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.     

Modification of a Palaeoproterozoic porphyry-like system: Integration of structural,geochemical, petrographic,and fluid inclusion data from the Aitik Cu–Au–Ag deposit,northern Sweden

The Aitik Cu–Au–Ag deposit in the Gällivare area in northern Sweden is Sweden's largest sulphide mine with an annual production of 35 Mt of ore, and the biggest open pit operation in northern Europe. It is proposed in the present study that the Aitik deposit represents a Palaeoproterozoic, strongly metamorphosed porphyry copper deposit that was affected ca. 100 Ma later by a regional IOCG-type hydrothermal event. Consequently, the Aitik deposit might represent a mixed ore system where an early copper mineralisation of porphyry type has been overprinted by later regional IOCG mineralisation.Several attempts have previously been made to genetically classify the Aitik Cu–Au–Ag deposit as a distinct ore type. New geochemical, petrographic, structural, and fluid inclusion results combined with published data have provided the opportunity to present new ideas on the genesis and evolution of the Aitik Cu–Au–Ag deposit. The emplacement of a ca. 1.9 Ga quartz monzodiorite that host the ore at Aitik was related to subduction processes and volcanic arc formation, and synchronous with quartz vein stockwork formation and porphyry copper mineralisation. Highly saline aqueous (38 wt.% NaCl) fluid inclusions in the stockwork veins suggest entrapment at 300 °C and a pressure of nearly 3 kbar, a high pressure for a typical porphyry copper ore, but consistent with conditions at associated deep root zones of intrusion-related magmatic–hydrothermal systems. The highly saline fluid formed disseminated and vein-type ore of mainly chalcopyrite and pyrite within comagmatic volcaniclastic rocks, and caused potassic alteration (biotite, microcline) of the host rocks. The early porphyry copper mineralising event was followed, and largely overprinted, by CO₂ and aqueous medium- to high-salinity (16–57 wt.% salts) fluids related to a ca. 1.8 Ga tectonic and metamorphic event (peak conditions 500–600 °C and 4–5 kbar). Extensive deformation of rocks and redistribution of metals occurred. Magnetite enrichment locally found within late veins, and late amphibole–scapolite and K feldspar alterations within the deposit, are some of the features at Aitik implying that aqueous fluids responsible for IOCG-mineralisation (200–500 °C and ~ 1 kbar) and extensive Na–Ca alteration in the region during the 1.8 Ga tectonic event also affected the Aitik rocks, possibly leading to addition of copper ± gold.     

The origin and alteration of calcite cement in tight sandstones of the Jurassic Shishugou Group,Fukang Sag,Junggar Basin,NW China: implications for fluid–rock interactions and porosity evolution

The Shishugou Group, which consists of Middle Jurassic Toutunhe Formation and Upper Jurassic Qigu Formation, is currently an important hydrocarbon exploration target in the Fukang Sag of Junggar Basin, China. The Shishugou Group sandstones experienced a complex diagenetic history with deep burial (3600–5800 m) to develop low–ultralow porosity and permeability reservoir with some high-quality reservoirs found in the tight sandstones owing to the reservoir heterogeneity. This integrated petrographic and geochemical study aims to unravel the origin and alteration of calcite cement in the Shishugou Group sandstones and predict fluid–rock interaction and porosity evolution. The Shishugou Group sandstones (Q_43.8F_7.4R_48.8) have a dominant calcite cement with strong heterogeneity forming in two generations: poikilotopic, pore-filling masses that formed at an early diagenetic stage and isolated rhombs or partial grain replacements that formed at a late stage. The Shishugou Group, which are lacustrine sediments formed in low–medium salinity lake water in a semiarid–arid climatic environment, provided the alkaline diagenetic environment needed for precipitation of chlorite and early calcite cements in early diagenesis. The Ca²⁺ of the pore-filling calcite cements was sourced from weathering or dissolution of volcanic clasts in the sediment source or during transport in under oxidising conditions. The δ¹⁸O_V-PDB and δ¹³C_V-PDB values of calcite were significantly controlled by distance from the top unconformity and underlying coal-bearing stratum with carbon sourced from atmospheric CO₂, and organic matter. The early carbonate cement inhibited burial compaction producing intergranular pore spaces with enhanced reservoir properties by late dissolution under acidic conditions. Anhydrite cement reflects reaction of organic acid and hydrocarbon with the sandstones and is associated with fluid migration pathways. The fluid–rock interactions and porosity evolution of the tight deep sandstones produced secondary pores that filled with hydrocarbon charge that forms this deep high-quality reservoir.     

Geological,fluid inclusion and isotopic studies of the Yinshan Cu–Au–Pb–Zn–Ag deposit,South China: Implications for ore genesis and exploration

The Yinshan Cu–Au–Pb–Zn–Ag deposit is located in Dexing, South China. Ore bodies are primarily hosted in low-grade phyllite of the Neoproterozoic Shuangqiaoshan Group along EW- and NNW-striking fault zones. Pb–Zn–Ag mineralization is dictated by Jurassic rhyolitic quartz porphyries (ca. 172 Ma), whereas Cu–Au mineralization is associated with Jurassic dacite porphyries (ca. 170 Ma). The main ore minerals are pyrite, chalcopyrite, galena, sphalerite, tetrahedrite–tennatite, gold, silver, and silver sulphosalt, and the principal gangue minerals are quartz, sericite, calcite, and chlorite. Two-phase liquid-rich (type I), two-phase vapor-rich (type II), and halite-bearing (type III) fluid inclusions can be observed in the hydrothermal quartz-sulfides veins. Type I inclusions are widespread and have homogenization temperatures of 187–303 °C and salinities of 4.2–9.5 wt.% NaCl equivalent in the Pb–Zn–Ag mineralization, and homogenization temperatures of 196–362 °C and salinities of 3.5–9.9 wt.% NaCl equivalent in the Cu–Au mineralization. The pervasive occurrence of type I fluid inclusions with low-moderate temperatures and salinities implies that the mineralizing fluids formed in epithermal environments. The type II and coexisting type III inclusions, from deeper levels below the Cu–Au ore bodies, share similar homogenization temperatures of 317–448 °C and contrasting salinities of 0.2–4.2 and 30.9–36.8 wt.% NaCl equivalent, respectively, which indicates that boiling processes occurred. The sulfur isotopic compositions of sulfides (δ³⁴S = −1.7‰ to +3.2‰) suggest a homogeneous magmatic sulfur source. The lead isotopes of sulfides (²⁰⁶Pb/²⁰⁴Pb = 18.01–18.07; ²⁰⁷Pb/²⁰⁴Pb = 15.55–15.57; and ²⁰⁸Pb/²⁰⁴Pb = 38.03–38.12) are consistent with those of volcanic–subvolcanic rocks (²⁰⁶Pb/²⁰⁴Pb = 18.03–18.10; ²⁰⁷Pb/²⁰⁴Pb = 15.56–15.57; and ²⁰⁸Pb/²⁰⁴Pb = 38.02–38.21), indicating a magmatic origin for lead in the ore. The oxygen and hydrogen isotope compositions (δ¹⁸O = +7.8‰ to +10.5‰, δD = −66‰ to −42‰) of inclusion water in quartz imply that ore-forming fluids were mainly derived from magmatic sources. The local boiling process beneath the epithermal Cu–Au ore-forming system indicates the possibility that porphyry-style ore bodies may exist at even deeper zones.     

Stable isotope,petrological, and fluid inclusion studies of minor mineral deposits from the McArthur Basin: Implications for the genesis of some sediment‐hosted base metal mineralization from the Northern Territory

The geology, stable isotopes and fluid inclusions from mineralized and unmineralized Middle Proterozoic sequences of the McArthur Basin, Northern Territory, have been studied at Eastern Creek, Bulman Mines, Beetle Springs, and other localities in the McArthur Basin where disseminated sulphides in unmineralized black shales were available from drill core. At Eastern Creek, galena and minor chalcopyrite (δ³⁴S+3.6 to +11.2%o) occur in an evaporitic sedimentary sequence. Barite (δ³⁴S+18.4 to +24.7%o) also occurs, and saline brines are trapped along healed fractures in the barite. Pressure‐corrected trapping temperatures in the barite (95–138°C), and in vein dolomite (158–168°C) agree with temperature estimates from the degree of maturation of the sedimentary organic matter. The δ¹⁸O and δ¹³C_Co2 values of the mineralizing fluid were calculated to be +3.5 to +4.5%o and ‐2.7%o, respectively. Sedimentary dolomite has restricted δ¹³C and δ¹⁸O ranges, within the reported ranges for non‐mineralized Middle Proterozoic dolomite. An ore formation model developed for Eastern Creek, in which a basinal fluid at about 200°C carrying base metals and sulphide was released from underlying sediments during local fault movement, may be applicable to a number of other deposits. The mineralization deposited from these fluids occurs only below the pre‐Roper Group unconformity, implying that it may be older than the basal Roper Group. The δ³⁴S values of iron sulphides in fine grained black dolostones (not associated with mineral deposits) from the McArthur Basin were assessed in the light of the values found for sulphides in modern organic‐rich sedimentary environments. The data so obtained suggest that the considerable concentration of iron sulphide in the mineral deposits formed, at least in part, from heated basinal waters and that disseminated iron sulphides remote from mineralization also formed from a similar source.     

Petrography,mineral chemistry,fluid inclusion microthermometry and Re–Os geochronology of the Küre volcanogenic massive sulfide deposit (Central Pontides,Northern Turkey)

The Re–Os isotopic system is applied for the first time to the sulfide ores and the overlying black-shales at the Küre volcanogenic massive sulfide deposit of the Central Pontides, Northern Turkey. The ore samples collected include predominantly pyrite, accompanied by chalcopyrite, sphalerite and other species. Massive ore is almost free of gangues, whereas the stockwork ore includes quartz and calcite gangue. The composition of sphalerite is similar to ancient and modern massive sulfide mineralizations globally. Microthermometric studies from quartz from the stockwork ore has shown two populations of two-phase fluid inclusions with vapor/liquid ratios between 4 to 28%, low to intermediate T_h (161.5–317.0 °C) and low salinities (0.9–5 wt.% NaCl equiv.) which are mostly in good agreement with the ranges for volcanogenic massive sulfide mineralizations. These studies also suggest a H₂O–CaCl₂–KCl–MgCl₂ ore-forming fluid system in a shallower subsurface near the seafloor vents. The Re–Os dating of the LLHR sulfides yield a nominal depositional age of upper Toarcian for the massive sulfide mineralization. Two largely different model ages obtained are attributed to other pyrite crystallization events prior to and postdating the main sulfide deposition. Some lower homogenization temperatures (< 200 °C) from the quartz of the stockwork may also similarly be related to the post-VMS events. It is concluded that a submarine volcanic extrusion episode has continued until upper Toarcian in the Küre Basin, when it has entered a stagnation period that allowed the discharge of hydrothermally circulated sulfide-laden fluids from the seafloor vents. This age data promotes the palaeotectonic models interpreting the Küre Basin as a Permian–early Jurassic marginal back-arc basin of the Devonian-Triassic Karakaya Ocean. The Re–Os data from the overlying black-shale provide a glimpse to the initial Os isotope ratio of the water column at the time of the sedimentation (0.45–0.46 for 180 Ma). The lack of common Os from the sulfides does not let us to infer a source of Os and initial ¹⁸⁷Os/¹⁸⁸Os ratios from the black shale are not statistically robust to make a significant deduction. A further detailed study on the isotopic composition of the black shale strata may help us to make an apporach to the Os source(s) in the deposition environment of the Küre VMS deposit.     

A fluid inclusion and isotopic study of an intrusion-related gold deposit (IRGD) setting in the 380 Ma South Mountain Batholith,Nova Scotia,Canada: evidence for multiple fluid reservoirs

A set of sheeted quartz veins cutting 380 Ma monzogranite at Sandwich Point, Nova Scotia, Canada, provide an opportunity to address issues regarding fluid reservoirs and genesis of intrusion-related gold deposits. The quartz veins, locally with arsenopyrite (≤5%) and elevated Au–(Bi–Sb–Cu–Zn), occur within the reduced South Mountain Batholith, which also has other zones of anomalous gold enrichment. The host granite intruded (P = 3.5 kbars) Lower Paleozoic metaturbiditic rocks of the Meguma Supergroup, well known for orogenic vein gold mineralization. Relevant field observations include the following: (1) the granite contains pegmatite segregations and is cut by aplitic dykes and zones (≤1–2 m) of spaced fracture cleavage; (2) sheeted veins containing coarse, comb-textured quartz extend into a pegmatite zone; (3) arsenopyrite-bearing greisens dominated by F-rich muscovite occur adjacent the quartz veins; and (4) vein and greisen formation is consistent with Riedel shear geometry. Although these features suggest a magmatic origin for the vein-forming fluids, geochemical studies indicate a more complex origin. Vein quartz contains two types of aqueous fluid inclusion assemblages (FIA). Type 1 is a low-salinity (≤3 wt.% equivalent NaCl) with minor CO₂ (≤2 mol%) and has T _h = 280–340°C. In contrast, type 2 is a high-salinity (20–25 wt.% equivalent NaCl), Ca-rich fluid with T _h = 160–200°C. Pressure-corrected fluid inclusion data reflect expulsion of a magmatic fluid near the granite solidus (650°C) that cooled and mixed with a lower temperature (400°C), wall rock equilibrated, Ca-rich fluid. Evidence for fluid unmixing, an important process in some intrusion-related gold deposit settings, is lacking. Stable isotopic (O, D, S) analyses for quartz, muscovite and arsenopyrite samples from vein and greisens indicate the following: (1) δ¹⁸O_qtz = +11.7‰ to 17.8‰ and δ¹⁸O_musc = +10.7‰ to +11.2‰; (2) δD_musc = −44‰ to−54‰; and (3) δ³⁴S_aspy = +7.8‰ to +10.3‰. These data are interpreted, in conjunction with fluid inclusion data, to reflect contamination of a magmatic-derived fluid (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  ≤ +10‰) by an external fluid (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  ≥ +15‰), the latter having equilibrated with the surrounding metasedimentary rocks. The δ³⁴S data are inconsistent with a direct igneous source based on other studies for the host intrusion (d¹⁸O_H2O {\delta^{{{18}}}}{{\hbox{O}}_{{{{\rm{H}}_{{2}}}{\rm{O}}}}}  = +5‰) and are, instead, consistent with an external reservoir for sulphur based on δ³⁴S_H2S data for the surrounding metasedimentary rocks. Divergent fluid reservoirs are also supported by analyses of Pb isotopes for pegmatitic K-feldspar and vein arsenopyrite. Collectively the data indicate that the vein- and greisen-forming fluids had a complex origin and reflect both magmatic and non-magmatic reservoirs. Thus, although the geological setting suggests a magmatic origin, the geochemical data indicate involvement of multiple reservoirs. These results suggest multiple reservoirs for this intrusion-related gold deposit setting and caution against interpreting the genesis of intrusion-related gold deposit mineralization in somewhat analogous settings based on a limited geochemical data set.     

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

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

Geochemical,fluid inclusion and isotopic (O,H and S) constraints on the origin of Pb–Zn ± Au vein-type mineralizations in the Eastern Pontides Orogenic Belt (NE Turkey)

The mineralization area (Altınpınar, Torul–Gümüşhane) is situated in the Southern Zone of the Eastern Pontides Orogenic Belt (EPOB), which is one of the important metallogenic provinces in the Alpine–Himalayan belt and is intruded by the late Carboniferous granitic rocks (Gümüşhane Granitoid), an early to middle Jurassic volcano-sedimentary unit consisting mainly of basaltic–andesitic volcanic and pyroclastic rocks (Şenköy Formation) and Eocene basaltic–andesitic volcanic rocks (Alibaba Formation). The studied Pb–Zn ± Au mineralizations are related to silica veins ranging from a few millimeters to a maximum of 40 cm in thickness and are localized within fracture zones developed along the contact between the Gümüşhane Granitoid and Şenköy Formation. Silicic, sulfidic, hematitic, argillic, intense chloritic and carbonate alteration are the most common types from the fault lines toward the outer zones. Cavity filling and banded structures are widely observed. The mineral paragenesis comprises galena, sphalerite, pyrite, chalcopyrite, tennantite and quartz. Mineral chemistry studies indicate that ion exchange occurs between Zn and Fe in sphalerites, and the Zn/Cd ratio of sphalerites varies between 50.65 and 144.64. The homogenization temperatures measured from fluid inclusions vary between 170 °C and 380 °C, especially between 250 °C and 300 °C, and the wt.% NaCl eqv. salinity of ore-forming fluids is between 2.4 and 7.3 (4.7 on average), supporting an epithermal system in their origin. The values of sulfur isotopes, which are obtained from pyrite and galena minerals, range between − 8.3‰ and − 2.3‰, indicating that sulfur, which enables mineral formation, originates from magmatic genesis. The average formation temperature of the ore is 317 °C as determined with a sulfur isotope geothermometer. The values of oxygen and hydrogen isotopes vary between 8.5‰ and 10.2‰ and − 91‰ and −73‰, respectively. With regard to the compositions of oxygen and hydrogen isotopes, fluids comprising the mineralization are formed by the mixture of magmatic water and meteoric water. This situation is supported by the fact that the increase in the homogenization temperature indicates dilution with surface water but depends on the increase in the salinity of fluid inclusions. Considering all the data, it is clear that the studied mineralization is an epithermal vein-type mineralization that is related to granitic magmas.     

Further evidence for a Jurassic mineralizing event in central Europe: K–Ar dating of hydrothermal alteration and fluid inclusion systematics in wall rocks of the Käfersteige fluorite vein deposit in the northern Black Forest, Germany

The hydrothermal fluorite vein deposit of `Käfersteige' ranks among the biggest in central Europe. It is located along the suture zone that separates the Moldanubian and Saxothuringian units in the northern Black Forest, and is hosted in Bunter sandstone and underlying granitic basement. K–Ar ages of authigenic illite from the wall rocks give a Jurassic formation age of around 145?Ma for the deposit. Age data scatter down to 80?Ma in illite from the clay gouge and indicate a younger Cretaceous-Tertiary hydrothermal overprint. The pyrophyllite component in authigenic illite from wall rocks and the re-equilibration of illite suggest a formation temperature around 200?°C. Secondary fluid inclusions in quartz from the wall rocks define a syn-mineralization fluid episode involving Ca–Mg–K–Na–Cl-rich brines (about 27 wt% NaCl_eq) with a T _h of about 125?°C, and a post-mineralization Na–Cl-rich fluid overprint with a T _h of about 100?°C. Both generations of fluid inclusions relate to the final event of each cycle, while authigenic illite composition and re-equilibration of illite in the clay gouge may document initial temperatures of formation. The Upper Jurassic fluid system can be traced all over western Europe. It is probably an expression of continent-wide rifting and concomitant regional fluid circulation in connection with major tectonic disturbances, magmatism and abnormal heat flow during the opening of the North Atlantic ocean. The younger barren fluid overprint could be related to the onset of the Alpine orogeny.