Genesis of massive sulfide deposits in the Verkhneural’sk ore district, the South Urals, Russia: Evidence for magmatic contribution of metals and fluids

Melt inclusions and aqueous fluid inclusions in quartz phenocrysts from host felsic volcanics, as well as fluid inclusions in minerals of ores and wall rocks were studied at the Cu-Zn massive sulfide deposits in the Verkhneural’sk ore district, the South Urals. The high-temperature (850–1210°C) magmatic melts of volcanic rocks are normal in alkalinity and correspond to rhyolites of the tholeiitic series. The groups of predominant K-Na-type (K₂O/Na₂O = 0.3–1.0), less abundant Na-type (K₂O/Na₂O = 0.15–0.3), and K-type (K₂O/Na₂O = 1.9–9.3) rhyolites are distinguished. The average concentrations (wt %) of volatile components in the melts are as follows: 2.9 H₂O (up to 6.5), 0.13 Cl (up to 0.28), and 0.09 F (up to 0.42). When quartz was crystallizing, the melt was heterogeneous, contained magnetite crystals and sulfide globules (pyrrhotite, pentlandite, chalcopyrite, bornite). High-density aqueous fluid inclusions, which were identified for the first time in quartz phenocrysts from felsic volcanics of the South Urals, provide evidence for real participation of magmatic water in hydrothermal ore formation. The fluids were homogenized at 124–245°C in the liquid phase; the salinity of the aqueous solution is 1.2–6.2 wt % NaCl equiv. The calculated fluid pressure is very high: 7.0–8.7 kbar at 850°C and 5.1–6.8 kbar at 700°C. The LA-ICP-MS analysis of melt and aqueous fluid inclusions in quartz phenocrysts shows a high saturation of primary magmatic fluid and melt with metals. This indicates ore potential of island-arc volcanic complexes spatially associated with massive sulfide deposits. The systematic study of fluid inclusions in minerals of ores and wall rocks at five massive sulfide deposits of the Verkhneural’sk district furnished evidence that ore-forming fluids had temperature of 375–115°C, pressure up to 1.0–0.5 kbar, chloride composition, and salinity of 0.8–11.2 (occasionally up to 22.8) wt % NaCl equiv. The H and O isotopic compositions of sericite from host metasomatic rocks suggest a substantial contribution of seawater to the composition of mineral-forming fluids. The role of magmatic water increases in the central zones of the feeding conduit and with depth. The dual nature of fluids with the prevalence of their magmatic source is supported by S, C, O, and Sr isotopic compositions. The TC parameters of the formation of massive sulfide deposits are consistent with the data on fluid inclusions from contemporary sulfide mounds on the oceanic bottom.     

Tourmaline from deposits of the Birgil’da-Tomino ore cluster, South Urals

Tourmalines from the Kalinovka porphyry copper deposit with epithermal bismuth-gold-basemetal mineralization and the Michurino gold-silver-base-metal prospect have been studied in the South Urals. Tourmaline from the Kalinovka deposit occurs as pockets and veinlets in quartz-sericite metasomatic rock and propylite. The early schorl-“oxy-schorl” [Fe_tot/(Fe_tot + Mg) = 0.66?0.81] enriched in Fe³⁺ is characterized by the homovalent isomorphic substitution of Fe³⁺ for Al typical of propylites at porphyry copper deposits. The overgrowing tourmalines of the second and third generations from propylite and quartz-sericite metasomatic rock are intermediate members of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.05?0.46] with homovalent substitution of Mg for Fe²⁺ and coupled substitution of ^X _? + ^YAl for ^XNa + ^YMg. These substitutions differ from the coupled substitution of ^YAl + ^WO^2? for ^YFe²⁺ + ^WOH^? in tourmaline from quartz-sericite rocks at porphyry copper deposits. At the Michurino prospect, the tourmaline hosted in the chlorite-pyrite-quartz veins and veinlets with Ag-Au-Cu-Pb-Zn mineralization is an intermediate member of the dravite-magnesio-foitite solid solution series [Fe_tot/(Fe_tot + Mg) = 0.20?0.31] with homovalent substitution of Mg for Fe²⁺ and coupled substitutions of ^X _? + ^YAl for ^XNa + ^YMg identical to that of late tourmaline at the Kalinovka deposit. Thus, tourmalines of the porphyry and epithermal stages are different in isomorphic substitutions, which allow us to consider tourmaline as an indicator of super- or juxtaposed mineralization.     

Relationship of the thermal conductivity of rocks in the Komsomol’sk ore district (Khabarovsk Territory) with minerageny and metasomatism

Statistical data are given on the thermal conductivity of rocks in the Komsomol’sk ore district (Khabarovsk Territory). The regularities of variations in the thermal-conductivity and thermal-inhomogeneity factors of the studied types of rocks are considered in relation to their mineral composition, texture, structure, and degree of metasomatic alteration. Thermophysical sections of the studied mineralized zones are presented. The conclusion is substantiated that the thermal properties of rocks are highly informative and detailed thermophysical studies of sections might be useful for their lithological subdivision.© 2015, V.S. Sobolev IGM, Siberian Branch of the RAS. Published by Elsevier B.V. All rights reserved.     

Tectonics and metallogeny of the Khakandzha ore district in the Okhotsk–Chukotka volcanic belt

The data on the structure, geodynamics, and metallogeny of the Khakandzha ore district in northwestern Okhotsk region are analyzed and the two main factors responsible for the localization of ore deposits are defined. The magmatic factor controls the confinement of the ore district to the tectono-magmatic structure of the central type (source of ore matter), which determines the concentric zoning patterns in the distribution of ore mineralization. The tectonic factor determines the confinement of the ore districts, deposits, and ore occurrences of the region to the meridional left-lateral shear structure, which controls the magma and fluid distribution. Local extension (transtension) in this structure against the background of general lateral compression (transpression) provided tectonic environments most favorable for ore accumulation.     

Petrology of volcanic and plutonic rocks from the Uimen-Lebed’ terrain,Gorny Altai

The Uimen-Lebed’ volcanoplutonic terrane is located at the junction of the Gorny Altai, Gornaya Shoriya, and western Sayan structures and is part of the Devonian-Early Carbonaceous Salair-Altai volcanoplutonic belt. The volcanic facies of the terrane composes the contrasting Nyrnin-Sagan Group, which includes basalt-basaltic andesite and basalt-rhyolite associations. The plutonic facies makes up the multiplet Elekmonar Group, which includes two independent complexes: monzogabbro-monzodiorite-granodiorite-granite and granodiorite-granite-leucogranite. The volcanic and plutonic rocks are asymmetrically distributed: volcanic sequences fill inherited depressions in the eastern part of the terrane, whereas plutonic complexes are located in its western part at the fault system branching from the transregional Kuznetsk-Teletsk-Kurai fault zone. The basalts of the Nyrnin-Sagan Group show geochemical signatures of both suprasubduction and rift-related rocks. The evolution of basaltoid magmatism reflects the formation and development of a suprasubduction mantle wedge in the inner part of an active continental margin accompanied by the influence of an intraplate mantle source. The silicic volcanism was generated under lower crustal conditions (P > 10 kbar) at the expense of metabasic materials and was accompanied by the influx of potassium into the anatectic zones. The gabbroids of the Elekmonar Group show suprasubduction geochemical features and no signatures of rift-related structures. The composition of the Elekmonar granitoids indicates significantly shallower (compared with the silicic volcanics) depths of their generation. The Uimen-Lebed’ volcanoplutonic terrane in the northeastern part of Gorny Altai was formed in the inner part of an active continental margin of the Andean type. Its magmatic complexes were formed over a considerable time range, from the early Emsian, when the formation of the active continental margin began, to the end of the Eifelian or, more likely, the beginning of the Givetian stage.     

Mechanism of mineralization in the Changjiang uranium ore field,South China: Evidence from fluid inclusions,hydrothermal alteration,and H–O isotopes

The Changjiang uranium ore field, which contains >10,000 tonnes of recoverable U with a grade of 0.1–0.5%, is hosted by Triassic two-mica and Jurassic biotite granites, and is one of the most important uranium ore fields in South China. The minerals associated with alteration and mineralization can be divided into two stages, namely syn-ore and post-ore. The syn-ore minerals are primarily quartz, pitchblende, hematite, hydromica, chlorite, fluorite, and pyrite; the post-ore minerals include quartz, calcite, fluorite, pyrite, and hematite. The fluid inclusions of the early syn-ore stage characteristically contain O₂, and those of the late syn-ore and post-ore stage contain H₂ and CH₄. The fluid inclusions in quartz of the syn-ore stage include H₂O, H₂O–CO₂, and CO₂ types, and they occur in clusters or along trails. Homogenization temperatures (T_h) for the H₂O–CO₂ and two-phase H₂O inclusions range from 106 °C to >350 °C and cluster in two distinct groups for each type; salinities are lower than 10 wt% NaCl equiv. The ore-forming fluids underwent CO₂ effervescence or phase separation at ∼250 °C under a pressure of 1000–1100 bar. The U/Th values of the altered granites are lowest close to the ore, increase outwards, but subsequently decrease close to unaltered granites. From the unaltered granites to the ore, the lowest Fe₂O₃/FeO values become lower and the highest values higher. The REE patterns of the altered granites and the ores are similar to each other. The U contents of the ores show a positive correlation with total REE contents but a negative correlation with LREE/HREE ratios, indicating the pitchblende is REE-bearing and selectively HREE-rich. The δEu values of the ore show a positive correlation with U contents, indicating the early syn-ore fluids were oxidizing. The δCe values show a negative correlation, indicating the later mineralization environment became reducing. The water–rock interactions of the early syn-ore stage resulted in oxidization of altered granites and reduction of the ore-forming fluids, and it was this reduction that led to the uranium mineralization. During alteration in the early syn-ore stage, the oxidizing fluids leached uranium from granites close to faults, and Fe₂O₃/FeO ratios increased in the alteration zones. The late syn-ore and post-ore alteration decreased the Fe₂O₃/FeO ratios in the alteration zones. The δ¹⁸O_W–SMOW values of the ore-forming fluids range from −1.8‰ to 5.4‰, and the δD_W–SMOW values range from −104.4‰ to −51.6‰, suggesting meteoric water. The meteoric water underwent at least two stages of water–rock interaction: the first caused the fluids to become uranium-bearing, and the second stage, which was primarily associated with ore-bearing faults, led to uranium deposition as pitchblende, accompanied by CO₂ effervescence.     

Maucherite from metamorphic-hydrothermal assemblages of the Noril’sk ore field

In the Noril’sk ore field, maucherite, Ni₁₁As₈, occurs in magmatic pentlandite-pyrrhotite-chalcopyrite ores transformed into pyrite-millerite-chalcopyrite and millerite-bornite ores under conditions of prehnite-pumplellyite and zeolite facies of metamorphism. Maucherite spatially associated with aggregates of Pd and Pt minerals, probably, as a pseudomorph after mayakite, PdNiAs, contains up to 1.5 wt % Pd. Maucherite is relatively abundant in metamorphic-hydrothermal apophyllite-anhydrite-calcite veins hosted in metaore. In these veins, maucherite occurs as finely split and long-prismatic crystals, their intergrowths, and as a constituent of complexly zoned antimonide-sulfoarsenide-arsenide nodules. Maucherite from veins contains up to 0.6 wt % S and Sb, whereas Pd, Pt, and Au are below the detection limit of an electron microprobe.     

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.     

Sources and formation conditions of sulfide-silicate magmas in the Noril’sk district

Geology, tectonomagmatic reactivation of the Noril??sk district, as well as stratigraphy and geochemistry of the volcanic sequence are considered. Sources and formation mechanism of ore-bearing magma and the scope of ore formation are discussed. The Permian-Triassic flood-basalt magmatism of the Noril??sk district developed in part of the Siberian Platform with Archean-Paleoproterozoic basement broken into blocks and overlapped by a sedimentary cover up to 13 km thick and a volcanic sequence reaching 3.7 km in thickness. The geophysical data show that remnants of the subducted ancient oceanic crust exist in the mantle and fragments of transitional magma chambers and conduits are retained at different levels of the Earth??s crust. The cyclic tectonomagmatic evolution of the territory was characterized by alternation of extension with intense volcanic activity and compression accompanied by waning of volcanic eruptions. The early rifting, transitional stage, and late dispersed spreading are distinguished. The associations of volcanic (lavas and tuffs) and intrusive rocks were formed during each stage. The volcanic sequence is subdivided into 11 formations. The intrusions of the Talnakh and Noril??sk ore fields are distinguished by two-level structure with the Upper Noril??sk ore-bearing intrusions above and the Lower Noril??sk barren intrusions below. Two types of primary magmas differ in geochemistry of lavas and intrusions: (1) OIB-type high-Ti magma (iv, sv, gd formations of the first stage from bottom to top) and (2) low-Ti magma (hk, tk, nd formations of the second stage and mr-mk formations of the third stage). The nd formation depleted in ore elements and the ore-bearing cumulus composed of silicate and sulfide melts in combination with early silicate minerals and chromite are products of the fractionation of the primary low-Ti magma. As follows from geochemical parameters, intrusions of the Lower Noril??sk type are comagmatic to the evolved lavas of the nd₃ subformation, whereas intrusions of the Upper Noril??sk type are comagmatic to the lavas of the mr-mk formations. Geochemical similarity with volcanic rocks provides evidence for the composition of the initial magma and the time of intrusion emplacement. The ore-bearing intrusions of the Upper Noril??sk type were formed at the onset of the third stage, when the primitive low-Ti magma similar to the lavas of mr-mk formations in composition was emplaced. When intruding, this melt captured and transported ore-bearing cumulus (drops of sulfide melt, early olivine and chromite grains) into the magma chamber. Separate portions of sulfide liquid were involved into movement as a self-dependent intrusive subphase during formation of the Talnakh and Kharaelakh intrusions. An extremal effect of pressure on sulfur concentration in fluid-bearing and sulfide-saturated mafic magmas has been established in experiments to be P = 1?2 GPa. In this interval of pressure, the S concentration in sulfide-saturated magmas increases in the following sequence: dry magma ??(H₂O + CO₂)-bearing magma <H₂O-bearing magma. In the regions of low (<0.3 GPa) and high (>2.5 GPa) pressures, the S contents (0.1?C0.2 wt %) are commensurable. The extremal baric relationship of S concentration in fluid-bearing and sulfide-saturated mafic magmas may be important for the formation of ore-bearing magmas. The calculation results show that the amount of sulfides in the known deposits does not exceed 2% of geological resources of the sulfides separated from the flood basalts. Therefore, the chance of discovery of new deposits remains rather high. Proceeding from the conditions of ore-bearing magma formation and geological setting of the known deposits, criteria for recognition of potentially ore-bearing areas are proposed and such areas are outlined.     

Redox problems in the “metallogenic specialization” of magmatic rocks and the genesis of hydrothermal ore mineralization

Considering the history and current state of the problem of the so-called metallogenic specialization of magmatic rocks, the paper places emphasis onto various aspects of the genesis of ore mineralization depending on the redox state of magmas (as a logical continuation of S. Ishihara’s works), fluids, and host rocks. These problems were inadequately poorly explored and discussed by researchers dealing with ore deposits. Various possible variants of ore-forming redox processes for different types of mineral deposits, with ore mineralization affiliated to granites (Ta, Sn, W, Mo, and Be) and mafic magmas (Au, Ag, U, Cu, Zn, Pb, As, Sb, and Hg) and, accordingly, to crustal and mantle origin, are discussed. On the basis of analyzed geological data, including those published over the past three decades, it is shown that the redox state of ore-producing magmas commonly significantly impacted not only the ore potential of magmatic complexes but also the genetic type of the ore mineralization. The redox state of the fluids predetermined the transport and precipitation speciation of metals. Influence mechanisms of hydrocarbons from sedimentary country rocks and gaseous products of their pyrolysis on ore deposition of various metals are considered. Understanding these mechanisms can be helpful for predicting the possible precipitation sites of ore mineralization of noble, radioactive, and chalcophile metals.     

Composition and geodynamic setting of the volcanic rocks from ophiolites of the Ust’-Belaya Mountains,Chukchi Peninsula

In addition to ophiolites in the structure of the Otrozhnaya sheet, the igneous rocks were established within the Middle Devonian-Lower Carboniferous tuffaceous-terrigenous complex earlier considered to be the cover of the ophiolite association. In order to establish their geodynamic formation setting, the geochemical study of igneous rocks was conducted. The volcanic rocks from the ophiolite complex are similar to MORB; subvolcanic rocks of tuffaceous-terrigenous complex have a suprasubduction origin. An abundance of pyroclastic rocks and the type of sediments allow us to conclude about their formation in an island arc setting. The existence of the Middle Devonian-Lower Carboniferous island arc complex within the Ust’-Belaya Mountains gives rise to continue the Koni-Taigonos arc inside the region and testifies to its subsistence in the Devonian.     

Structure and geochemical characteristics of trap rocks from the Noril’sk Trough,Northwestern Siberian craton

Modern analytical methods (XRF and ICP-MS) were employed for the first time to investigate the geochemical characteristics of rocks from the Noril’sk Trough. It differs from other folded structures of the region in the presence of massifs with high-grade Pt-Cu-Ni ores at relatively high levels in the section of the platform cover, in the middle part of the tuff-lava sequence. This provides an opportunity of directaions of observe geologic relationships between the extrusive and intrusive rocks of the Siberian Traps and more reliably test the possibility of their comagmatic origin, because other intrusions with massive ores occur at a deeper stratigraphic level in the Devonian sequences (Kharaerlakhsky and Talnakhsky massifs in the Kharaerlakhsky Trough). A comparison of the volcanic sections of the Noril’sk Trough and other parts of the region suggests that the tectonic structures were initiated before or simultaneously with trap development. By the example of the sill of the Maslovsky intrusion, it was shown that the ore-bearing gabbro-dolerites were formed in post-Nadezhdinsky time. The geochemical characteristics of the rocks of the Noril’sk 1 and Maslovsky intrusions were compared with those of the supposedly comagmatic rocks of the Gudchikhinsky, Tuklonsky, Nadezhdinsky, and Morongovsky formations. It was found that the Gudchikhinsky picritic basalts show higher Gd/Yb values compared with the picritic gabbro-dolerites (on average, 2.5 and 1.5, respectively) and higher nickel and calcium contents in olivine (0.44 and 0.22 wt % NiO and 0.30 and 0.12 wt % CaO for Fo₈₂, respectively). The high-magnesium rocks of the Tuklonsky Formation are depleted in U and enriched in Eu relative to their intrusive analogues and also differ with respect to NiO and CaO contents in olivine (0.11 and 0.21 wt % NiO and 0.21 and 0.12 wt % CaO for Fo₇₈, respectively). The rocks of the Nadezhdinsky Formation show strongly enriched incompatible trace element patterns, especially for LREE. Although the Morongovsky Formation is geochemically similar to the intrusions of the Noril’sk complex, it shows a lower weighted mean MgO content (6–7 wt % as compared with 11–12 wt % for the gabbro-dolerites). Thus, it was shown by the example of the geologic setting and compositional features of the Maslovsky intrusion that the massifs with high-grade mineralization are not analogues of volcanic complexes, but were produced by an independent magmatic stage.     

Channelized fluids in subducted continental crust: constraints from δD–δ18O of quartz and fluid inclusions in quartz veins from the Chinese Continental Scientific Drilling Project

Fluid inclusions hosted by quartz veins in high-pressure to ultrahigh-pressure (HP-UHP) metamorphic rocks from the Chinese Continental Scientific Drilling (CCSD) Project main drillhole have low, varied hydrogen isotopic compositions (δD?=??97‰ to??69‰). Quartz δ¹⁸O values range from??2.5‰ to 9.6‰; fluid inclusions hosted in quartz have correspondingly low δ¹⁸O values of??11.66‰ to 0.93‰ (T _h?=?171.2～318.8°C). The low δD and δ¹⁸O isotopic data indicate that protoliths of some CCSD HP-UHP metamorphic rocks reacted with meteoric water at high latitude near the surface before being subducted to great depth. In addition, the δ¹⁸O of the quartz veins and fluid inclusions vary greatly with the drillhole depth. Lower δ¹⁸O values occur at depths of ～900–1000 m and ～2700 m, whereas higher values characterize rocks at depths of about 1770 m and 4000 m, correlating roughly with those of wall-rock minerals. Given that the peak metamorphic temperature of the Dabie-Sulu UHP metamorphic rocks was about 800°C or higher, much higher than the closure temperature of oxygen isotopes in quartz under wet conditions, such synchronous variations can be explained by re-equilibration. In contrast, δD values of fluid inclusions show a different relationship with depth. This is probably because oxygen is a major element of both fluids and silicates and is much more abundant in the quartz veins and silicate minerals than is hydrogen. The oxygen isotope composition of fluid inclusions is evidently more susceptible to late-stage re-equilibration with silicate minerals than is the hydrogen isotope composition. Therefore, different δD and δ¹⁸O patterns imply that dramatic fluid migration occurred, whereas the co-variation of oxygen isotopes in fluid inclusions, quartz veins, and wall-rock minerals can be better interpreted by re-equilibration during exhumation.

Quartz veins in the Dabie-Sulu UHP metamorphic terrane are the product of high-Si fluids. Given that channelized fluid migration is much faster than pervasive flow, and that the veins formed through precipitation of quartz from high-Si fluids, the abundant veins indicate significant fluid mobilization and migration within this subducted continental slab. Many mineral reactions can produce high-Si fluids. For UHP metamorphic rocks, major dehydration during subduction occurred when pressure–temperature conditions exceeded the stability of lawsonite. In contrast, for low-temperature eclogites and other HP metamorphic rocks with peak metamorphic P–T conditions within the stability field of lawsonite, dehydration and associated high-Si fluid release may have occurred as hydrous minerals were destabilized at lower pressure during exhumation. Because subduction is a continuous process whereas only a minor fraction of the subducted slabs returns to the surface, dehydration during underflow is more prevalent than exhumation even in subducted continental crust, which is considerably drier than altered oceanic crust.     

Mixed messages in iron oxide–copper–gold systems of the Cloncurry district,Australia: insights from PIXE analysis of halogens and copper in fluid inclusions

Proterozoic rocks of the Cloncurry district in NW Queensland, Australia, are host to giant (tens to hundreds of square kilometers) hydrothermal systems that include (1) barren regional sodic–calcic alteration, (2) granite-hosted hydrothermal complexes with magmatic–hydrothermal transition features, and (3) iron oxide–copper–gold (IOCG) deposits. Fluid inclusion microthermometry and proton-induced X-ray emission (PIXE) show that IOCG deposits and the granite-hosted hydrothermal complexes contain abundant high temperature, ultrasaline, complex multisolid (type 1) inclusions that are less common in the regional sodic–calcic alteration. The latter is characterized by lower salinity three-phase halite-bearing (type 2) and two-phase (type 3) aqueous inclusions. Copper contents of the type 1 inclusions (>300 ppm) is higher than in type 2 and 3 inclusions (<300 ppm), and the highest copper concentrations (>1,000 ppm) are found both in the granite-hosted systems and in inclusions with Br/Cl ratios that are consistent with a magmatic source. The Br/Cl ratios of the inclusions with lower Cu contents are consistent with an evaporite-related origin. Wide ranges in salinity and homogenization temperatures for fluid inclusions in IOCG deposits and evidence for multiple fluid sources, as suggested by halogen ratios, indicate fluid mixing as an important process in IOCG genesis. The data support both leaching of Cu by voluminous nonmagmatic fluids from crustal rocks, as well as the direct exsolution of Cu-rich fluids from magmas. However, larger IOCG deposits may form from magmatic-derived fluids based on their higher Cu content.     

Geology,fluid inclusions,and geochemistry of the Zhazixi Sb–W deposit,Hunan, South China

The Zhazixi Sb–W deposit in the Xuefeng uplift, South China, exhibits a unique metal association of W and Sb, where the W orebodies are hosted by interlayer fractures and the Sb orebodies are contained within NW-trending faults. This study proposes that the W and Sb mineralization took place in two separate periods. The mineral paragenesis of the W mineralization reveals a mass of quartz, scheelite and minor calcite. The mineral assemblage of the Sb mineralization developed after W mineralization and consists of predominantly quartz and stibnite, and small amounts of native Sb, berthierite, chalcostibnite, pyrite, and chalcopyrite. Fluid inclusions in quartz and coexisting scheelite are dominated by two-phase, liquid-rich, aqueous inclusions at room temperature. Microthermometric studies suggest that ore-forming fluids for W mineralization are characterized by moderate temperatures (170–270 °C), low salinity (3–7 wt% NaCl equiv.), low density (0.75–0.95 g/cm³), and moderate to high pressure (57.2–99.7 MPa) and these fluids experienced a cooling and dilution evolution during W mineralization. Ore-forming fluids for Sb mineralization are epithermal types with low temperatures (150–230 °C), low salinity (4–6 wt% NaCl equiv.), moderate density (0.82–0.94 g/cm³), and high pressure (42.2–122.5 MPa) and these fluids display an evident decline in homogenization temperature during Sb mineralization. Laser Raman analyses of the vapor phase indicate that the ore-forming fluids for both W and Sb mineralization contain a small amount of CO₂.The ore-forming fluids for Sb mineralization are identified as predominantly originating from the continental crust, as suggested by the low ³He values (0.009 × 10⁻¹² cc.STP/g) and ³He/⁴He ratios (0.002–0.056 Ra) as well as high ³⁶Ar values (1.93 × 10⁻⁹ cc.STP/g) and ⁴⁰Ar/³⁶Ar ratios (909.5–2279.7). The source of S is identified to be the Neoproterozoic Wuqiangxi Formation, as traced by the δ³⁴S_V-CDT values of stibnite (3.1–9.4‰). The ²⁰⁸Pb/²⁰⁴Pb (37.643–40.222), ²⁰⁷Pb/²⁰⁴Pb (15.456–15.681), and ²⁰⁶Pb/²⁰⁴Pb (17.093–20.042) ratios suggest a mixture of lower crustal and supracrustal Pb sources.It is thus concluded that the ore genesis of the Zhazixi Sb–W deposit is related to the intracontinental orogeny during the early Mesozoic. Fluid mixing is considered to be the critical mechanism involved in W mineralization, whereas a fluid cooling process is responsible for Sb mineralization. Furthermore, the absence of Au is attributed to the low Σa_s content in Sb-mineralizing fluids.     

Submicron-sized fluid inclusions and distribution of hydrous components in jadeite,quartz and symplectite-forming minerals from UHP jadeite–quartzite in the Dabie Mountains,China: TEM and FTIR investigation

Fluid inclusions and clusters of water molecules at nanometer-to submicron-scale in size have been investigated using transmission electron microscopy (TEM) and Fourier transform infrared spectroscopy (FTIR) in jadeite, quartz and symplectite aegirine–augite, albite, taramite and magnetite corona minerals from ultrahigh-pressure (UHP) jadeite–quartzite at Shuanghe, the Dabie Mountains, China. Fluid inclusions from 0.003 μm to 0.78 μm in size occur in jadeite and quartz crystals, and a small number of fluid inclusions from 0.001 μm to 0.25 μm have also been detected in symplectite-forming minerals. Most of the fluid inclusions have round or negative crystal morphology and contain aqueous fluids, but some contain CO₂-rich fluids. They are usually connected to dislocations undetectable at an optical scale. The dislocations represent favorable paths for fluid leakage, accounting for non-decrepitation of most fluid inclusions when external pressure decreased at later stages, although there was partial decrepitation of some fluid inclusions unconnected to defect microstructures resulting from internal overpressure. Non-decrepitation and partial decrepitation of fluid inclusions resulted in changes of original composition and/or density. It is clear that identification of hidden re-equilibration features has significant implications for the petrological interpretation of post-peak metamorphic processes. Micro-FTIR results show that all jadeite and quartz samples contain structural water occurring as hydroxyl ions (OH⁻) and free water (H₂O) in the form of clusters of water molecules. The H₂O transformed from OH⁻ during exhumation and could have triggered and enhanced early retrograde metamorphism of the host rocks and facilitated plastic deformation of jadeite and quartz grains by dislocation movement, and thus the H₂O released during decompression might represent early-stage retrograde metamorphic fluid. The nominally anhydrous mineral (NAM) jadeite is able to transport aqueous fluids in concentrations of at least several hundred ppm water along a subduction zone to mantle depths in the form of clusters of water molecules and hydroxyl ions within crystals.     

The Late Paleozoic porphyry–epithermal spectrum of the Birgilda–Tomino ore cluster in the South Urals,Russia

The Birgilda–Tomino ore cluster in the East Uralian zone, South Urals, Russia, hosts a variety of Late Paleozoic porphyry copper deposits (Birgilda, Tomino, Kalinovskoe, etc.), high- and low sulfidation epithermal deposits (Bereznyakovskoe, Michurino), and skarn-related base metal mineralization (Biksizak) in carbonate rocks. The deposits are related to quartz diorite and andesite porphyry intrusions of the K–Na calc-alkaline series, associated to a subduction-related volcanic arc. We report microprobe analyses of ore minerals (tetrahedrite–tennantite, sphalerite, Bi tellurides and sulfosalts, Au and Ag tellurides), as well as fluid inclusion data and mineral geothermometry. On the basis of these data we propose that the Birgilda–Tomino ore cluster represents a porphyry–epithermal continuum, with a vertical extent of about 2–3 km, controlled by temperature decreases and fS₂ and fTe₂ increase from deeper to shallow levels.     

Cl/Br ratios and stable chlorine isotope analysis of magmatic–hydrothermal fluid inclusions from Butte,Montana and Bingham Canyon,Utah

A bulk geochemical study has been carried out on fluid inclusion leachates extracted from quartz veins from porphyry Cu deposits in Butte, Montana, USA and Bingham Canyon, Utah, USA. The leachates mostly represent low-salinity magmatic–hydrothermal fluid inclusions. Their halogen ratios (Br/Cl) of fluid inclusion leachates were determined by ion chromatography, and δ³⁷Cl values of the leachates were measured by continuous-flow isotope ratio mass spectrometry. Br/Cl ratios from early pre-Main stage and later Main stage veins at Butte range from 0.60 to 1.88 × 10⁻³ M. Ratios are similar in pre-Main stage veins with sericite bearing selvages and Main stage samples ranging from 0.81 to 1.08 × 10⁻³ and from 0.92 to 1.88 × 10⁻³ M, respectively, clustering below seawater (1.54 × 10⁻³ M) and overlapping mantle values (~1–2 × 10⁻³ M). Two samples associated with early pre-Main stage potassic alteration yield distinctly lower Br/Cl ratios of 0.60 and 0.64 × 10⁻³ M. Butte δ³⁷Cl values range from −0.8‰ to −2.3‰ with no significant difference between pre-Main stage and Main stage samples. Br/Cl ratios for quartz veins from Bingham Canyon range from 0.18 to 3.68 × 10⁻³ M. Br/Cl ratios from Bingham range above and below previously reported for porphyry copper deposits. In contrast to Butte, δ³⁷Cl values for Bingham are lower, ranging from −0.9‰ to −4.1‰. In the absence of any processes which can significantly fractionate chlorine isotopes at high temperatures, we suggest that the porphyry system at Bingham, and to a lesser extent at Butte, have inherited negative chlorine isotopic signatures from the subducting slab generated at low temperatures.