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.     

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.     

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.     

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

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

Carbon-oxygen isotopic geochemistry of the Yangla Cu skarn deposit,SW China: Implications for the source and evolution of hydrothermal fluids

The Yangla Cu deposit is the largest Cu skarn deposit in the Jinshajiang tectonic belt. Based on the detailed observation of crosscutting relationships, three mineralization stages (i.e., pre-ore, ore and supergene) have been identified in the Yangla deposit. The pre-ore stage is dominated by prograde skarn. The ore stage is characterized by the precipitation of hydrous silicate minerals, Fe-oxides, Fe-Cu-Mo-sulfides, quartz and calcite, whose mineral assemblages were formed in the early and late sub-ore stages. The early sub-ore stage is marked by retrograde alteration with the deposition of hydrous silicate minerals (e.g., actinolite, epidote and chlorite), Fe-oxides, abundant Fe-Cu-Mo-sulfides, quartz and minor calcite. Whilst, the late sub-ore stage, associated with silicic and carbonate alteration, is represented by widespread thick quartz or calcite veins with disseminated pyrite, chalcopyrite, galena and sphalerite. We present new carbon-oxygen (C-O) isotopic compositions of the ore-hosting marble and hydrothermal calcite of this deposit. The hydrothermal calcite in the Yangla deposit was precipitated from both the early and late sub-ore stages. Calcite I from the early sub-ore stage is anhedral, and occurs as spot in the skarn or locally replaces the skarn minerals. Calcite II from the late sub-ore stage is distinguished by being coarse-grained, subhedral to euhedral and its occurrence in thick veins. Calcite I contains lower δ¹³C_PDB (−7.0‰ to −5.0‰) and δ¹⁸O_SMOW (7.2‰ to 12.7‰) than Calcite II (δ¹³C_PDB = −4.5‰ to −2.3‰; δ¹⁸O_SMOW = 10.7‰ to 19.4‰). In the δ¹³C_PDB vs. δ¹⁸O_SMOW diagram, the Calcite I and Calcite II data fall close to the igneous carbonatite field and between the fields of igneous carbonatite and marine carbonates, respectively. This suggests a dominantly magmatic origin for the early sub-ore fluids, and there might have been increasing carbonate wall rock involvement towards the late sub-ore stage. The ore-hosting marble (δ¹³C_PDB = −4.8‰ to −0.3‰; δ¹⁸O_SMOW = 10.2‰ to 23.9‰) also shows a positive δ¹³C_PDB vs. δ¹⁸O_SMOW correlation, which is interpreted to reflect the decreasing alteration intensity during the interactions between the hydrothermal fluids and ore-hosting carbonates. Simulated calculation suggests that both the Calcite I and Calcite II precipitated at 350 °C to 250 °C and 250 °C to 150 °C, respectively. We proposed that CO₂ degassing and water/rock interactions were likely the two major processes that precipitated the calcite and led to the observed C-O isotopic features of the Yangla Cu deposit.     

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.     

Nanhuan manganese deposits within restricted basins of the southeastern Yangtze Platform,China: Constraints from geological and geochemical evidence

The Nanhuan manganese deposits in the southeastern Yangtze Platform occur in the black shale series in the lower part of the Datangpo Formation. In order to constrain the genesis of the deposits, a detailed study was undertaken that involved field observations, major and trace element analyses, organic carbon analyses, and isotope analyses (C, O, S). The major findings are as follows. (1) The ore-bearing rock series, morphology of the ore bodies, and characteristics of ores in several deposits are similar. The ore minerals are rhodochrosite and manganocalcite. The gangue minerals are mainly quartz, feldspar, dolomite, and illite. Minor apatite and bastnaesite occur in the manganese ores. (2) The ores are enriched in Ca and Mg, whereas they are depleted in Si, Al, K, and Ti compared to wall rocks. The ores normalized to average Post-Archean Australian shale (PAAS) are enriched in Co, Mo, and Sr. The chondrite-normalized rare earth element (REE) patterns for ores and wall rocks are between those of typical hydrogenous and hydrothermal type manganese deposits. Additionally, the ores have positive Ce anomalies with an average Ce/Ce* of 1.23 and positive Eu anomalies with an average Eu/Eu* of 1.18 (normalized to PAAS). (3) The average content of organic carbon is 2.21% in the samples, and the average organic carbon isotopic value (δ¹³C_V-PDB) is − 33.44‰. The average inorganic carbon isotopic value (δ¹³C_V-PDB) of carbonates in Gucheng is − 3.07‰, while the values are similar in the other deposits with an average of − 8.36‰. The oxygen isotopic compositions (δ¹⁸O_V-PDB) are similar in different deposits with an average of − 7.72‰. (4) The sulfur isotopic values (δ³⁴S_V-CDT) of pyrite are very high and range from + 37.9‰ to + 62.6‰ (average of 52.7‰), which suggests that the pyrite was formed in restricted basins where sulfate replenishment was limited. The sulfate concentrations in the restricted basins were extremely low and enriched in δ³⁴S, which resulted in the very high δ³⁴S values for the pyrite that formed in the manganese deposits. Therefore, a terrigenous weathering origin for manganese can be excluded; otherwise, the sulfate would have been introduced into the basins together with terrigenous manganese, which would have decreased the δ³⁴S values of pyrites. The manganese, which originated from hydrothermal processes, was enriched in the restricted and anoxic basins, and then, it was oxidized to manganese oxyhydroxide in the overlying oxic waters whereby the products precipitated into the sediments. The manganese oxyhydroxide in the sediment was then reduced to Mn^2 + and released to the pore waters during the process of diagenesis. Some organic carbon was oxidized to CO₃^2 −, which made the depletion of ¹³C in manganese carbonates. Therefore, we suggest that the Nanhuan manganese deposits are hydrothermal–sedimentary/diagenetic type deposits.     

Magmatic hydrothermal origin of the Hadamengou-Liubagou Au-Mo deposit,Inner Mongolia,China: Constrains on geology,stable and Re-Os isotopes

The Hadamengou-Liubagou Au-Mo deposit is the largest gold deposit in Inner Mongolia of North China. It is hosted by amphibolite to granulite facies metamorphic rocks of the Archean Wulashan Group. To the west and north of the deposit, there occur three alkaline intrusions, including the Devonian-Carboniferous Dahuabei granitoid batholith, the Triassic Shadegai granite and the Xishadegai porphyritic granite with molybdenum mineralization. Over one hundred subparallel, sheet-like ore veins are confined to the nearly EW-trending faults in the deposit. They typically dip 40° to 80° to the south, with strike lengths from hundreds to thousands of meters. Wall rock alterations include potassic, phyllic, and propylitic alteration. Four distinct mineralization stages were identified at the deposit, including K-feldspar-quartz-molybdenite stage (I), quartz-pyrite-epidote/chlorite stage (II), quartz-polymetallic sulfide-gold stage (III), and carbonate-sulfate-quartz stage (IV). Gold precipitated mainly during stage III, while Mo mineralization occurred predominantly in stage I. The δD_H2O and δ¹⁸O_H2O values of the ore-forming fluids range from −125‰ to −62‰ and from 1.4‰ to 7.5‰, respectively, indicating that the fluids were dominated by magmatic water with a minor contribution of meteoric water. The δ¹³C_PDB and δ¹⁸O_SMOW values of hydrothermal carbonate minerals vary from −10.3‰ to −3.2‰ and from 3.7‰ to 15.3‰, respectively, suggesting a magmatic carbon origin. The δ³⁴S_CDT values of sulfides from the ores vary from −21.7‰ to 5.4‰ and are typically negative (mostly −20‰ to 0‰). The wide variation of the δ³⁴S_CDT values, the relatively uniform δ¹³C values of carbonates (typically −5.5‰ to −3.2‰), as well as the common association of barite with sulfides suggest that the minerals were precipitated under relatively high fo₂ conditions, probably in a magmatic fluid with δ³⁴S_ƩS ≈ 0‰. The Re-Os isotopic dating on molybdenite from Hadamengou yielded a weighted average age of 381.6 ± 4.3 Ma, indicating that the Mo mineralization occurred in Late Devonian. Collectively, previous ⁴⁰Ar-³⁹Ar and Re-Os isotopic dates roughly outlined two ranges of mineralizing events of 382–323 Ma and 240–218 Ma that correspond to the Variscan and the Indosinian epochs, respectively. The Variscan event is approximately consistent with the Mo mineralization at Hadamengou-Liubagou and the emplacement of the Dahuabei Batholith, whereas the Indosinian event roughly corresponds to the possible peak Au mineralization of the Hadamengou-Liubagou deposit, as well as the magmatic activity and associated Mo mineralization at Xishadegai and Shadegai. Geologic, petrographic and isotopic evidence presented in this study suggest that both gold and molybdenum mineralization at Hadamengou-Liubagou is of magmatic hydrothermal origin. The molybdenum mineralization is suggested to be associated with the magmatic activity during the southward subduction of the Paleo-Asian Ocean beneath the North China Craton (NCC) in Late Devonian. The gold mineralization is most probably related to the magma-derived hydrothermal fluids during the post-collisional extension in Triassic, after the final suturing between the Siberian and NCC in Late Permian.     

Geology and isotope geochemistry (C–O–S) of the Diyadin gold deposit,Eastern Turkey: A newly-discovered Carlin-like deposit

Diyadin mineralization is the first reported gold deposit located in a collisional tectonic environment in Eastern Anatolia. The mineralization is related to N–S and N10–20°W-trending fault systems and hosted within the Paleozoic metamorphic basement rocks of the Anatolide–Toride microcontinent. Calc-schist, dolomitic marble and Miocene and Quaternary volcanic rocks comprise the exposed units in the mineralized area. Geochemical signatures, alteration types and host rock characteristics of the Diyadin gold deposit resemble those of Carlin-type deposits. Mineralization is constrained by alteration of overlying volcanic rocks to younger than ~ 14 Ma (K–Ar).Carbon and oxygen stable isotope measurements of carbonate rocks were made on six drill holes (n = 81) with an additional four samples of fresh carbonate rocks from surface outcrops. Background carbonate rocks have δ¹³C_V-PDB ~ 1.8‰ and δ¹⁸O_V-SMOW ~ 27‰. Isotopically-altered host rock samples have decreased δ¹⁸O (down to ~+11.4‰) and variable δ¹³C (from − 3.6 to + 4.8‰). Postore carbonate veins and cave-fill material have distinctly different isotopic signatures, particularly carbon (from δ¹³C = + 8.4 to + 9.8‰). Whether this post-ore carbonate is simply very late in mineralization associated with the gold system, or is a completely different, younger system utilizing the same pathways, is unclear at present. Within the host rock sample set, there is no correlation between gold and δ¹³C, and a weak correlation between gold and δ¹⁸O, indicative of water–rock interaction and isotopic alteration. Both the isotopic data and structural mapping suggest that the main upflow zone for the deposit is near the northern portion of the drill fence. Additional data at multiple scales are required to clarify the relationship(s) between fluid flow and mineralization.     

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).     

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.     

The source and paleoclimatic implication of hydrogen isotopic composition of n-alkanes in sediments from the Yixian Formation,western Liaoning Province,NE China

Hydrogen isotopic composition of n-alkanes was measured in sediments from an excavated profile of the Early Cretaceous Yixian Formation in Liaoning Province, NE China, aiming to assess the significance of the δD value of n-alkanes in ancient lacustrine sediments as the indicator for determining the source inputs of organic matters and paleoclimatic conditions. The δD values of n-alkanes are in the range of − 250‰ to − 85‰ and display an obvious three-stage variation pattern through the profile, which is consistent with the distribution of the dominated n-alkanes and the profile of their δ¹³C values. The δD and δ¹³C values of n-alkanes suggest that short-chain n-alkanes are primarily derived from photosynthetic bacteria and algae; n-C₂₉ and n-C₃₁ are mainly originated from terrestrial higher plants; n-C₂₈ and n-C₃₀ may be derived from the same precursor but via the different biological mechanism of hydrogen isotopic fractionation; while the source inputs of medium-chain n-alkanes are more complicated, with n-C₂₃ being derived from some specific algae or biosynthesized by various aquatic organisms. The paleoclimatic conditions are reconstructed via two approaches. The reconstructed hydrogen isotopic values of lake water and meteoric water (expressed as δD_LW and δD_MW, respectively) were at the intervals of − 51.8‰ to 17.0‰ and − 118.1‰ to − 43.5‰, respectively, indicating a general climate transition from semi-arid to arid. The calculated ΔδD_LW-MW values vary from 37.0‰ to 89.1‰ and display a similar but a significant large-scale variation trend with the ΔδD_{C23 ‐ long} (− 28.8‰ to 85.0‰; long represents long-chain n-alkanes) and ΔδD_mid-long (− 15.4‰ to 43.4‰; mid represents medium-chain n-alkanes) values. The discrepancy may be attributed to the source input overlap for n-alkanes and the uncertainties of ε_water/lipid values. The coupling of ΔδD_{C23 ‐ long}, ΔδD_mid-long and ΔδD_LW-MW values with the paleoclimatic evidence indicates that the δD values of n-alkanes could be more sensitive to the change of paleoclimatic conditions.     

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.     

Geology and fluid characteristics of the Ulu Sokor gold deposit,Kelantan, Malaysia: Implications for ore genesis and classification of the deposit

The Ulu Sokor gold deposit is one of the most famous and largest gold deposits in Malaysia and is located in the Central Gold Belt. This deposit consists of three major orebodies that are related to NS- and NE-striking fractures within fault zones in Permian-Triassic meta-sedimentary and volcanic rocks of the East Malaya Block. The faulting events represent different episodes that are related to each orebody and are correlated well with the mineralogy and paragenesis. The gold mineralization consists of quartz-dominant vein systems with sulfides and carbonates. The hydrothermal alteration and mineralization occurred during three stages that were characterized by (I) silicification and brecciation; (II) carbonatization, sericitization, and chloritization; and (III) quartz–carbonate veins.Fluid inclusions in the hydrothermal quartz and calcite of the three stages were studied. The primary CO₂–CH₄–H₂O–NaCl fluid inclusions in stage I are mostly related to gold mineralization and display homogenization temperatures of 269–389 °C, salinities of 2.77–11.89 wt.% NaCl equivalent, variable CO₂ contents (typically 5–29 mol%), and up to 15 mol% CH₄. In stage II, gold was deposited at 235–398 °C from a CO₂ ± CH₄–H₂O–NaCl fluid with a salinity of 0.83–9.28 wt.% NaCl equivalent, variable CO₂ contents (typically 5–63 mol%), and up to 4 mol% CH₄. The δ¹⁸O_H2O and δD values of the ore-forming fluids from the stage II quartz veins are 4.5 to 4.8‰ and − 44 to − 42‰, respectively, and indicate a metamorphic–hydrothermal origin. Oxygen fugacities calculated for the entire range of T-P-X_CO2 conditions yielded log f_O2 values between − 28.95 and − 36.73 for stage I and between − 28.32 and − 39.18 for stage II. These values indicate reduced conditions for these fluids, which are consistent with the mineral paragenesis, fluid inclusion compositions, and isotope values.The presence of daughter mineral-bearing aqueous inclusions is interpreted to be a magmatic signature of stage IIIa. Combined with the oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 6.8 to 11.9‰, δD = − 77 to − 62‰), these inclusions indicate that the initial fluid was likely derived from a magmatic source. In stage IIIb, the gold was deposited at 263° to 347 °C from a CO₂–CH₄–H₂O–NaCl fluid with a salinity of 5.33 to 11.05 wt.% NaCl equivalent, variable CO₂ contents (typically 9–15 mol%), and little CH₄. The oxygen and hydrogen isotopic compositions of this fluid (δ¹⁸O_H2O = 8.1 to 8.8‰, δD = − 44 to − 32‰) indicate that it was mainly derived from a metamorphic–hydrothermal source. The CO₂–H₂O ± CH₄–NaCl fluids that were responsible for gold deposition in the stage IIIc veins had a wide range of temperatures (214–483 °C), salinities of 1.02 to 21.34 wt.% NaCl equivalent, variable CO₂ contents (typically 4–53 mol%), and up to 7 mol% CH₄. The oxygen and hydrogen isotopic compositions (δ¹⁸O_H2O = 8.5 to 9.8‰, δD = − 70 to − 58‰) were probably acquired at the site of deposition by mixing of the metamorphic–hydrothermal fluid with deep-seated magmatic water and then evolved by degassing at the site of deposition during mineralization. The log f_O2 values from − 28.26 to − 35.51 also indicate reduced conditions for this fluid in stage IIIc. Moreover, this fluid had a near-neutral pH and δ³⁴S values of H₂S of − 2.32 to 0.83‰, which may reflect the derivation of sulfur from the subducted oceanic lithospheric materials.The three orebodies represent different gold transportation and precipitation models, and the conditions of ore formation are related to distinct events of hydrothermal alteration and gold mineralization. The gold mineralization of the Ulu Sokor deposit occurred in response to complex and concurrent processes involving fluid immiscibility, fluid–rock reactions, and fluid mixing. However, fluid immiscibility was the most important mechanism for gold deposition and occurred in these orebodies, which have corresponding fluid properties, structural controls, geologic characteristics, tectonic settings, and origins of the ore-forming matter. These characteristics of the Ulu Sokor deposit are consistent with its classification as an orogenic gold deposit, while some of the veins are genetically related to intrusions.     

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.     

Molecular and stable carbon isotopic compositions of saturated fatty acids within one sedimentary profile in the Shenhu,northern South China Sea: Source implications

This study examined the distributions and stable carbon isotopic compositions of saturated fatty acids (SaFAs) in one 300 cm long sedimentary profile, which was named as Site4B in Shenhu, northern South China Sea. The concentrations of total SaFAs in sediments ranged from 1.80 to 10.16 μg/g (μg FA/g dry sediment) and showed an even-over-odd predominance in the carbon chain of C₁₂ to C₃₂, mostly with n-C₁₆ and n-C₁₈ being the two major components. The short-chain fatty acids (ScFAs; n-C₁₂ to n-C₁₈) mainly from marine microorganisms had average δ¹³C values of −26.7‰ to −28.2‰, whereas some terrigenous-sourced long-chain fatty acids (LcFAs; n-C₂₁ to n-C₃₂) had average δ¹³C values of −29.6‰ to −34.1‰. The other LcFAs (n-C₂₄ & n-C₂₆ ∼ n-C₂₈; average δ¹³C values are −26.1‰ to −28.0‰) as well as n-C₁₉ and n-C₂₀ SaFAs (average δ¹³C values are −29.1‰ and −29.3‰, respectively) showed a mixed signal of carbon isotope compositions.The relative bioproductivity calculation (marine vs. terrigenous) demonstrated that most of organic carbon accumulation throughout the sedimentary profile was contributed by marine organism. The high marine productivity in Shenhu, South China Sea may be related to the hydrocarbon seepage which evidenced by diapiric structures. Interestingly, there is a sever fluctuation of terrigenous inputs around the depth of 97 cm below the seafloor (bsf), probably resulting from the influence of the Dansgaard–Oeschger events and the Younger Dryas event as revealed by ¹⁴C age measurements.     

Geology and geochemistry of the sediment-hosted Cheshmeh-Konan redbed-type copper deposit,NW Iran

The several-hundred-m-thick Miocene Upper Red Formation in northwestern Iran hosts stratiform and fault-controlled copper mineralization. Copper enrichment in the percent range occurs in dm-thick carbonaceous sandstone and shale units within the clastic redbed sequence and consists of fine-grained disseminated copper sulfides (chalcopyrite, bornite, chalcocite) and supergene alteration minerals (covellite, malachite and azurite). The copper mineralization formed after calcite cementation of the primary rock permeability. Copper sulfides occur mainly as replacement of diagenetic pyrite, which, in turn, replaced organic matter. Electron microprobe analysis on bornite, chalcocite and covellite identifies elevated silver contents in these minerals (up to 0.12, 0.72 and 1.21 wt%, respectively), whereas chalcopyrite and pyrite have only trace amounts of silver (<0.26 and 0.06 wt%, respectively). Microthermometric data on fluid inclusions in authigenic quartz and calcite indicate that the Cu mineralization is related to a diagenetic fluid of moderate-to low temperature (Th = 96–160 °C) but high salinity (25–38 wt% CaCl₂ equiv.). The range of δ³⁴S in pyrite is −41.9 to −16.4‰ (average −31.4‰), where framboidal pyrite shows the most negative values between −41.9 and −31.8‰, and fine-grained pyrite has relatively heavier δ³⁴S values (−29.2 to −16.4‰), consistent with a bacteriogenic derivation of the sulfur. The Cu-sulfides (chalcopyrite, bornite and chalcocite) show slightly heavier values from −14.6 to −9.0‰, and their sulfur sources may be both the precursor pyrite-S and the bacterial reduction of sulfate-bearing basinal brines. Carbonates related to the ore stage show isotopically light values of δ¹³C_V-PDB from −8.2 to −5.1‰ and δ¹⁸O_V-PDB from −10.3 to −7.2‰, indicating a mixed source of oxidation of organic carbon (ca. −20‰) and HCO₃⁻ from seawater/porewater (ca. 0‰). The copper mineralization is mainly controlled by organic matter content and paleopermeability (intragranular space to large fracture patterns), enhanced by feldspar and calcite dissolution. The Cheshmeh-Konan deposit can be classified as a redbed-type sediment-hosted stratiform copper (SSC) 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.     

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.     

Carbon and sulfur isotopic fluctuations associated with the end-Guadalupian mass extinction in South China

Concentrations of total organic matter (TOC), carbon isotopic compositions of carbonate and organic matter (δ¹³C_carb, δ¹³C_org), and sulfur isotopic compositions of carbonate associated sulfate (δ³⁴S_sulfate) across the Guadalupian–Lopingian (G–L) boundary were analyzed from identical samples of Tieqiao section, Laibin, Guangxi province, South China. The δ¹³C_carb values show a positive excursion from − 0.45‰ to the peak of 3.80‰ in the Laibin limestone member of the Maokou Formation, followed by a drastic drop to − 2.60‰ in the lowest Heshan formation, then returned to about 1.58‰. Similar to the trends of the δ¹³C_carb values, Δ¹³C_carb–org values also show a positive excursion followed by a sharp negative shift. The onset of a major negative carbon isotope excursion postdates the end Guadalupian extinction that indicates subsequent severe disturbance of the ocean–atmosphere carbon cycle. The first biostratigraphic δ³⁴S_sulfate values during the G–L transition exhibit a remarkable fluctuation: a dramatic negative shift followed by a rapid positive shift, ranging from 36.88‰ to − 37.41‰. These sulfate isotopic records suggest that the ocean during the G–L transition was strongly stratified, forming an unstable chemocline separating oxic shallow water from anoxic/euxinic deep water. Chemocline excursions, together with subsequent rapid transgression and oceanic anoxia, were likely responsible for the massive diversity decline of the G–L biotic crisis.