The origin of the Dapingzhang volcanogenic Cu–Pb–Zn ore deposit,Yunnan province,SW China: Constraints from host rock geochemistry and ore Os–Pb–S–C–O–H isotopes

The Dapingzhang volcanogenic Cu–Pb–Zn sulfide deposit is located in the Lancangjiang tectonic zone within the Sanjiang region, Yunnan province of southwestern China. The deposit occurs within a felsic volcanic dome belonging to a mid-Silurian volcanic belt stretching for more than 100 km from Dapingzhang to Sandashan. The mineralized volcanic rocks are predominantly keratophyre and quartz keratophyre with subordinate spilite. The Dapingzhang deposit is characterized by well-developed vertical zonation with stockwork ores in the bottom, disseminated sulfide ores in the middle, and massive sulfide ores in the top, overlain by a thin layer of chemical sedimentary exhalative rocks (chert and barite). The Re–Os age of the pyrites from the deposit is 417 ± 23 Ma, indistinguishable from the age of the associated felsic volcanic rocks. The associated felsic volcanic rocks are characterized by negative Nb–Ta anomalies and positive ε_Nd(t) values (+ 4.4–+6.5), similar to the coeval calc-alkaline volcanic rocks in the region. This observation supports the interpretation that the felsic volcanic rocks associated with the Dapingzhang deposit are the derivatives of arc basaltic magma by extensive fractional crystallization. The δ³⁴S values of the sulfides from the deposit vary from − 1.24 to + 4.32‰, indicating a predominantly magmatic source for the sulfur. The sulfides are also characterized by homogeneous and relatively low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.310–18.656, ²⁰⁷Pb/²⁰⁴Pb = 15.489–15.643 and ²⁰⁸Pb/²⁰⁴Pb = 37.811–38.662), similar to the Pb isotopic compositions of the associated volcanic rocks. The Pb isotopic data indicate that mantle-derived Pb is more prevalent than crust-derived Pb in the deposit. The S–Pb isotopic data indicate that the important ore-forming materials were mainly derived from the associated volcanic rocks. The δ¹³C_PDB and δ¹⁸O_SMOW values of the associated hydrothermal calcite crystals vary from − 2.3‰ to + 0.27‰ and from + 14.6 to + 24.4‰, respectively. These values are between the mantle and marine carbonate values. The narrow range of the δ¹³C_PDB values for the calcite indicates that carbon-bearing species in the hydrothermal fluids were primarily derived from marine carbonates. The δ¹⁸O values for the hydrothermal fluids, calculated from the measured values for quartz, are between − 2.1‰ and + 3.5‰. The corresponding δD values for the fluids range from − 59‰ to − 84‰. The O–H isotopic data indicate mixing between magmatic fluids and seawater in the ore-forming hydrothermal system. Similar to a typical volcanogenic massive sulfide (VMS) deposit, the ore-forming fluids contained both magmatic fluids and heated seawater; the ore metals and regents were derived from the underlying magma as well as felsic country rocks.     

Geology,geochemistry and genesis of the Qianfanling quartz-vein Mo deposit in Songxian County,Western Henan Province,China

The Qianfanling Mo deposit, located in Songxian County, western Henan province, China, is one of the newly discovered quartz-vein type Mo deposits in the East Qinling–Dabie orogenic belt. The deposit consists of molybdenite in quartz veins and disseminated molybdenite in the wall rocks. The alteration types of the wall rocks include silicification, K-feldspar alteration, pyritization, carbonatization, sericitization, epidotization and chloritization. On the basis of field evidence and petrographic analysis, three stages of hydrothermal mineralization could be distinguished: (1) pyrite–barite–quartz stage; (2) molybdenite–quartz stage; (3) quartz–calcite stage.Two types of fluid inclusions, including CO₂-bearing fluid inclusions and water-rich fluid inclusions, have been recognized in quartz. Homogenization temperatures of fluid inclusions vary from 133 °C to 397 °C. Salinity ranges from 1.57 to 31.61 wt.% NaCl eq. There are a large number of daughter mineral-CO₂-bearing inclusions, which is the result of fluid immiscibility. The ore-forming fluids are medium–high temperature, low to moderate salinity H₂O–NaCl–CO₂ system. The δ³⁴S values of pyrite, molybdenite, and barite range from − 9.3‰ to − 7.3‰, − 9.7‰ to − 7.3‰ and 5.9‰ to 6.8‰, respectively. The δ¹⁸O values of quartz range from 9.8‰ to 11.1‰, with corresponding δ¹⁸O_fluid values of 1.3‰ to 4.3‰, and δ¹⁸D values of fluid inclusions of between − 81‰ and − 64‰. The δ¹³C_V-PDB values of fluid inclusions in quartz and calcite have ranges of − 6.7‰ to − 2.9‰ and − 5.7‰ to − 1.8‰, respectively. Sulfur, hydrogen, oxygen and carbon isotope compositions show that the sulfur and ore-forming fluids derived from a deep-seated igneous source. During the peak collisional period between the North China Craton and the Yangtze Craton, the ore-forming fluids that derived from a deep igneous source extracted base and precious metals and flowed upwards through the channels that formed during tectonism. Fluid immiscibility and volatile exsolution led to the crystallization of molybdenite and other minerals, and the formation of economic orebodies in the Qianfanling Mo deposit.     

Late Cretaceous magmatism and related metallogeny in the Tengchong area: Evidence from geochronological,isotopic and geochemical data from the Xiaolonghe Sn deposit,western Yunnan,China

Xiaolonghe is a poorly studied greisen-type tin deposit that is hosted by biotite granite in the western Yunnan tin belt. The mineralisation-related metaluminous and weak peraluminous granite is characterised by high Si, Al and K and low Mg, Fe and Ca, with an average A/CNK of 1.02. The granite is enriched in LILEs (K and Rb), LREEs and HFSEs (Zr, Hf, Th, U and Ce) and depleted in Ba, Nb, Sr, P, and Ti, with zircon εHf(t) = − 10.8 to − 7.5 (T_DM2 = 1.61–1.82 Ga). These characteristics indicate that the magma was generated by the partial melting of a thickened ancient crust. LA-ICP-MS U–Pb dating of igneous zircon and hydrothermal cassiterite yield ages of 71.4 ± 0.4 Ma and 71.6 ± 4.8 Ma, respectively. The igneous biotite and hydrothermal muscovite samples show Ar–Ar plateau ages of 72.3 ± 0.4 Ma and 70.6 ± 0.2 Ma, respectively. The close temporal relationship between the igneous emplacement and hydrothermal activity suggests that the tin mineralisation was closely linked to the igneous emplacement. The δ¹⁸O and δD values for the deposit range from + 3.11‰ to − 4.5‰ and from − 127.3‰ to − 94.7‰, respectively. The hydrothermal calcite C and O isotopic data show a wide range of δ¹³C_PDB values from − 5.7‰ to − 4.4‰, and the δ¹⁸O_SMOW values range from + 1.4‰ to + 11.2‰. The δ³⁴S_V-CDT data range from + 4.8‰ to + 8.9‰ for pyrite, and the ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb ratios range from 18.708 to 18.760, from 15.728 to 15.754 and from 39.237 to 39.341, respectively. The stable isotopic (C–H–O–S–Pb) compositions are all similar to those of magmatic and mantle-derived fluids, which indicate that the ore-forming fluids and materials were mainly derived from magmatic sources that were accompanied by meteoric water. The tin mineralisation in the Xiaolonghe district was closely associated with the Late Cretaceous crustal-melting S-type granites that formed during the subduction of the Neo-Tethys oceanic lithosphere. Combined with the tin deposits in the Southeast Asian tin belt, Tengchong block and Central Lhasa, we interpreted that a giant intermittent tin mineralisation belt should be present along the Asian Neo-Tethys margin.     

SHRIMP zircon U–Pb geochronology,geochemistry and H–O–Si–S–Pb isotope systematics of the Kanggur gold deposit in Eastern Tianshan,NW China: Implication for ore genesis

The Kanggur gold deposit is located in the southern margin of the Central Asia Orogenic Belt and in the western segment of the Kanggur–Huangshan ductile shear belt in Eastern Tianshan, northwestern China. The orebodies of this deposit are hosted in the Lower Carboniferous volcanic rocks of the Aqishan Formation and mainly consist of andesite, dacite and pyroclastic rocks. The SHRIMP zircon U–Pb age data of the andesite indicate that the volcanism in the Kanggur area might have occurred at ca. 339 Ma in the Early Carboniferous, and that the mineralization age of the Kanggur gold deposit was later than the age of volcanic rocks in the area. Geochemically, the andesite rocks of the Aqishan Formation belong to low-tholeiite and calc-alkaline series and display relative depletions in high field strength elements (HFSEs; i.e. Nb, Ta and Ti). The δ¹⁸O_w and δD_w values vary from − 9.1‰ to + 3.8‰ and − 66.0‰ to − 33.9‰, respectively, indicating that the ore-forming fluids were mixtures of metamorphic and meteoric waters. The δ³⁰Si values of 13 quartz samples range from − 0.3‰ to + 0.1‰ with an average of − 0.15‰, and the δ³⁴S values of 18 sulphide samples range from − 0.9‰ to + 2.2‰ with an average of + 0.54‰. The ²⁰⁶Pb/²⁰⁴Pb, ²⁰⁷Pb/²⁰⁴Pb and ²⁰⁸Pb/²⁰⁴Pb values of 10 sulphide samples range from 18.166 to 18.880, 15.553 to 15.635 and 38.050 to 38.813, respectively, showing similarities to orogenic Pb; these values are consistent with those of the andesite from the Kanggur area, suggesting a common lead source. All of the silicon, sulphur and lead isotopic systems indicate that the ore-forming fluids and materials were mainly derived from the Aqishan Formation, and that the host volcanic rocks of the Aqishan Formation probably played a significant role in the Kanggur gold mineralization. Integrating the data obtained from studies on geology, geochronology, petro-geochemistry and H–O–Si–S–Pb isotope systematics, we suggest that the Kanggur gold deposit is an orogenic-type deposit formed in Eastern Tianshan orogenic belt during the Permian post-collisional tectonism.     

Boron,sulphur and copper isotope systematics in the orogenic gold deposits of the Archaean Hattu schist belt,eastern Finland

The Hattu schist belt is located in the western part of the Archaean Karelian domain of the Fennoscandian Shield. The orogenic gold deposits with Au–Bi–Te geochemical signatures are hosted by NE–SW, N–S and NW–SE oriented shear zones that deform 2.76–2.73 Ga volcanic and sedimentary sequences, as well as 2.75–2.72 Ga tonalite–granodiorite intrusions and diverse felsic porphyry dykes. Mo–W mineralization is also present in some tonalite intrusions, both separate from, and associated with Au mineralization. Somewhat younger, unmineralized leucogranite intrusions (2.70 Ga) also intrude the belt. Lower amphibolite facies peak metamorphism at 3–5 kbar pressures and at 500–600 °C temperatures affected the belt at around 2.70 Ga and post-date hydrothermal alteration and ore formation. In this study, we investigated the potential influence of magmatic-hydrothermal processes on the formation of orogenic gold deposits on the basis of multiple stable isotope (B, S, Cu) studies of tourmaline and sulphide minerals by application of in situ SIMS and LA ICP MS analytical techniques.Crystal chemistry of tourmaline from a Mo–W mineralization hosted by a tonalite intrusion in the Hattu schist belt is characterized by Fe^3 +–Al^3 +-substitution indicating relatively oxidizing conditions of hydrothermal processes. The range of δ¹¹B data for this kind of tourmaline is from − 17.2‰ to − 12.2‰. The hydrothermal tourmaline from felsic porphyry dyke swith gold mineralization has similar crystal chemistry (e.g. dravite–povondraite compositional trend with Fe^3 +–Al^3 + substitution) and δ¹¹B values between − 19.0‰ and − 9.6‰. The uvite–foitite compositional trend and δ¹¹B ‰ values between − 24.1% and − 13.6% characterize metasomatic–hydrothermal tourmaline from the metasediment-hosted gold deposits. Composition of hydrothermal vein-filling and disseminated tourmaline from the gold-bearing shear zones in metavolcanic rocks is transitional between the felsic intrusion and metasedimentary rock hosted hydrothermal tourmaline but the range of average boron isotope data is essentially identical with that of the metasediment-hosted tourmaline. Rock-forming (magmatic) tourmaline from leucogranite has δ¹¹B values between − 14.5‰ and − 10.8‰ and the major element composition is similar to that of the metasediment-hosted tourmaline.The range of δ³⁴S_VCDT values measured in pyrite, chalcopyrite and pyrrhotite is from − 9.1 to + 8.5‰, which falls within the typical range of sulphur isotope data for Archaean orogenic gold deposits. In the Hattu schist belt, positive δ³⁴S_VCDT values characterize metasediment-hosted gold ores with sulphide parageneses dominated by pyrrhotite and arsenopyrite. The δ³⁴S_VCDT values are both positive and negative in ore mineral parageneses within felsic intrusive rocks in which variable amounts of pyrrhotite are associated with pyrite. Purely negative values were only recorded from the pyrite-dominated gold mineralization within metavolcanic units. Therefore the shift of δ³⁴S_VCDT values to the negative values reflects precipitation of sulphide minerals from relatively oxidizing fluids. The range of measured δ⁶⁵Cu_NBS978 values from chalcopyrite is from − 1.11 to 1.19‰. Positive values are common for mineralization in felsic intrusive rocks and negative values are more typical for deposits confined to metasedimentary rocks. Positive and negative δ⁶⁵Cu_NBS978 values occur in the ores hosted by metavolcanic rocks. There is no correlation between sulphur and copper isotope data obtained in the same chalcopyrite grains.Evaluation of sulphur and boron isotope data together and comparisons with other Archaean orogenic gold provinces supports the hypothesis that the metasedimentary rocks were the major sources of sulphur and boron in the orogenic gold deposits in the Hattu schist belt. Variations in major element and boron isotope compositions in tourmaline, as well as in the δ³⁴S_VCDT values in sulphide minerals are attributed to localized involvement of magmatic fluids in the hydrothermal processes. The results of copper isotope studies indicate that local sources of copper in orogenic gold deposits may potentially be recognized if the original, distinct signatures of the sources have not been homogenized by widespread interaction of fluids with a large variety of rocks and provided that local chemical variations have been too small to trigger changes in the oxidation state of copper during hydrothermal processes.     

Geologic and geochemical insights into the formation of the Taiyangshan porphyry copper–molybdenum deposit,Western Qinling Orogenic Belt,China

Taiyangshan is a poorly studied copper–molybdenum deposit located in the Triassic Western Qinling collisional belt of northwest China. The intrusions exposed in the vicinity of the Taiyangshan deposit record episodic magmatism over 20–30 million years. Pre-mineralization quartz diorite porphyries, which host some of the deposit, were emplaced at 226.6 ± 6.2 Ma. Syn-collisional monzonite and quartz monzonite porphyries, which also host mineralization, were emplaced at 218.0 ± 6.1 Ma and 215.0 ± 5.8 Ma, respectively. Mineralization occurred during the transition from a syn-collisional to a post-collisional setting at ca. 208 Ma. A barren post-mineralization granite porphyry marked the end of post-collisional magmatism at 200.7 ± 5.1 Ma. The ore-bearing monzonite and quartz monzonite porphyries have a ε_Hf(t) range from − 2.0 to + 12.5, which is much more variable than that of the slightly older quartz diorite porphyries, with T_DM2 of 1.15–1.23 Ga corresponding to the positive ε_Hf(t) values and T_DM1 of 0.62–0.90 Ga corresponding to the negative ε_Hf(t) values. Molybdenite in the Taiyangshan deposit with 27.70 to 38.43 ppm Re suggests metal sourced from a mantle–crust mixture or from mafic and ultramafic rocks in the lower crust. The δ³⁴S values obtained for pyrite, chalcopyrite, and molybdenite from the deposit range from + 1.3‰ to + 4.0‰, + 0.2‰ to + 1.1‰, and + 5.3‰ to + 5.9‰, respectively, suggesting a magmatic source for the sulfur. Calculated δ¹⁸O_fluid values for magmatic K-feldspar from porphyries (+ 13.3‰), hydrothermal K-feldspar from stockwork veins related to potassic alteration (+ 11.6‰), and hydrothermal sericite from quartz–pyrite veins (+ 8.6 to + 10.6‰) indicate the Taiyangshan deposit formed dominantly from magmatic water. Hydrogen isotope values for hydrothermal sericite ranging from − 85 to − 50‰ may indicate that magma degassing progressively depleted residual liquid in deuterium during the life of the magmatic–hydrothermal system. Alternatively, δD variability may have been caused by a minor amount of mixing with meteoric waters. We propose that the ore-related magma was derived from partial melting of the ancient Mesoproterozoic to Neoproterozoic middle to lower continental crust. This crust was likely metasomatized during earlier subduction, and the crustal magmas may have been contaminated with lithospheric mantle derived magma triggered by MASH (e.g., melting, assimilation, storage, and homogenization) processes during collisional orogeny. In addition, a significant proportion of the metals and sulfur supplied from mafic magma were simultaneously incorporated into the resultant hybrid magmas.     

Geochemical comparison between gas in fluid inclusions and gas produced from the Upper Triassic Xujiahe Formation,Sichuan Basin,SW China

Natural gas in the Xujiahe Formation of the Sichuan Basin is dominated by hydrocarbon (HC) gas, with 78–79% methane and 2–19% C₂₊ HC. Its dryness coefficient (C₁/C_1–5) is mostly < 0.95. The gas in fluid inclusions, which has low contents of CH₄ and heavy hydrocarbons (C₂₊) and higher contents of non-hydrocarbons (e.g. CO₂), is a typical wet gas produced by thermal degradation of kerogen. Gas produced from the Upper Triassic Xujiahe Formation (here denoted field gas) has light carbon isotope values for methane (δ¹³C₁: −45‰ to −36‰) and heavier values for ethane (δ¹³C₂: −30‰ to −25‰). The case is similar for gas in fluid inclusions, but δ¹³C₁ = −36‰ to −45‰ and δ¹³C₂ = −24.8‰ to −28.1‰, suggesting that the gas experienced weak isotopic fractionation due to migration and water washing. The field gas has δ¹³C_CO2 values of −15.6‰ to −5.6‰, while the gas in fluid inclusions has δ¹³C_CO2 values of −16.6‰ to −9‰, indicating its organic origin. Geochemical comparison shows that CO₂ captured in fluid inclusions mainly originated from source rock organic matter, with little contribution from abiogenic CO₂. Fluid inclusions originate in a relatively closed system without fluid exchange with the outside following the gas capture process, so that there is no isotopic fractionation. They thus present the original state of gas generated from the source rocks. These research results can provide a theoretical basis for gas generation, evolution, migration and accumulation in the basin.     

Hydrothermal He and CO2 at Wudalianchi intra-plate volcano,NE China

Chemical and isotopic compositions have been measured for CO₂-rich bubbling gases discharging from cold springs in Wudalianchi intra-plate volcanic area, NE China. Observed ³He/⁴He ratios (2–3 R_A) and δ¹³C values of CO₂ (−5‰ to −3‰) indicate the occurrence of a mantle component released and transferred to the surface by the Cenozoic extension-related magmatic activities. The CO₂/³He ratios are in wide range of (0.4–97 × 10⁹). Based on the apparent mixing trend in a ³He/⁴He and δ¹³C of CO₂ diagram from all published data, the extracted magmatic end-member in the Wudalianchi Volcano has ³He/⁴He, δ¹³C and CO₂/³He value of ∼3.2 R_A, ∼−4.6‰ and ∼6 × 10¹⁰, respectively. These values suggest that the volatiles originate from the sub-continental lithospheric mantle (SCLM) in NE China and represent ancient fluids captured by prior metasomatic events, as revealed by geothermal He and CO₂ from the adjacent Changbaishan volcanic area.     

Characterisation and isotopic evolution of saline waters of the Outokumpu Deep Drill Hole,Finland – Implications for water origin and deep terrestrial biosphere

The isotopic composition of water and dissolved Sr as well as other geochemical parameters at the 2516 m deep Outokumpu Deep Drill Hole, Finland were determined. The drill hole is hosted by Palaeoproterozoic turbiditic metasediments, ophiolite-derived altered ultramafic rocks and pegmatitic granitoids. Sodium–Ca–Cl and Ca–Na–Cl-rich waters (total dissolved solids up to ca. 70 g L⁻¹) containing significant amounts of gas, mainly CH₄ (up to 32 mmol L⁻¹), N₂ (up to 10 mmol L⁻¹), H₂ (up to 3.1 mmol L⁻¹) and He (up to 1.1 mmol L⁻¹) discharge from fracture zones into the drill hole. This water is distinct from the shallow fresh groundwater of the area, and has an isotopic composition typical of shield brines that have been modified during long-term water–rock interaction. Based on water stable isotopes and geochemistry, the drill hole water profile can be divided into five water types, each discharging from separate fracture systems and affected by the surrounding rocks. The δ²H varies from −90‰ to −56‰ (VSMOW) and δ¹⁸O from −13.5‰ to −10.4‰ (VSMOW), plotting clearly above the Global and Local Meteoric Water Lines on a δ²H vs. δ¹⁸O diagram. The ⁸⁷Sr/⁸⁶Sr ratios range between 0.72423 and 0.73668. Simple two-component mixing between ²H and ¹⁸O rich end-member brine and meteoric water cannot explain the water stable isotopic composition and trends observed. Instead, hydration of silicates by ancient groundwaters recharged under different climatic conditions, warmer than at present, is the most likely mechanism to have caused the variation of the δ²H and δ¹⁸O values. Water types correlate with changes in microbial communities implying that different ecosystems occur at different depths. The different water types and microbial populations have remained isolated from each other and from the surface for long periods of time, probably tens of millions of years.     

Geology and genesis of the Xiaguan Ag–Pb–Zn orefield in Qinling orogen,Henan province,China: Fluid inclusion and isotope constraints

The Xiaguan Ag–Pb–Zn orefield (Neixiang County, Henan Province), hosting the Yindonggou, Zhouzhuang, Yinhulugou and Laozhuang fault-controlled lode deposits, is situated in the Erlangping Terrane, eastern Qinling Orogen. The quartz-sulfide vein mineralization is dominated by main alteration styles of silicic-, sericite-, carbonate-, chlorite- and sulfide alteration. Major Ag-bearing minerals are freibergite, argentite and native Ag. The deposits were formed by a CO₂-rich, mesothermal (ca. 250–320 °C), low-density and low salinity (< 11 wt.% NaCl equiv.), Na⁺–Cl⁻-type fluid system. Trapping pressures of the carbonic-type fluid inclusions (FIs) decreased from ca. 280–320 MPa in the early mineralization stage to ca. 90–92 MPa in the late mineralization stage, indicating that the ore-forming depths had become progressively shallower. This further suggests that the metallogenesis may have occurred in a tectonic transition from compression to extension. Geological- and ore fluid characteristics suggest that the Xiaguan Ag–Pb–Zn orefield belongs to orogenic-type systems.The δ¹⁸O_H2O values change from the Early (E)-stage (7.8–10.8 ‰), through Middle (M)-stage (6.0–9.4 ‰) to Late (L)-stage (− 1.5–3.3 ‰), with δD values changing from E-stage − 95 to − 46 ‰, through M-stage − 82 to − 70 ‰ to L-stage − 95 to − 82 ‰. δ¹³C_CO2 values of the ore fluids in the E- and M-stage quartz vary between 0.1 ‰ and 0.9 ‰ (average: 0.3 ‰); δ¹³C_CO2 values of L-stage FIs are − 0.2–0.1 ‰ in quartz and − 6.8 ‰ to − 3.5 ‰ in calcite. The H–O–C isotopic data indicate that the initial ore fluids were sourced from the underthrusted Qinling Group marine carbonates, and were then interacted with the ore-hosting Erlangping Group metasedimentary rocks. Inflow of circulated meteoric water may have dominated the L-stage fluid evolution.Sulfur (δ³⁴S = 1.9–8.1 ‰) and lead isotopic compositions (²⁰⁶Pb/²⁰⁴Pb = 18.202–18.446, ²⁰⁷Pb/²⁰⁴Pb = 15.567–15.773 and ²⁰⁸Pb/²⁰⁴Pb = 38.491–39.089) of sulfides suggest that the ore-forming materials were mainly sourced from the ore-hosting metasedimentary strata. The stepped heating sericite ⁴⁰Ar/³⁹Ar detection suggests that the mineralization occurred in the Middle Jurassic to Early Cretaceous (ca. 187 − 124 Ma). Considering the regional tectonic evolution of the Erlangping Terrane, we propose that the Xiaguan Ag–Pb–Zn orefield was formed in a continent–continent collisional tectonic regime, in accordance with the tectonic model for continental collision, metallogeny and fluid flow (CMF).     

Hydrogeochemistry of thermal and mineralized waters in the Diyadin (Ağri) area,Eastern Turkey

The Diyadin Geothermal area, located in the eastern part of Anatolia (Turkey) where there has been recent volcanic activity, is favorable for the formation of geothermal systems. Indeed, the Diyadin geothermal system is located in an active geodynamic zone, where strike-slip faults and tensional cracks have developed due to N–S regional compression. The area is characterized by closely spaced thermal and mineralized springs, with temperatures in the range 30–64 °C, and flowrates 0.5–10 L/s. Thermal spring waters are mainly of Ca(Na)-HCO₃ and Ca(Mg)-SO₄ types, with high salinity, while cold groundwater is mostly of Ca(Na, Mg)-HCO₃ type, with lower salinity. High contents of some minor elements in thermal waters, such as F, B, Li, Rb, Sr and Cs probably derive from enhanced water–rock interaction.Thermal water samples collected from Diyadin are far from chemical equilibrium as the waters flow upward from reservoirs towards spring vents and possibly mix with cooler waters. The temperatures of the deep geothermal reservoirs are estimated to be between 92 and 156 °C in Diyadin field, based on quartz geothermometry, while slightly lower estimates are obtained using chalcedony geothermometers. The isotopic composition of thermal water (δ¹⁸O, δ²H, δ³H) indicates their deep-circulating meteoric origin. The waters are likely to have originated from the percolation of rainwater along fractures and faults to the deep hot reservoir. Subsequent heating by conduction due to the presence of an intrusive cupola associated with the Tendurek volcano, is followed by the ascent of deep waters to the surface along faults and fractures that act as hydrothermal conduits.Modeling of the geothermal fluids indicates that the fluid is oversaturated with calcite, aragonite and dolomite, which matches travertine precipitation in the discharge area. Likewise, the fluid is oversaturated with respect to quartz, and chalcedony indicating the possibility of siliceous precipitation near the discharge areas. A conceptual hydro-geochemical model of the Diyadin thermal waters based on the isotope and chemical analytical results, has been constructed.     

Determination of germanium isotopic compositions of sulfides by hydride generation MC-ICP-MS and its application to the Pb–Zn deposits in SW China

Determining Ge isotopic compositions of sulfides is important to understand the ore-forming processes. Single step anion-exchange chromatography was previously used to recover Ge from silicates and lignites. We apply this procedure to recover Ge from sulfides before determining Ge isotopic compositions by hydride generation (HG)-MC-ICP-MS. Germanium is quantitatively recovered by the proposed sample preparation method. There are no obvious isotope biases for Ge-bearing solutions containing significant amounts of Cu, Sn, and W. However, δ⁷⁴Ge values show obvious shifts if the solutions contain high Zn, Pb, and Sb, which is possibly attributed to suppression of germane formation that fractionates Ge isotopes. The long-term reproducibility for Ge standard solution is about ± 0.18‰ for δ⁷⁴Ge. Spex and Merck standard solutions yield mean δ⁷⁴Ge values of − 0.70 ± 0.19‰ and − 0.36 ± 0.08‰, respectively. The calculated δ⁷⁴Ge value (− 5.13‰) of sphalerite standard based on doping experiments is indistinguishable from those of sphalerite without doping (− 5.05‰ and − 5.01‰). Sulfides from the Jinding, Shanshulin, and Tianqiao Pb–Zn deposits in SW China have δ⁷⁴Ge values of − 4.94‰ to + 2.07‰. The paragenetic sequence of sulfides from the Shanshulin and Tianqiao Pb–Zn deposits is pyrite, sphalerite and galena from early to late. Sulfides from the same ore show a trend of δ⁷⁴Ge_pyrite < δ⁷⁴Ge_sphalerite < δ⁷⁴Gegalena, which may be controlled by the kinetic or Rayleigh fractionation.     

Boron isotope ratios of surface waters in Guadeloupe,Lesser Antilles

Large variations are reported in the B concentrations and isotopic ratios of river and thermal spring waters in Guadeloupe, Lesser Antilles. Rivers have δ¹¹B values around 40‰ and B concentrations lower than 30 μg/L, while thermal springs have δ¹¹B of 8–15‰ and B concentrations of 250–1000 μg/L. River samples strongly impacted by hydrothermal inputs have intermediate δ¹¹B and B contents. None of these surface water samples have δ¹¹B comparable to the local unweathered volcanic rocks (around 0‰), implying that a huge isotopic fractionation of 40‰ takes place during rock weathering, which could be explained by preferential incorporation of ¹⁰B during secondary mineral formation and adsorption on clays, during rock weathering or in the soils. The soil-vegetation B cycle could also be a cause for such a fractionation. Atmospheric B with δ¹¹B of 45‰ represents 25–95% of the river B content. The variety of the thermal spring chemical composition renders the understanding of B behavior in Guadeloupe hydrothermal system quite difficult. Complementary geochemical tracers would be helpful.     

Using dual isotopic data to track the sources and behaviors of dissolved sulfate in the western North China Plain

This paper investigated the sources and behaviors of sulfate in groundwater of the western North China Plain using sulfur and oxygen isotopic ratios. The groundwaters can be categorized into karst groundwater (KGW), coal mine drainage (CMD) and pore water (subsurface saturated water in interstices of unconsolidated sediment). Pore water in alluvial plain sediments could be further classified into unconfined groundwater (UGW) with depth of less than 30 m and confined groundwater (CGW) with depth of more than 60 m. The isotopic compositions of KGW varied from 9.3‰ to 11.3‰ for δ³⁴S_SO4 with the median value of 10.3‰ (n = 4) and 7.9‰ to 15.6‰ for δ¹⁸O_SO4 with the median value of 14.3‰ (n = 4) respectively, indicating gypsum dissolution in karst aquifers. δ³⁴S_SO4 and δ¹⁸O_SO4 values of sulfate in CMD ranged from 10.8‰ to 12.4‰ and 4.8‰ to 8.7‰ respectively. On the basis of groundwater flow path and geomorphological setting, the pore water samples were divided as three groups: (1) alluvial–proluvial fan (II₁) group with high sulfate concentration (median values of 2.37 mM and 1.95 mM for UGW and CGW, respectively) and positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 8.8‰ and 6.9‰ for UGW, 12.0‰ and 8.0‰ for CGW); (2) proluvial slope (II₂) group with low sulfate concentration (median values of 1.56 mM and 0.84 mM for UGW and CGW, respectively) and similar δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 9.0‰ and 7.4‰ for UGW, 10.2‰ and 7.7‰ for CGW); and (3) low-lying zone (II₃) group with moderate sulfate concentration (median values of 2.13 mM and 1.17 mM for UGW and CGW, respectively) and more positive δ³⁴S_SO4 and δ¹⁸O_SO4 values (median values of 10.7‰ and 7.7‰ for UGW, 20.1‰ and 8.8‰ for CGW). In the present study, three major sources of sulfate could be differentiated as following: sulfate dissolved from Ordovician to Permian rocks (δ³⁴S_SO4 = 10–35‰ and δ¹⁸O_SO4 = 7–20‰), soil sulfate (δ³⁴S_SO4 = 5.9‰ and δ¹⁸O_SO4 = 5.8‰) and sewage water (δ³⁴S_SO4 = 10.0‰ and δ¹⁸O_SO4 = 7.6‰). Kinetic fractionations of sulfur and oxygen isotopes as a result of bacterial sulfate reduction (BSR) were found to be evident in the confined aquifer in stagnant zone (II₃), and enrichment factors of sulfate–sulfur and sulfate–oxygen isotopes calculated by Rayleigh equation were −12.1‰ and −4.7‰ respectively along the flow direction of groundwater at depths of 60–100 m. The results obtained in this study confirm that detailed hydrogeological settings and identification of anthropogenic sources are critical for elucidating evolution of δ³⁴S_SO4 and δ¹⁸O_SO4 values along with groundwater flow path, and this work also provides a useful framework for understanding sulfur cycling in alluvial plain aquifers.     

Geochemical and isotopic variations in shallow groundwater in areas of the Fayetteville Shale development,north-central Arkansas

Exploration of unconventional natural gas reservoirs such as impermeable shale basins through the use of horizontal drilling and hydraulic fracturing has changed the energy landscape in the USA providing a vast new energy source. The accelerated production of natural gas has triggered a debate concerning the safety and possible environmental impacts of these operations. This study investigates one of the critical aspects of the environmental effects; the possible degradation of water quality in shallow aquifers overlying producing shale formations. The geochemistry of domestic groundwater wells was investigated in aquifers overlying the Fayetteville Shale in north-central Arkansas, where approximately 4000 wells have been drilled since 2004 to extract unconventional natural gas. Monitoring was performed on 127 drinking water wells and the geochemistry of major ions, trace metals, CH₄ gas content and its C isotopes (δ¹³C_CH4), and select isotope tracers (δ¹¹B, ⁸⁷Sr/⁸⁶Sr, δ²H, δ¹⁸O, δ¹³C_DIC) compared to the composition of flowback-water samples directly from Fayetteville Shale gas wells. Dissolved CH₄ was detected in 63% of the drinking-water wells (32 of 51 samples), but only six wells exceeded concentrations of 0.5 mg CH₄/L. The δ¹³C_CH4 of dissolved CH₄ ranged from −42.3‰ to −74.7‰, with the most negative values characteristic of a biogenic source also associated with the highest observed CH₄ concentrations, with a possible minor contribution of trace amounts of thermogenic CH₄. The majority of these values are distinct from the reported thermogenic composition of the Fayetteville Shale gas (δ¹³C_CH4 = −35.4‰ to −41.9‰). Based on major element chemistry, four shallow groundwater types were identified: (1) low (<100 mg/L) total dissolved solids (TDS), (2) TDS > 100 mg/L and Ca–HCO₃ dominated, (3) TDS > 100 mg/L and Na–HCO₃ dominated, and (4) slightly saline groundwater with TDS > 100 mg/L and Cl > 20 mg/L with elevated Br/Cl ratios (>0.001). The Sr (⁸⁷Sr/⁸⁶Sr = 0.7097–0.7166), C (δ¹³C_DIC = −21.3‰ to −4.7‰), and B (δ¹¹B = 3.9–32.9‰) isotopes clearly reflect water–rock interactions within the aquifer rocks, while the stable O and H isotopic composition mimics the local meteoric water composition. Overall, there was a geochemical gradient from low-mineralized recharge water to more evolved Ca–HCO₃, and higher-mineralized Na–HCO₃ composition generated by a combination of carbonate dissolution, silicate weathering, and reverse base-exchange reactions. The chemical and isotopic compositions of the bulk shallow groundwater samples were distinct from the Na–Cl type Fayetteville flowback/produced waters (TDS ∼10,000–20,000 mg/L). Yet, the high Br/Cl variations in a small subset of saline shallow groundwater suggest that they were derived from dilution of saline water similar to the brine in the Fayetteville Shale. Nonetheless, no spatial relationship was found between CH₄ and salinity occurrences in shallow drinking water wells with proximity to shale-gas drilling sites. The integration of multiple geochemical and isotopic proxies shows no direct evidence of contamination in shallow drinking-water aquifers associated with natural gas extraction from the Fayetteville Shale.     

Boron isotopic constraints on the Nb and Ta mineralization of the syenitic dikes in the ~ 260 Ma Emeishan large igneous province (SW China)

Both Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes in the Panxi region (SW China) are spatially and temporally associated with syenitic plutons, which are part of the ~ 260 Ma Emeishan large igneous province. These syenitic dikes are NW-striking, and have width varying from 1 to 5 m and length from 50 to 300 m. The dikes are mainly composed of K-feldspar, albite, aegirine and arfvedsonite, however, mineral modes are different in the Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes. The major Nb–Ta-bearing mineral in the dikes is pyrochlore, which is closely associated with albite and occurs in places with intensive albitization. Rocks of the Nb–Ta-mineralized syenitic dikes contain more albite and less K-feldspar than the Nb–Ta-poor dikes, and have compositions more evolved than the Nb–Ta-poor dikes, indicating that the Nb–Ta-mineralized syenitic dikes formed from a highly evolved magma. We analyzed the B concentrations and B isotopic compositions of the samples of both Nb–Ta-mineralized and Nb–Ta-poor syenitic dikes and associated syenitic pluton using a single column purification method and ICP-AES and MC-ICP-MS techniques. The samples of the Nb–Ta-mineralized syenitic dikes have whole-rock B concentrations ranging from 11.4 to 23.9 ppm and δ¹¹B values from − 17.95 to − 14.54‰, whereas the samples of the Nb–Ta-poor dikes and syenitic plutons have B concentrations varying from 3.32 to 16.5 ppm and δ¹¹B values from − 13.45 to − 10.02‰. The high B concentration of the Nb–Ta-mineralized dikes relative to the Nb–Ta-poor dikes is consistent with that B is incompatible and tends to be rich in more evolved magma. The relatively low δ¹¹B values of the Nb–Ta-mineralized dikes indicate that the B isotopes may have fractionated between fluids and rocks in a transitional, magmatic–hydrothermal stage. We propose that the highly evolved magmas in a transitional, magmatic–hydrothermal stage may have Nb– and Ta–fluorine complexes dissolved in the hydrothermal fluids in the presence of Na⁺. Albite crystallization due to intensive albitization in this stage resulted in the decrease of Na⁺ in the fluids, decomposing the Nb– and Ta–fluorine complexes. The released Nb and Ta from the complexes were then dissolved in the fluids and finally entered the lattice of pyrochlore crystals in the stage of albitization.     

Geochemical and isotopic evidence for a magmatic-hydrothermal origin of the polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen,South China

Polymetallic vein-type Zn-Pb deposits are located in the Xiangxi–Qiandong zinc-lead metallogenic belt (XQMB) of the northwestern margin of the Jiangnan Orogen, South China. Ores are mainly found in fault-bounded quartz veins hosted in the upper part of the Banxi Group that consists of low-grade metamorphic sandstone, siltstone with minor tuff interbeds. The Zn-Pb deposits primarily contain sphalerite, galena, chalcopyrite and pyrite, accompanied by quartz and minor calcite. Zinc, lead, copper, indium and gallium are enriched in these ores. Investigation of the ore fluid reveals low temperature (87–262 °C) with scattered salinity (range from 2.73 to 26.64 wt% NaCl_eqv.). Hydrogen and oxygen isotopic compositions of fluid inclusions in quartz indicate mixing of magmatic hydrothermal fluid and meteoric water (δ¹⁸O_{H2O SMOW} = 0.2‰ to 4.2‰; δD_{H2O SMOW} = −126‰ to −80‰). Carbon and oxygen isotopic composition of carbonate samples indicate the magmatic hydrothermal origin of CO₃²⁻ or CO₂ in ore-forming fluid (δ¹³C_PDB = −6.9‰ to −5.7‰, δ¹⁸O_SMOW = 11.3‰ to 12.7‰). Sulfur and lead isotopic compositions (δ³⁴S_VCDT = 8.8–14.2‰ and ²⁰⁶Pb/²⁰⁴Pb = 17.156–17.209, ²⁰⁷Pb/²⁰⁴Pb = 15.532–15.508, ²⁰⁸Pb/²⁰⁴Pb = 37.282–37.546) demonstrate that sulfur sources were relatively uniform, and low radiogenic lead isotopic compositions indicate that ore metals were derived from a relatively unradiogenic source, probably by mixing of mantle with crust. Therefore, polymetallic vein-type Zn-Pb mineralization in this area probably arose from a magmatic-related hydrothermal system, and the deposition of sulfides occurred in response to cooling and boiling of magmatic hydrothermal fluids (high salinity, high δ¹⁸O_H2O and δD_H2O and metal-bearing), and is mainly the result of emplacement into open space and mixing with meteoric water (low salinity, low δ¹⁸O_H2O and δD_H2O). This study provides direct evidence that magmatism was involved in the ore-forming processes of the low temperature metallogenic district, South China, and it raises awareness about the presence of polymetallic vein-type Zn-Pb deposits in the northwest margin of Jiangnan Orogen and their potential as a source of zinc, copper, indium and gallium.     

Geology,C–H–O–S–Pb isotope systematics and geochronology of the Yindongpo gold deposit,Tongbai Mountains,central China: Implication for ore genesis

The Yindongpo gold deposit is located in the Weishancheng Au–Ag-dominated polymetallic ore belt in Tongbai Mountains, central China. The ore bodies are stratabound within carbonaceous quartz–sericite schists of the Neoproterozoic Waitoushan Group. The ore-forming process can be divided into three stages, represented by early barren quartz veins, middle polymetallic sulfide veinlets and late quartz–carbonate stockworks, with most ore minerals, such as pyrite, galena, native gold and electrum being formed in the middle stage. The average δ¹⁸O_water values changed from 9.7‰ in the early stage, through 4.9‰ in the middle stage, to − 5.9‰ in the late stage, with the δD values ranging between − 65‰ and − 84‰. The δ¹³C_CO2 values of ore fluids are between − 3.7‰ and + 6.7‰, with an average of 1.1‰. The H–O–C isotope systematics indicate that the ore fluids forming the Yindongpo gold deposit were probably initially sourced from a process of metamorphic devolatilization, and with time gradually mixed with meteoric water. The δ³⁴S values range from − 0.3‰ to + 5.2‰, with peaks ranging from + 1‰ to + 4‰. Fourteen sulfide samples yield ²⁰⁶Pb/²⁰⁴Pb values of 16.990–17.216, ²⁰⁷Pb/²⁰⁴Pb of 15.419–15.612 and²⁰⁸Pb/²⁰⁴Pb of 38.251–38.861. Both S and Pb isotope ratios are similar to those of the main lithologies of the Waitoushan Group, but differ from other lithologic units and granitic batholiths in the Tongbai area, which suggest that the ore metals and fluids originated from the Waitoushan Group. The available K–Ar and ⁴⁰Ar/³⁹Ar ages indicate that the ore-forming process mainly took place in the period of 176–140 Ma, during the transition from collisional compression to extension and after the closure of the oceanic seaway in the Qinling Orogen. The Yindongpo gold deposit is interpreted as a stratabound orogenic-style gold system formed during the transition phase from collisional compression to extension.The ore metals in the Waitoushan Group were extracted, transported and then accumulated in the carbonaceous sericite schist layer. The carbonaceous sericite schist layer, especially at the junction of collapsed anticline axis and fault structures, became the most favorable locus for the ore bodies.     

The origin of the Maozu carbonate-hosted Pb–Zn deposit,southwest China: Constrained by C–O–S–Pb isotopic compositions and Sm–Nd isotopic age

The Maozu Pb–Zn deposit, located on the western margin of the Yangtze Block, southwest China, is a typical carbonate-hosted deposit in the Sichuan–Yunnan–Guizhou Pb–Zn metallogenic province with Pb + Zn reserves of about 2.0 million tonnes grading 4.15 wt.% Pb and 7.25 wt.% Zn. Its ore bodies are hosted in Sinian (635–541 Ma) Dengying Formation dolostone and show stratiform, vein and irregular textures. Ores are composed of sphalerite, galena, pyrite, calcite, dolomite, quartz and fluorite with massive, banded, disseminated and veined structures. The C–O–Sm–Nd isotopic compositions of hydrothermal calcites and S–Pb isotopic compositions of sulfides were analyzed to constrain the origin of the Maozu deposit. δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal calcites range from −3.7‰ to −2.0‰ and +13.8‰ to +17.5‰, respectively, and plot near the marine carbonate rocks field in a plot of δ¹³C_PDB vs. δ¹⁸O_SMOW, with a negative correlation. It suggests that CO₂ in the hydrothermal fluids was mainly originated from marine carbonate rocks, with limited influence from sedimentary organic matter. δ³⁴S_CDT values of sulfides range from +9.9‰ to +19.2‰, similar to that of Cambrian to Triassic seawater sulfate (+15‰ to +35‰) and evaporate (+15‰ to +30‰) in the Cambrian to Triassic sedimentary strata. It suggests that reduced sulfur was derived from evaporate in sedimentary strata by thermo chemical sulfate reduction. Sulfides have low radiogenic Pb isotope compositions (²⁰⁶Pb/²⁰⁴Pb = 18.129–18.375, ²⁰⁷Pb/²⁰⁴Pb = 15.640–15.686 and ²⁰⁸Pb/²⁰⁴Pb = 38.220–38.577) that plot in the field between upper crust and the orogenic belt evolution curve in the plot of ²⁰⁷Pb/²⁰⁴Pb vs. ²⁰⁶Pb/²⁰⁴Pb, and similar to that of age corrected Proterozoic basement rocks (Dongchuan and Kunyang Groups). This indicates that ore-forming metals were mainly derived from basement rocks. Hydrothermal calcite yields a Sm–Nd isotopic age of 196 ± 13 Ma, possibly reflecting the timing of Pb–Zn mineralization in the SYG province, younger than the Permian Emeishan mantle plume (∼260 Ma). All data combined suggests that hydrothermal fluids circulated through basement rocks where they picked up metals and migrated to surface, mixed with reduced sulfur-bearing fluids and precipitated metals. Ore genesis of the Maozu deposit is different from known magmatic–hydrothermal, Sedimentary Exhalative or Mississippi Valley-types, which maybe represent a unique ore deposit type, named as the SYG-type.     

Stable isotopic signatures of the modern land snail Eremina desertorum from a low-latitude (hot) dry desert—A study from the Petrified Forest,New Cairo,Egypt

This study was conducted on recent desert samples—including (1) soils, (2) plants, (3) the shell, and (4) organic matter from modern specimens of the land snail Eremina desertorum—which were collected at several altitudes (316–360 m above sea level) from a site in the New Cairo Petrified Forest. The soils and shell_{E. desertorum} were analyzed for carbonate composition and isotopic composition (δ¹⁸O, δ¹³C). The plants and organic matter_{E. desertorum} were analyzed for organic carbon content and δ¹³C. The soil carbonate, consisting of calcite plus minor dolomite, has δ¹⁸O values from −3.19 to −1.78‰ and δ¹³C values −1.79 to −0.27‰; covariance between the two values accords with arid climatic conditions. The local plants include C3 and C4 types, with the latter being dominant. Each type has distinctive bulk organic carbon δ¹³C values: −26.51 to −25.36‰ for C3-type, and −13.74 to −12.43‰ for C4-type plants.The carbonate of the shell_{E. desertorum} is composed of aragonite plus minor calcite, with relatively homogenous isotopic compositions (δ¹⁸O_mean = −0.28 ± 0.22‰; δ¹³C_mean = −4.46 ± 0.58‰). Most of the δ¹⁸O values (based on a model for oxygen isotope fractionation in an aragonite-water system) are consistent with evaporated water signatures. The organic matter_{E. desertorum} varies only slightly in bulk organic carbon δ¹³C values (−21.78 ± 1.20‰) and these values suggest that the snail consumed more of C3-type than C4-type plants. The overall offset in δ¹³C values (−17.32‰) observed between shell_{E. desertorum} carbonate and organic matter_{E. desertorum} exceeds the value expected for vegetation input, and implies that 30% of carbon in the shell_{E. desertorum} carbonate comes from the consumption of limestone material.