO₂ present during metamorphism of the complex was internally derived through carbonate breakdown. Pure to low salinity (0.00–10.1 wt% NaCl equivalent) aqueous intra-/intergranular inclusions showing unimodal normal distribution of final ice-melting temperature (T_m) and temperature of homogenization (T_h) are present only in quartz within the granite. These represent re-equilibrated inclusions within the quartz host that were entrapped at the metamorphic peak. Rare, chemically precipitated graphite along the walls of carbonic inclusions is interpreted as a post-entrapment reaction product formed during decompression. The fluid inclusion evidence is consistent with rapid exhumation of a thickened lower crust following the mid-Neoproterozoic granulite facies metamorphic event. The study suggests that mantle CO₂, transported by alkaline magma into the crust, was locked up within carbonates and released during granulite metamorphism.     

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

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

Long-lived magmatic systems and implications on the recognition of granite–pegmatite genetic relations: Characterization of the Pavia granitic pegmatites (Ossa-Morena Zone,Portugal)

It is generally accepted that pegmatites are derived from large masses of granite but, even in areas where complete mineralogical, chemical and isotopic datasets are available, the relation between pegmatites and host granitic rocks or nearby plutons is usually not simple to address. The Pavia pluton, located in the Ossa-Morena Zone (Iberian Massif), is a multiphase intrusive body constructed over ∼11 m.y. by the amalgamation of several batches of magma. At the first glance, pegmatites seem to constitute a very homogeneous pegmatite field. They are mainly “intragranitic” thin tabular dikes, unzoned, layered, or with simple internal structure and are composed by the ordinary minerals that constitute the different classes of igneous rocks. They also present identical whole rock major and trace elements geochemistry and isotopic signature [(⁸⁷Sr/⁸⁶Sr)_i = 0.70434–0.70581, ɛNd_t = −1.3 to −3.7 and δ¹⁸O = 8.2–9.6‰] but, based on previously published geochronological data, three generations of pegmatites were identified. Two of these are coeval with the emplacement of the host granites (s.l.) at 328 Ma and ca. 324 Ma. The other is related to a later magmatic event at 319–317 Ma. A similar and rather juvenile source is suggested for host granites (s.l.) and pegmatites but a simple and continuous process of intra-chamber magmatic differentiation is not supported by our data. It is suggested that pegmatites derived from slightly evolved batches of magma that interacted with fresh, newly emplaced, batches (from the same or from a similar source) with limited interaction with the crust. Therefore, the Pavia pegmatites do not represent the final products of magmatism at this level of the crust but slightly differentiated products of different batches of magma. This study demonstrates how long-lived magmatic systems can potentially affect the recognition of granite–pegmatite genetic relationships.     

Segregation of magmatic fluids and their potential in the mobilization of platinum-group elements in the South Kawishiwi Intrusion,Duluth Complex,Minnesota — Evidence from petrography,apatite geochemistry and coexisting fluid and melt inclusions

Pegmatitic and other felsic rock pockets and dike-like intrusions are abundant in the South Kawishiwi Intrusion of the Duluth Complex, including the basal, Cu–Ni–PGE mineralized units. These occurrences are found as pockets, pods or as veins and contain abundant accessory apatite and quartz. Quartz hosts primary fluid inclusions as well as silicate melt inclusions. Combined microthermometry and Raman spectroscopy helped to determine the bulk composition of primary fluid inclusions that are CO₂-rich (95 mol%) and contain small amounts of H₂O (4.5 mol%), CH₄ (0.4 mol%) and trace N₂, respectively. This combined technique also made it possible to measure total homogenization temperatures of the inclusions (Th_tot = ~ 225 ± 10 °C), otherwise not detectable during microthermometry. Silicate melt inclusions have been quenched to produce homogeneous glasses corresponding to the original melt. Composition of the entrapped melt is granitoid, peraluminous and is very poor in mafic components. We interpret the melt as a product of partial melting of the footwall rocks due to the contact effect of the South Kawishiwi Intrusion. The presence of CO₂ in the vapor bubbles of the quenched melt inclusions and petrographic evidence suggest that the fluid and melt inclusion assemblages are coeval. The composition of the fluid and melt phase implies that the fluid originates from the mafic magma of the South Kawishiwi Intrusion and the fluid and melt phases coexisted as a heterogeneous melt–fluid system until entrapment of the inclusions.Coexistence of primary fluid and melt inclusions makes it possible to calculate a minimum entrapment pressure (~ 1.7 kbar) and thus estimate formation depth (~ 5.8 km) for the inclusions. Chlorine is suggested to behave compatibly in the silicate melt phase in the fluid–melt system represented by the inclusions, indicated by the high (up to 0.3%) Cl-concentrations of the silicate melt and CO₂-rich nature of the fluid.Apatite halogen-contents provide further details on the behavior of Cl. Apatite in pegmatitic pockets often has elevated Cl-concentrations compared to troctolitic rocks, suggesting enrichment of Cl with progressive crystallization. Systematic trends of Cl-loss at some differentiated melt pockets suggest that in some places Cl exsolved into a fluid phase and migrated away from its source. The segregation of Cl from the melt is probably inhibited by the presence of CO₂-rich fluids until the last stages of crystallization, increasing the potential for the development of late-stage saline brines.Platinum-group minerals are often present in microcracks in silicate minerals, in late-stage differentiated sulfide veinlets and in association with chlorapatite, indicating the potential role of Cl-bearing fluids in the final distribution of PGEs.     

Metallogenesis at the Carris W–Mo–Sn deposit (Gerês,Portugal): Constraints from fluid inclusions,mineral geochemistry,Re–Os and He–Ar isotopes

The Carris orebody consists of two partially exploited W–Mo–Sn quartz veins formed during successive shear stages and multipulse fluid fillings. They cut the Variscan post-D3 Gerês I-type granite. The most important ore minerals are wolframite, scheelite, molybdenite and cassiterite. There are two generations of wolframite. The earlier generation of wolframite is rare and has the highest WO₄Mn content (91 mol%) and the most common wolframite contains 26–57 mol% WO₄Mn. Re–Os dating of molybdenite from the ore quartz veins and surrounding granite yields ages of 279 ± 1.2 Ma and 280.3 ± 1.2 Ma, respectively which are in very good agreement with the previous ID-TIMS U–Pb zircon age for the Carris granite (280 ± 5 Ma).³He/⁴He ratio of pyrite ranging between 0.73 and 2.71 Ra (1 Ra = 1.39 × 10^− 6) and high ³He/³⁶Ar (0.8–5 × 10^− 3) indicate a mixture of a crustal radiogenic helium fluid with a mantle derived-fluid.The fluid inclusion studies on quartz intergrown with wolframite and scheelite, beryl and fluorite reveal that two distinct fluid types were involved in the genesis of this deposit. The first was a low to medium salinity aqueous carbonic fluid (CO₂ between 4 and 14 mol%) with less than 1.95 mol% N₂, which was only found in quartz associated with wolframite. The other was a low salinity aqueous fluid found in all the four minerals. The homogenization temperatures indicate minimum entrapment temperatures of 226–310 °C (average 280 °C) for the H₂O–CO₂–N₂–NaCl fluid and average temperatures of 266 °C for scheelite and 242 °C, 190 °C and 160 °C for the last generations of beryl, fluorite and quartz, respectively. It was estimated that wolframite was deposited ~ 7 km depth, assuming a lithostatic pressure, probably due to strong pressure fluctuation caused by seismic events triggered by brittle tectonics during the exhumation event. Precipitation of scheelite and sulphides took place later, at the same depth, but under a hydrostatic or suprahydrostatic pressure regime, and probably caused by mixing between the magmatic–hydrothermal fluid and meteoric waters that deeply penetrated the basement during post-Variscan decompression.     

Fluid inclusions,muscovite Ar–Ar age,and fluorite trace elements at the Baiyanghe volcanic Be–U–Mo deposit,Xinjiang, northwest China: Implication for its genesis

The Baiyanghe Be–U–Mo deposit is located in the Late Paleozoic Xuemisitan–Kulankazi island arc of the northwestern margin of the Junggar plate, Northwest China. It is the largest Be deposit (2.2 M tons of ore with grades ranging from 0.2% to 1.4%) in Asia. Orebodies in the deposit occur as fractures along contact zones between the Yangzhuang granite porphyry intrusion and Devonian pyroclastic country rocks and within the porphyry itself. Muscovite–fluorite veins are closely associated with the Be–U–Mo mineralization. A new Ar–Ar dating of the muscovite in this study yields a plateau age of 303.0 ± 1.6 Ma, which constrains the timing of the Be–U–Mo mineralization of the deposit. Three stages of fluorite of different colors have been identified at the deposit, with the earliest dark-purple fluorite more closely associated with the mineralization. Microthermometry of fluid inclusions obtained from the three stages of fluorite suggests that the fluorites were precipitated as veins from low temperature (120–150 °C) hydrothermal fluids with salinity ranging from 4.7 to 19.7 wt.% NaCl eqv. Based on the trace elemental concentrations and REE patterns of the fluorite, the style of veining, and the low salinity and low temperature characters of the fluid inclusions, it is suggested that Be and U were most likely transported as fluoride complexes and Mo as hydroxyl complexes. Pb isotopic compositions of the ores and country rocks, as well as O and H isotopic characters of the ore-related muscovite, indicate mixing between magmatic and meteoric waters; both contributed to formation of the ore-forming fluids. Metallic Be, U, and Mo were most likely leached out from the granite porphyry by the fluids. The fluid mixing led to the reduction of U, Mo, and Be and their precipitation at the deposit.     

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.     

The Jiguanshan porphyry Mo deposit in the Xilamulun metallogenic belt,northern margin of the North China Craton,U–Pb geochronology,isotope systematics,geochemistry and fluid inclusion studies: Implications for a genetic model

The Jiguanshan porphyry Mo deposit is located in the southern part of Xilamulun metallogenic belt at the northern margin of the North China Craton (NCC). In the Jiguanshan mining district, two stages of granitoids intrusions have been recognized: a pre-ore granite porphyry with stockworks and veins of Mo mineralization, and a granite porphyry with disseminated Mo mineralization. Zircon U–Pb data and Hf isotope analyses show that the dissemination-mineralized granite porphyry yielded a weighted mean ²⁰⁶Pb/²³⁸U age of 156.0 ± 1.3 Ma, with a crustal ε_Hf(t) values from − 5.6 to + 0.2, and that the main group of magmatic zircons from the pre-ore granite porphyry have a weighted mean ²⁰⁶Pb/²³⁸U age of 167.7 ± 1.7 Ma with ε_Hf(t) values from − 3.2 to + 1.0. Combined with groundmass Ar–Ar age data of the granite porphyry and molybdenite Re–Os age, it is suggested that the Mo mineralization of Jiguanshan deposit was formed in the late Jurassic (153 ~ 155 Ma) during tectonic and magmatic events that affected northeast China. The Mo mineralization was a little bit later than the host granite porphyry. Besides disseminated in the host granite porphyry, Mo mineralization also presents in middle Jurassic pre-ore granite porphyry, Jurassic fine-grained diabase, Triassic quartz porphyry, and in rhyolitic volcanic rocks as well as syenite of Devonian age.The Jiguanshan mining district was affected by the tectonic events associated with the Paleo-Asian Ocean closure, and later by far-field tectonism, related to subduction of the Paleo-Pacific plate (Izanagi) in the Jurassic-Cretaceous. The tectonic and thermal events linked with the latter are commonly referred to as Yanshanian tectono-thermal event, and consists of a series of geodynamic, magmatic and ore-forming processes, which in the mining district area included the intrusion of the pre-ore granite porphyry, the host granite porphyry, Mo mineralization, and fine-grained diabase. Major and trace element analyses show that the host granite porphyry is characterized by high silica abundances (SiO₂ = 77.16 to 77.51%), high Rb/Sr ratios (13.57 to 14.83), high oxidation (Fe₂O₃/FeO = 34.25 to 62.00) and high alkalies (Na₂O + K₂O = 8.21 to 8.38%). Petrographic and microthermometry studies of the fluid inclusions from Mo mineralized veins, characterized by plenty of daughter mineral-bearing inclusions, showed that the predominant homogenization temperatures range from 250 to 440 °C. Combined with Laser Raman analysis of the fluid inclusions, it is indicated that Mo mineralization is related to a high-temperature, hypersaline and high-oxygen fugacity H₂O–NaCl fluid system, with high F contents.Based on geology, geochronology, isotope systematics, geochemistry and fluid inclusion studies as well as regional geology, we propose, for the first time, a genetic model for the Jiguanshan porphyry Mo deposit. During the Jurassic geodynamic evolution of northeast China, high silicic, high oxidized and alkaline-rich granitic magma probably derived from partial melting of the lower crust, episodically intruded along faults into the country rocks. This fluid system, fractionating from the highly differentiated granitic magma and bearing Mo with minor Cu metals, migrated upwards and interacted with the older wall rocks and associated fractures, in which the ore minerals precipitated, resulting in the development of what we refer to as the “Jiguanshan-type” porphyry Mo deposit.     

Geochemistry,Sr–Nd–Pb–Hf isotopes systematics and geochronological constrains on petrogenesis of the Xishan A-type granite and associated W–Sn mineralization in Guangdong Province,South China

The Xishan deposit, located in the western Guangdong Province in South China, is a quartz-vein type W-Sn deposit with an average Sn grade of 0.1–0.4 wt%. The deposit is temporally and spatially associated with Xishan alkali feldspar granite. The W–Sn mineralization is present mainly as veins that are hosted by the granite. In this paper we present new zircon U–Pb age, whole-rock geochemical data, Sr–Nd–Pb–Hf isotopic data and Re–Os age in order to constrain the nature and timing of magmatism and mineralization in the Xishan mining district with implications on geodynamic settings. LA–ICP–MS zircon U–Pb analyses yielded an age of 79.14 ± 0.31 Ma for the alkali feldspar granite, consistent with the molybdenite Re–Os age of 79.41 ± 1.11 Ma. The alkali feldspar granite shows high contents of SiO₂ (71.52–76.25 wt%), high total alkalis (Na₂O + K₂O = 9.35–13.51 wt%), high field strength elements (e.g. Zr = 95.4–116 ppm, Y = 97.1–138 ppm, Nb = 36.1–55.5 ppm, Ga = 97.1–138 ppm), and rare earth elements (total REE = 171.8–194.0 ppm) as well as high Ga/Al ratios (10,000 × Ga/Al = 3.23–3.82) suggesting that it has the geochemical characteristics of A-type granite and shows an A₂ subtype affinity. Sr–Nd isotopes of the alkali feldspar granite show that (⁸⁷Sr/⁸⁶Sr)_i values range from 0.7111 to 0.7183, and the ε_Nd(t) values and Nd model ages (T_2DM) vary from −6.8 to −6.5 and 1414 to 1433 Ma, respectively. The Pb isotopic compositions are variable, with ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values ranging from 18.783 to 18.947, 15.709 to 15.722 and 38.969 to 39.244, respectively, indicating that the alkali feldspar granite was derived from a mantle-crust mixed source. In situ Hf isotopic analyses reveal that the alkali feldspar granite has ε_Hf(t) values ranging from −9.69 to −0.04 and two-stage Hf model ages from 1145 Ma to 1755 Ma, indicating that the alkali feldspar granite was formed by the partial melting of Mesoproterozoic crusts of the Cathaysia Block with additions of mantle-derived materials. These results, together with previously presented regional geological relationships, suggest that the formation of the Xishan granite and associated W–Sn mineralization is related to lithospheric extension and asthenospheric upwelling that are attributed to a directional change of Pacific plate motion.     

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.     

The synorogenic pegmatitic quartz veins of the Guacha Corral Shear zone (Sierra de Comechingones,Argentina): A textural,chemical, isotopic,cathodoluminescence and fluid inclusion study

The quartz veins and pegmatites of the Sierra de Comechingones (Sierras de Córdoba, NE Argentina) belong to the Comechingones Pegmatite field (CPF). For the quartz veins and the zoned pegmatites related parental granites are missing. The country rock of the quartz veins are mylonitic augengneisses in granulite to upper amphibolite facies. Field relations, microscopy, cathodoluminescence, radiometric age data, fluid inclusion, chemical and isotopic composition and literature define the quartz veins as synorogenic formed during the high-temperature phase of the Famatinian (480–460 Ma) event. During the Famatinian up to the Achalian (382–366 Ma) event the synorogenic quartz veins were subjected to high temperature ductile deformation documented by folding, boudinage and finally brittle shearing. K-Ar ages of illite from the shear zones of about 166 Ma document the final cooling of the Sierras Pampeanas below 100 °C. The long lasting thermal and deformational history of the study area is reflected by very different populations of fluid inclusions in vein quartz with remarkably high contents of thermogenic hydrocarbons in the early-formed fluid inclusions. LA–ICP–MS analysis reveals very low lattice-bound trace element contents, i.e. high purity quartz.     

Downward penetration and mixing of sedimentary brines and dilute hot waters at 5 km depth in the granite basement at Soultz-sous-Forêts (Rhine graben,France)

Fluids trapped in granite microfissures around 5 km depth in the GPK2 drilling from the European Hot Dry Rock (HDR) Energy program at Soultz-sous-Forêts, can be related to the rather recent (post-Oligocene) fluid flow due to the rifting of the Rhine graben. Most of fluid inclusions planes were healed by fluids similar to those trapped in hydrothermal quartz veins from the shallower levels of the granite. The fluid inclusion dataset indicates a model of mixing between a sedimentary brine rich in divalent cations (around 20 wt.% eq. NaCl) and a dilute fluid slightly hotter than the brine, and characterized by a temperature close to the present-day measured temperature. The penetration of brines down to 5 km is significant, as well as the lack of homogenization of the reservoir fluids, i.e., each fluid is characterized by a specific salinity in between the two fluid end-members.     

The origin and evolution of skarn-forming fluids from the Phu Lon deposit,northern Loei Fold Belt,Thailand: Evidence from fluid inclusion and sulfur isotope studies

The Phu Lon skarn Cu–Au deposit is located in the northern Loei Fold Belt (LFB), Thailand. It is hosted by Devonian volcano-sedimentary sequences intercalated with limestone and marble units, intruded by diorite and quartz monzonite porphyries. Phu Lon is a calcic skarn with both endoskarn and exoskarn facies. In both skarn facies, andradite and diopside comprise the main prograde skarn minerals, whereas epidote, chlorite, tremolite, actinolite and calcite are the principal retrograde skarn minerals.Four types of fluid inclusions in garnet were distinguished: (1) liquid-rich inclusions; (2) daughter mineral-bearing inclusions; (3) salt-saturated inclusions; and (4) vapor-rich inclusions. Epidote contains only one type of fluid inclusion: liquid-rich inclusions. Fluid inclusions associated with garnet (prograde skarn stage) display high homogenization temperatures and moderate salinities (421.6–468.5 °C; 17.4–23.1 wt% NaCl equiv.). By contrast, fluid inclusions associated with epidote (retrograde skarn stage) record lower homogenization temperatures and salinities (350.9–399.8 °C; 0.5–8 wt% NaCl equiv.). These data suggest a possible mixing of saline magmatic fluids with external, dilute fluid sources (e.g., meteoric fluids), as the system cooled. Some fluid inclusions in garnet contain hematite daughters, suggesting an oxidizing magmatic environment. Sulfur isotope determinations on sulfide minerals from both the prograde and retrograde stages show a uniform and narrow range of δ³⁴S values (?2.6 to ?1.1 ‰ δ³⁴S), suggesting that the ore-forming fluid contained sulfur of orthomagmatic origin. Overall, the Phu Lon deposit is interpreted as an oxidized Cu–Au skarn based on the mineralogy and fluid inclusion characteristics.     

Hydrothermal alteration and Cu–Ni–PGE mobilization in the charnockitic rocks of the footwall of the South Kawishiwi intrusion,Duluth Complex,USA

In the Neoarchean (~ 2.7 Ga) contact metamorphosed charnockitic footwall of the Mesoproterosoic (1.1 Ga) South Kawishiwi intrusion of the Duluth Complex, the primary metamorphic mineral assemblage and Cu–Ni–PGE sulfide mineralization is overprinted by an actinolite + chlorite + cummingtonite + prehnite + pumpellyite + quartz + calcite hydrothermal mineral assemblage along 2–3 cm thick veins. In calcite, hosted by the hydrothermal alteration zones and in a single recrystallized quartz porphyroblast, four different fluid inclusion assemblages are documented; the composition of these fluid inclusions provide p–T conditions of the fluid flow, and helps to define the origin of the fluids and evaluate their role in the remobilization and reprecipitation of the primary metamorphic sulfide assemblage.Pure CO₂ fluid inclusions were found as early inclusions in recrystallized quartz porphyroblast. These inclusions may have been trapped during the recrystallization of the quartz during the contact metamorphism of the footwall charnockite in the footwall of the SKI. The estimated trapping pressure (1.6–2.0 kbar) and temperature (810–920 °C) conditions correspond to estimates based on felsic veins in the basal zones of the South Kawishiwi intrusion.Fluid inclusion assemblages with CO₂–H₂O–NaCl and CH₄–N₂–H₂O–NaCl compositions found in this study along healed microfractures in the recrystallized quartz porphyroblast establish the heterogeneous state of the fluids during entrapment. The estimated trapping pressure and temperature conditions (240–650 bar and 120–150 °C for CO₂–H₂O–NaCl inclusions and 315–360 bar and 145–165 °C for CH₄–N₂–H₂O–NaCl inclusions) are significantly lower than the p–T conditions (> 700 °C and 1.6–2 kbar) during the contact metamorphism, indicating that this fluid flow might not be related to the cooling of the Duluth Complex and its contact aureole. The presence of chalcopyrite inclusions in these fluid inclusions and in the trails of these fluid inclusion assemblages confirms that at least on local scale these fluids played a role in base metal remobilization. No evidences have been observed for PGE remobilization and transport in the samples. The source of the carbonic phase in the carbonic assemblages (CO₂; CH₄) could be the graphite, present in the metasedimentary hornfelsed inclusions in the basal zones of the South Kawishiwi intrusion.The hydrothermal veins in the charnockite can be characterized by an actinolite + cummingtonite + chlorite + prehnite + pumpellyite + calcite (I–II) + quartz mineral assemblage. Chlorite thermometry yields temperatures around 276–308 °C during the earliest phase of the fluid flow. In the late calcite (II) phase, high salinity (21.6–28.8 NaCl + CaCl₂ equiv. wt.%), low temperature (90–160 °C), primary aqueous inclusions were found. Chalcopyrite (± sphalerite ± millerite), replacing and intersecting the early hydrothermal phases, are associated to the late calcite (II) phase. The composition of the formational fluids in the Canadian Shield is comparable with the composition of the studied fluid inclusions. This suggests that the composition of the fluids did not change in the past 2 Ga and base metal remobilization by formational fluids could have taken place any time after the formation of the South Kawishiwi intrusion.Sulfur isotope studies carried out on the primary metamorphic (δ³⁴S = 7.4–8.9‰) and the hydrothermal sulfide mineral assemblage (δ³⁴S = 5.5–5.7‰) proves, that during the hydrothermal fluid flow the primary metamorphic ores were remobilized.     

Geology and geochemistry of the Triassic Wenquan Mo deposit and Mo-mineralized granite in the Western Qinling Orogen,China

The recently-discovered Wenquan porphyry Mo deposit hosted in the Wenquan granite of the West Qinling Orogen has been recognized as a product of the Indosinian metallogenesis. Three generations of mineral assemblage for the deposit are identified as follows: (1) quartz–biotite–K-feldspar; (2) quartz–sulfide and (3) sulfide–calcite. Geochemical study shows that the mafic microgranular enclaves (MMEs) in the ore-bearing Wenquan granite have lower SiO₂, and higher Mg# and Nb/Ta ratios than the host granite itself. Different from the granite which have zircon ε_Hf(t) values of − 3.6–3.0 and T_DM2 of 1234–890 Ma, the MMEs are characterized by the ε_Hf(t) values of − 10.1–10.8 and T_DM1 of 865–441 Ma. This can be interpreted to indicate a mixture origin of the Meso- and Neoproterozoic crust-derived component and Neoproterozoic SCLM-derived materials for the formation of the Wenquan granite, which played an essential role in the Mo mineralization. Comparative Pb isotopic data between ores and K-feldspar suggest that the Wenquan granitic magma originated from the middle-lower crust of the South China Block and the ore-forming materials were incorporated by hydrothermal fluid differentiated from the Triassic magmatic system, with minor contribution of sedimentary rocks. The δ³⁴S values of 5.0–11.7‰ with a pronounced mode at 5.0 to 6.1‰ for the ores probably represent the sulfur incorporation of a typical magmatic hydrothermal fluid contaminated by heavy sulfur of Devonian sediments. The granite yielded the zircon U–Pb ages of 218 ± 2.4 Ma and 221 ± 1.3 Ma, as the same as the ages of 217 ± 2.0 Ma and 218 ± 2.5 Ma obtained for the MMEs. These ages are indistinguishable with the molybdenite Re–Os isochron age of 219 ± 5.2 Ma which is the timing for the Mo mineralization. Tectonically, the magmatic mixture processes of the Wenquan granite and the Mo mineralization to form the Wenquan Mo deposit contemporaneously occurred during the transition of tectonic regime from syn- to post-collision orogeny in the Qinling Orogen in the Late Triassic.     

Geology and fluid evolution of the Wangfeng orogenic-type gold deposit,Western Tian Shan,China

The Wangfeng gold deposit is located in Western Tian Shan and the central section of the Central Asian Orogenic Belt (CAOB). The deposit is mainly hosted in Precambrian metamorphic rocks and Caledonian granites and is structurally controlled by the Shenglidaban ductile shear zone. The gold orebodies consist of gold-bearing quartz veins and altered mylonite. The mineralization can be divided into three stages: quartz–pyrite veins in the early stage, sulfide–quartz veins in the middle stage, and quartz–carbonate veins or veinlets in the late stage. Ore minerals and native gold mainly formed in the middle stage. Four types of fluid inclusions were identified based on petrography and laser Raman spectroscopy: CO₂–H₂O inclusions (C-type), pure CO₂ inclusions (PC-type), NaCl–H₂O inclusions (W-type), and daughter mineral-bearing inclusions (S-type). The early-stage quartz contains only primary CO₂–H₂O fluid inclusions with salinities of 1.62 to 8.03 wt.% NaCl equivalent, bulk densities of 0.73 to 0.89 g/cm³, and homogenization temperatures of 256 °C–390 °C. Vapor bubbles are composed of CO₂. The middle-stage quartz contains all four types of fluid inclusions, of which the CO₂–H₂O and NaCl–H₂O types yield homogenization temperatures of 210 °C–340 °C and 230 °C–300 °C, respectively. The CO₂–H₂O fluid inclusions have salinities of 0.83 to 9.59 wt.% NaCl equivalent and bulk densities of 0.77 to 0.95 g/cm³, with vapor bubbles composed of CO₂, CH₄, and N₂. Fluid inclusions in the late-stage quartz are NaCl–H₂O solution with low salinities (0.35–3.87 wt.% NaCl equivalent) and low homogenization temperatures (122 °C–214 °C). The coexistence of inclusions of these four types in middle-stage quartz suggests that fluid boiling occurred in the middle-stage mineralization. Trapping pressures estimated from CO₂–H₂O inclusions are 110–300 MPa and 90–250 MPa for the early and middle stages, respectively, suggesting that gold mineralization mainly occurred at depths of about 10 km. In general, the Wangfeng gold deposit originated from a metamorphic fluid system characterized by low salinity, low density, and enrichment of CO₂. Depressurized fluid boiling caused gold precipitation. Given the regional geology, ore geology, fluid-inclusion features, and ore-forming age, the Wangfeng gold deposit can be classified as a hypozonal orogenic gold deposit.     

Primary to re-equilibrated fluids and geochemical signatures for the evolution of the Nagthat siliciclastics in the Tons valley,Lesser Himalaya,India

Medium to coarse-grained Neo-Proterozoic Nagthat siliciclastic rocks form a part of the Krol Formation in the Lesser Himalayan geotectonic zone. Fluid inclusion and geochemical studies have been carried out on the Nagthat siliciclastics from the Tons valley to determine their provenance during the Proterozoic and their recrystallisation during maximum burial to uplift. Fluid inclusion studies have been carried out on detrital, recrystallised quartz grains and quartz overgrowths. Major and trace element analyses of the siliciclastics, the relationships of SiO₂ with various trace elements, and the association of various trace elements with mineral species suggest a granitic source for these siliciclastics. Primary Q1 aqueous brine inclusions and Q3 H₂O–CO₂ fluid with 0.9 gm/cm³ CO₂ density in detrital quartz grains characterised the protolith of the sandstone as granite or metamorphic rocks. H₂O–NaCl fluids participated in the cementation history, temperatures of quartz overgrowth from 198 to 232 °C show the effect of maximum burial. The re-equilibration of the primary fluid due to elevated internal pressure > confining pressure is evident from features like ‘C’ shaped cavities, stretching of the inclusions, their migration, decrepitation clusters, etc. During recrystallisation these inclusions were equilibrated at 187 ° and 235 °C in a restricted fluid of aqueous, moderately saline composition. The observed inclusion morphology is attributed to a decrease in external pressure related to isothermal decompression uplift.     

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

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

Ore-forming process of the Huijiabao gold district,southwestern Guizhou Province,China: Evidence from fluid inclusions and stable isotopes

The Huijiabao gold district is one of the major producers for Carlin-type gold deposits in southwestern Guizhou Province, China, including Taipingdong, Zimudang, Shuiyindong, Bojitian and other gold deposits/occurrences. Petrographic observation, microthermometric study and Laser Raman spectroscopy were carried out on the fluid inclusions within representative minerals in various mineralization stages from these four gold deposits. Five types of fluid inclusions have been recognized in hydrothermal minerals of different ore-forming stages: aqueous inclusions, CO₂ inclusions, CO₂–H₂O inclusions, hydrocarbon inclusions, and hydrocarbon–H₂O inclusions. The ore-forming fluids are characterized by a H₂O + CO₂ + CH₄ ± N₂ system with medium to low temperature and low salinity. From early mineralization stage to later ones, the compositions of the ore-forming fluids experienced an evolution of H₂O + NaCl → H₂O + NaCl + CO₂ + CH₄ ± N₂ → H₂O + NaCl ± CH₄ ± CO₂ with a slight decrease in homogenization temperature and salinity. The δ¹⁸O values of the main-stage quartz vary from 15.2‰ to 24.1‰, while the δD_H2O and calculated δ¹⁸O_H2O values of the ore-forming fluids range from −56.9 to −116.3‰ and from 2.12‰ to 12.7‰, respectively. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcite change in the range of −9.1‰ to −0.5‰ and 11.1–23.2‰, respectively. Stable isotopic characteristics indicate that the ore-forming fluid was mainly composed of ore- and hydrocarbon-bearing basinal fluid. The dynamic fractionation of the sulfur in the diagenetic pyrite is controlled by bacterial reduction of marine sulfates. The hydrothermal sulfides and the diagenetic pyrite from the host rocks are very similar in their sulfur isotopic composition, suggesting that the sulfur in the ore-forming fluids was mainly derived from dissolution of diagenetic pyrite. The study of fluid inclusions indicates that immiscibility of H₂O–NaCl–CO₂ fluids took place during the main mineralization stage and caused the precipitation and enrichment of gold.