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.     

Alteration mineralogy,lithochemistry and stable isotope geochemistry of the Murgul (Artvin,NE Turkey) volcanic hosted massive sulfide deposit: Implications for the alteration age and ore forming fluids

The Murgul (Artvin, NE Turkey) massive sulfide deposit is hosted dominantly by Late Cretaceous calc-alkaline to transitional felsic volcanics. The footwall rocks are represented by dacitic flows and pyroclastics, whereas the hanging wall rocks consist of epiclastic rocks, chemical exhalative rocks, gypsum-bearing vitric tuff, purple vitric tuff and dacitic flows. Multi-element variation diagrams of the hanging wall and footwall rocks exhibit similar patterns with considerable enrichment in K, Rb and Ba and depletion in Nb, Sr, Ti and P. The chondrite-normalized rare earth element (REEs) patterns of all the rocks are characterized by pronounced positive/negative Eu anomalies as a result of different degrees of hydrothermal alteration and the semi-protected effects of plagioclase fractionation.Mineralogical results suggest illite, illite/smectite + chlorite ± kaolinite and chlorite in the footwall rocks and illite ± smectite ± kaolinite and chlorite ± illite in the hanging wall rocks. Overall, the alteration pattern is represented by silica, sericite, chlorite and chlorite–carbonate–epidote–sericite and quartz/albite zones. Increments of Ishikawa alteration indexes, resulting from gains in K₂O and losses in Na₂O and the chlorite–carbonate–pyrite index towards to the center of the stringer zone, indicate the inner parts of the alteration zones. Calculations of the changes in the chemical mass imply a general volume increase in the footwall rocks. Abnormal volume increases are explained by silica and iron enrichments and a total depletion of alkalis in silica zone. Relative K increments are linked to the sericitization of plagioclase and glass shards and the formation of illite/smectite in the sericite zone. In addition, Fe enrichment is always met by pyrite formation accompanied by quartz and chlorite. Illite is favored over chlorite, smectite and kaolinite in the central part of the ore body due to the increase in the (Al + K)/(Na + Ca) ratio. Although the REEs were enriched in the silicification zone, light REEs show depletion in the silicification zone and enrichment in the other zones in contrast to the heavy REEs' behavior. Hydrothermal alteration within the hanging wall rocks, apart from the gypsum-bearing vitric tuffs, is primarily controlled by chloritization with proportional Fe and Mg enrichments and sericitization.The δ¹⁸O and δD values of clay minerals systematically change with increasing formation temperature from 6.6 to 8.7‰ and − 42 to − 50‰ for illites, and 8.6 and − 52‰ for chlorite, respectively. The O- and H-stable isotopic data imply that hydrothermal-alteration processes occurred at 253–332 °C for illites and 136 °C for chlorite with a temperature decrease outward from the center of the deposit. The positive δ³⁴S values (20.3 to 20.4‰) for gypsum suggest contributions from seawater sulfate reduced by Fe-oxide/-hydroxide phases within altered volcanic units. Thus, the hydrothermal alteration possibly formed via a dissolution–precipitation mechanism that operated under acidic conditions. The K–Ar dating (73–62 Ma) of the illites indicates an illitization process from the Maastrichtian to Early Danian period.     

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.     

Isotope (C and O) composition of auriferous quartz carbonate veins,central lode system,Gadag Gold Field,Dharwar Craton,India: Implications to source of ore fluids

Carbon (δ¹³C_PDB) and oxygen (δ¹⁸O_SMOW) isotopic compositions of auriferous quartz-carbonate veins (QCVs) of gold deposits from Sangli, Kabuliyatkatti, Nagavi, Nabapur and Mysore mining areas developed on the Central Lode system of the Gadag Gold Field (GGF) in the Neoarchaean Gadag schist belt of the Dharwar Craton, southern India have been examined for the first time to understand the origin of the mineralising fluids. In majority of the samples (46 out of 49), δ¹³C_pdb of carbonates of the QCVs fall in the range from − 2.2‰ to − 9.7‰ and the δ¹⁸O values range from 12.0‰ to 30.5‰ SMOW. The calculated fluid δ¹³C_∑ C compositions for these deposits range from − 2.1‰ to − 9.6‰ and δ¹⁸O_H2O from 6.8‰ to 25.9‰, respectively. Carbonate δ¹³C and fluid δ¹³C_∑ C compositions of the carbonates of the QCVs of the GGF are not only distinct from the carbon isotope range of marine carbonates or meta-sedimentary carbonates of the Chitradurga schist belt, but are consistent with C-isotope values of magmatic (− 5 ± 3‰, Burrows et al., 1986) and/or mantle (− 6 ± 2‰, Ohmoto, 1986) carbonates. As dissolution/decarbonation reactions during metamorphism of pre-existing carbonate/carbonated rocks produce CO₂ with δ¹³C values similar to or more enriched than parent rock, the carbonate or fluid δ¹³C ratios of the QCVs (which fall in the compositional range of mantle/magmatic derived CO₂ or carbonates) obtained in this work cannot be the result of metamorphism. The present study corroborates our previous reports from Ajjanahalli and G.R. Halli gold deposits (Sarangi et al., 2012) occurring in the vicinity of the southern extension of the same crustal scale shear zone on which all the GGF deposits are located.The age of gold mineralisation in this area has been reported to be 2522 ± 6 Ma by Sarma et al., 2011. Chardon et al. (2011) have proposed large-scale remobilization of the older gneissic basement, as well as, emplacement of juvenile granites between 2559 Ma and 2507 Ma, close to the crustal scale shear zone along the eastern margin of the Chitradurga schist belt. Based on these observations and our isotope studies, it is proposed that gold mineralising fluids were derived from mantle/juvenile magmatic melts and were channelled through crustal scale shear zones to give rise to the gold deposits in the GGF.     

海拉尔盆地乌尔逊凹陷幔源CO2充注对下白垩统砂岩储层质量的影响

海拉尔盆地乌尔逊凹陷下白垩统含片钠铝石砂岩部分记录了幔源CO_2-砂岩相互作用历史.为揭示幔源CO_2充注对储层质量的影响,通过偏光显微镜、扫描电镜观察和孔隙度、渗透率数据研究了海拉尔盆地乌尔逊凹陷含片钠铝石砂岩的岩石学和储层特征.幔源CO_2的充注导致了长石的部分溶解和片钠铝石及铁白云石的沉淀.长石的溶解形成了次生孔隙.片钠铝石以针状晶形为特征,其集合体呈束状、簇状、扇状和玫瑰花状.部分片钠铝石呈板状.片钠铝石以充填孔隙为主,少量交代长石和其他骨架碎屑颗粒.片钠铝石局部被铁白云石交代,说明铁白云石的形成晚于片钠铝石.片钠铝石的含量为1%～20%.相同深度段的含片钠铝石砂岩(n=597,h=1309.15～2140.71m)与普通砂岩(n=1550,h=1323.72～2141.3m)的孔隙度、渗透率数据统计表明,含片钠铝石砂岩的物性整体上低于普通砂岩,说明CO_2的充注导致了储层质量的改变.片钠铝石含量-孔隙度和片钠铝石含量-渗透率之间的关系,揭示片钠铝石含量是引起储层质量改变的主要因素.片钠铝石含量10%似乎是储层质量发生变化的界限,当片钠铝石含量＞10%,随片钠铝石含量增加,砂岩的孔隙度和渗透率降低;当片钠铝石含量＜10%,随片钠铝石含量增加,部分砂岩的孔隙度和渗透率表现出增加趋势.作者认为,片钠铝石含量高的砂岩长期处于高CO_2分压成岩环境,而片钠铝石含量低的砂岩则处于高CO_2分压成岩环境的时间相对较短.     

Isotope and fluid inclusion geochemistry and genesis of the Qiangma gold deposit,Xiaoqinling gold field,Qinling Orogen,China

The Qiangma gold deposit is hosted in the > 1.9 Ga Taihua Supergroup metamorphic rocks in the Xiaoqinling terrane, Qinling Orogen, on the southern margin of the North China Craton. The mineralization can be divided as follows: quartz-pyrite veins early, quartz-polymetallic sulfide veinlets middle, and carbonate-quartz veinlets late stages, with gold being mainly introduced in the middle stage. Three types of fluid inclusions were identified based on petrography and laser Raman spectroscopy, i.e., pure carbonic, carbonic-aqueous (CO₂–H₂O) and aqueous inclusions.The early-stage quartz contains pure carbonic and CO₂–H₂O inclusions with salinities up to 12.7 wt.% NaCl equiv., bulk densities of 0.67 to 0.86 g/cm³, and homogenization temperatures of 280−365 °C. The early-stage is related to H₂O–CO₂ ± N₂ ± CH₄ fluids with isotopic signatures consistent with a metamorphic origin (δ¹⁸O_water = 3.1 to 5.2‰, δD = − 37 to − 73‰). The middle-stage quartz contains all three types of fluid inclusions, of which the CO₂–H₂O and aqueous inclusions yield homogenization temperatures of 249−346 °C and 230−345 °C, respectively. The CO₂–H₂O inclusions have salinities up to 10.9 wt.% NaCl equiv. and bulk densities of 0.70 to 0.98 g/cm³, with vapor bubbles composed of CO₂ and N₂. The isotopic ratios (δ¹⁸O_water = 2.2 to 3.6‰, δD = − 47 to − 79‰) suggest that the middle-stage fluids were mixed by metamorphic and meteoric fluids. In the late-stage quartz only the aqueous inclusions are observed, which have low salinities (0.9−9.9 wt.% NaCl equiv.) and low homogenization temperatures (145−223 °C). The isotopic composition (δ¹⁸O_water = − 1.9 to 0.5‰, δD = − 55 to − 66‰) indicates the late-stage fluids were mainly meteoric water.Trapping pressures estimated from CO₂–H₂O inclusions are 100−285 MPa for the middle stage, suggesting that gold mineralization mainly occurred at depths of 10 km. Fluid boiling and mixing caused rapid precipitation of sulfides and native Au. Through boiling and inflow of meteoric water, the ore-forming fluid system evolved from CO₂-rich to CO₂-poor in composition, and from metamorphic to meteoric, as indicated by decreasing δ¹⁸O_water values from early to late. The carbon, sulfur and lead isotope compositions suggest the hostrocks within the Taihua Supergroup to be a significant source of ore metals. Integrating the data obtained from the studies including regional geology, ore geology, and fluid inclusion and C–H–O–S–Pb isotope geochemistry, we conclude that the Qiangma gold deposit was an orogenic-type system formed in the tectonic transition from compression to extension during the Jurassic−Early Cretaceous continental collision between the North China and Yangtze cratons.     

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.     

Monitoring of fluid–rock interaction and CO2 storage through produced fluid sampling at the Weyburn CO2-injection enhanced oil recovery site,Saskatchewan, Canada

The Weyburn Oil Field is a carbonate reservoir in south central Saskatchewan, Canada and is the site of a large CO₂ injection project for purposes of enhanced oil recovery. The Weyburn Field, in the Mississippian Midale Formation, was discovered in 1954 and was under primary production until secondary recovery by water flood began in 1964. The reservoir comprises two units, the Vuggy and the Marly, and primary and secondary recovery are thought to only have significantly depleted the Vuggy zone, leaving the Marly with higher oil saturations. In 2000, PanCanadian Resources (now EnCana), the operator of the field, began tertiary recovery by injection of CO₂ and water, primarily into the Marly. The advent of this project was an opportunity to study the potential for geological storage of CO₂.Using 43 Baseline samples collected in August 2000, before CO₂ injection at Weyburn, and 44 monitoring samples collected in March 2001, changes in the fluid chemistry and isotope composition have been tracked. The initial fluid distribution showed water from discovery through water flood in the Midale Formation with Cl ranging from 25,000 to 60,000 mg/L, from the NW to the SE across the Phase 1A area. By the time of Baseline sampling the produced water had been diluted to Cl of 25,000–50,000 mg/L as a result of the addition of make up water from the low TDS Blairmore Formation, but the pattern of distribution was still present. The Cl distribution is mimicked by the distribution of other dissolved ions and variables, with Ca (1250–1500 mg/L) and NH_{3 (aq)} increasing from NW to SE, and alkalinity (700–300 mg/L), resistivity, and H₂S (300–100 mg/L) decreasing. Based on chemical and isotopic data, the H₂S is interpreted to result from bacterial SO₄ reduction. After 6 months of injection of CO₂, the general patterns are changed very little, except that the pH has decreased by 0.5 units and alkalinity has increased, with values over 1400 mg/L in the NW, decreasing to 500 mg/L in the SE. Calcium has increased to range from 1250 to 1750 mg/L, but the pattern of NW–SE distribution is altered. Chemical and isotopic data suggest this change in distribution is caused by the dissolution of calcite due to water–rock reactions driven by CO₂. The Baseline samples varied from −22 to −12‰ δ¹³C (V-PDB) for CO₂ gas. The injected CO₂ has an isotope ratio of −20‰. The Monitor-1 samples of produced CO₂ ranged from −18 to −13‰, requiring a heavy source of C, most easily attributed to dissolution of carbonate minerals. Field measured pH had increased and alkalinity had decreased by the second monitoring trip (July 2001) to near Baseline values, suggesting continued reaction with reservoir minerals.Addition of CO₂ to water–rock mixtures comprising carbonate minerals causes dissolution of carbonates and production of alkalinity. Geochemical modeling suggests dissolution is taking place, however more detail on water–oil–gas ratios needs to be gathered to obtain more accurate estimates of pH at the formation level. Geological storage of CO₂ relies on the potential that, over the longer term, silicate minerals will buffer the pH, causing any added CO₂ to be precipitated as calcite. Some initial modeling of water–rock reactions suggests that silica sources are available to the water resident in the Midale Formation, and that clay minerals may well be capable of acting as pH buffers, allowing injected CO₂ to be stored as carbonate minerals. Further work is underway to document the mineralogy of the Midale Formation and associated units so as to define more accurately the potential for geological storage.     

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.     

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.     

One-year spatial and temporal monitoring of concentration and carbon isotopic composition of atmospheric CO2 in a Wrocław (SW Poland) city area

The main aim of this study was to assess the natural and anthropogenic contributions of CO₂ in the urban atmosphere of Wrocław City (SW Poland) using combined quantitative (CO₂ concentrations) and qualitative analysis (δ¹³C of CO₂). Between 21 January 2011 and 22 December 2011, 17 sampling campaigns were performed at 3-week intervals and in total 255 samples were collected. The mean CO₂ concentration was 469 ± 71 ppm and the mean δ¹³C(CO₂) was −10.8 ± 1‰.The measured δ¹³C(CO₂) values of major end-members for two winter heating seasons (−25.7‰ in January–March of 2011 and −27.6 ‰ in October–December of 2011) and for one vegetative season (−20.4‰ in April–September of 2011) suggest soil respiration as a main source of atmospheric CO₂ during the vegetative season, and a very significant impact of fossil fuel combustion during the winter heating seasons. There were significant increases of CO₂ concentrations at many sampling locations after the opening of a new motorway on 31 August 2011. The authors hypothesise that the new motorway contributes to the increase of CO₂ across the city.     

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.     

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.     

Mineralogy and major-element geochemistry of the lower Permian Greta Seam,Sydney Basin,Australia

The mineralogy of the high-volatile bituminous coals and associated strata from the Greta seam, Sydney Basin, Australia, has been evaluated in this study. Although the seam is not immediately overlain by marine strata, percolation of marine water into the original peat bed is indicated by the petrological, mineralogical and geochemical characteristics, which resemble those of coals with marine roof strata. The upper and lower sections of the seam have contrasting mineralogy. Pyrite typically comprises 40 to 56 wt% of the mineral assemblage in the marine-influenced upper part of the seam section. The lower part contains much less pyrite (typically <5 wt%, organic-free basis), and also relatively abundant dawsonite (up to 14 wt%, organic-free basis). The minerals within most coal plies are largely of authigenic origin. These include pyrite, siderite, clay minerals (mainly kaolinite and Na-rich mixed-layer illite/smectite), and quartz, most of which have a relatively early, syngenetic origin. Minor Ti-bearing minerals, anatase or rutile, and phosphate minerals, fluorapatite and goyazite, were probably also formed during early diagenesis. Other minerals have features that indicate late-stage precipitation. These include abundant cleat- and fracture-filling dawsonite, which may be the result of reactions between earlier-precipitated kaolinite and Na₂CO₃- or NaHCO₃-bearing fluids. Minor albite may also be epigenetic, possibly precipitated from the same Ca–Al bearing fluids that formed the dawsonite. The most abundant detrital minerals in the Greta coals are quartz, poorly ordered kaolinite, illite and mixed-layer illite/smectite (I/S). These occur mainly in the floor, roof and other epiclastic horizons of the seam, reflecting periods of greater clastic influx into those parts of the original peat-forming environment. Detrital minerals are rare in the coals away from the epiclastic horizons, probably owing to almost complete sediment bypassing in the depositional system. Alternatively, any detrital minerals that were originally present may have been leached from the peat bed by diagenetic or post-diagenetic processes.     

Geology,mineralization, stable isotope,and fluid inclusion characteristics of the Vostok-2 reduced W-Cu skarn and Au-W-Bi-As stockwork deposit,Sikhote-Alin,Russia

The large (>180 Kt WO₃ and at least 10–15 t Au) Vostok-2 deposit is situated in a metallogenic belt of W, Sn-W, Au, and Au-W deposits formed in late to post-collisional tectonic environment after cessation of active subduction. The deposit is related to an ilmenite-series high-K calc-alkaline plutonic suite that, by its petrologic signatures, is transitional between those at W-dominant and Au-dominant reduced intrusion-related deposits. Consistently, besides large W-Cu skarns of the reduced type, the deposit incorporates quartz stockworks with significant Au-W-Bi mineralization also formed in a reduced environment. The hydrothermal stages include prograde and retrograde, essentially pyroxene skarns, hydrosilicate (amphibole, chlorite, quartz) alteration, and phyllic (quartz, sericite, albite, apatite, and carbonate) alteration assemblages. These assemblages contain abundant scheelite associated with pyrrhotite, chalcopyrite and, at the phyllic stage, also with Bi minerals, As-Bi-Sb-Te-Pb-Zn sulfides and sulfosalts, as well as Au mineralization. The fluid evolution included hot, high-pressure (420–460 °C, 1.1–1.2 kbar), low-salinity (5.4–6.0 wt% NaCl-equiv.) aqueous fluids at the retrograde skarn stage, followed by lower temperature cyclic releases of high-carbonic, low salinity to non-carbonic moderate-salinity aqueous fluids. At the hydrosilicate stage, a high-carbonic, CH₄-dominated, hot (350–380 °C) low salinity fluid was followed by cooler (300–350 °C) non-carbonic moderate-salinity (5.7–14.9 wt% NaCl-equiv.) fluid. At the phyllic stage, a high-carbonic, CO₂-dominated, moderately-hot (330–355 °C, 0.9 kbar) low salinity fluid was followed by cooler (230–265 °C) non-carbonic moderate-salinity (6.6–12.0 wt% NaCl-equiv.) fluid. A homogenized magmatic source of water (δ¹⁸O_H2O = +8.3 to +8.7‰), and a sedimentary source of sulfur (δ³⁴S = −6.9 to −6.2‰) and carbon (δ¹³C_fluid = −20.1 to −14.9‰) at the hydrosilicate stage are suggested. A magmatic source of water (δ¹⁸O = +8.6 to +9.2‰) and a sedimentary source of sulfur (δ³⁴S = −9.3 to −4.1‰) but a magmatic (mantle- to crustal-derived) source of carbon (δ¹³C_fluid = −6.9 to −5.2‰) are envisaged for fluids that formed the early mineral assemblage of the phyllic stage. Then, the role of sedimentary carbon again increased toward the intermediate (δ¹³C_fluid = −16.4 to −14.5‰) and late (δ¹³C_fluid = −16.3 to −14.7‰) phyllic mineral assemblages. The magmatic differentiation was responsible for the fluid enrichment in W, whereas Au and Bi could also have been sourced from mafic magma. The decreasing temperatures, together with elevated Ca content in non-boiling fluids, promoted scheelite deposition at the early hydrothermal stages. The most intense scheelite deposition at the phyllic stage was caused by CO₂ removal due to boiling of CO₂-rich fluids; further cooling of non-boiling fluids favoured joint deposition of scheelite, Bi and Au.     

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.     

Carbonate dissolution in Mesozoic sand- and claystones as a response to CO2 exposure at 70 °C and 20 MPa

The response to CO₂ exposure of a variety of carbonate cemented rocks has been investigated using pressurised batch experiments conducted under simulated reservoir conditions, 70 °C and 20 MPa, and with a durations of up to14 months. Calcite, dolomite, ankerite and siderite cement were present in the unreacted reservoir rocks and caprocks. Core plugs of the reservoir rocks were used in order to investigate the alterations in situ. Crushing of the caprock samples was necessary to maximise reactions within the relatively short duration of the laboratory experiments. Synthetic brines were constructed for each batch experiment to match the specific formation water composition known from the reservoir and caprock formations in each well. Chemical matched synthetic brines proved crucial in order to avoid reactions due to non-equilibra of the fluids with the rock samples, for example observations of the dissolution of anhydrite, which were not associated with the CO₂ injection, but rather caused by mismatched brines.Carbonate dissolution as a response to CO₂ injection was confirmed in all batch experiments by both petrographical observations and geochemical changes in the brines. Increased Ca and Mg concentrations after 1 month reaction with CO₂ and crushed caprocks are ascribed to calcite and dolomite dissolution, respectively, though not verified petrographically. Ankerite and possible siderite dissolution in the sandstone plugs are observed petrographically after 7 months reaction with CO₂; and are accompanied by increased Fe and Mn contents in the reacted fluids. Clear evidence for calcite dissolution in sandstone plugs is observed petrographically after 14 months of reaction with CO₂, and is associated with increased amounts of Ca (and Mg) in the reacted fluid. Dolomite in sandstones shows only minor dissolution features, which are not clearly supported by increased Mg content in the reacted fluid.Silicate dissolution cannot be demonstrated, either by chemical changes in the fluids, as Si and Al concentrations remain below the analytical detection limits, nor by petrographical changes, as partly dissolved feldspar grains and authigenic analcime are present in the sediments prior to the experiments. It is noteworthy, that authigenic K-feldspar and authigenic albite in sandstones show no signs of dissolution and consequently seem to be stable under the experimental conditions.     

Geological,geochronological, and H–O isotopic constraints on the genesis of the Tongjing Cu–Au deposit in the Ningwu basin,east China

The Tongjing Cu–Au deposit is a medium-sized deposit within the Ningwu volcanic basin, east China, and is hosted by Cretaceous volcanic rocks of the Dawangshan and Niangniangshan Formations. The veined and lenticular Cu–Au orebodies are spatially and temporally related to the volcanic and subvolcanic rocks of the Niangniangshan Formation in the ore district. The wall-rock alteration is dominated by silicification, siderite alteration, carbonation, sericitization, chloritization, and kaolinization. On the basis of field evidence and petrographic observations, two stages of mineralization are recognized: (1) a siderite–quartz–sulfide stage (Stage 1) associated with the formation of chalcopyrite and pyrite in a quartz and siderite gangue; and (2) a quartz–bornite stage (Stage 2) cutting the Stage 1 phases. Stage 1 is the main mineralization stage. Quartz that formed in Stage 1 has δ¹⁸O_H2O values of − 4.3‰ to 3.5‰ with δD values of fluid inclusion waters of − 97.1‰ to − 49.9‰, indicating that the ore-forming fluids were derived from early magmatic fluids and may have experienced oxygen isotopic exchange with meteoric water during Stage 1 mineralization.LA–MC–ICP–MS zircon U–Pb dating of the mineralization-related nosean-bearing phonolite and nosean-bearing phonolitic brecciated tuff at Tongjing yields ages of 129.8 ± 0.5 Ma and 128.9 ± 1.1 Ma, respectively. These results are interpreted as the crystallization age of the volcanic rocks of the Niangniangshan Formation. A hydrothermal sericite sample associated with Cu–Au mineralization at Tongjing yields a plateau ⁴⁰Ar–³⁹Ar age of 131.3 ± 1.3 Ma. These results confirm a genetic link between the volcanism and associated Cu–Au mineralization. The Tongjing Cu–Au deposit in the Ningwu basin is genetically and possibly tectonically similar to alkaline intrusion-related gold deposits elsewhere in the world.     

Geochemistry and origin of the Neoproterozoic Dahongliutan banded iron formation (BIF) in the Western Kunlun orogenic belt,Xinjiang (NW China)

The Neoproterozoic (593–532 Ma) Dahongliutan banded iron formation (BIF), located in the Tianshuihai terrane (Western Kunlun orogenic belt), is hosted in the Tianshuihai Group, a dominantly submarine siliciclastic and carbonate sedimentary succession that generally has been metamorphosed to greenschist facies. Iron oxide (hematite), carbonate (siderite, ankerite, dolomite and calcite) and silicate (muscovite) facies are all present within the iron-rich layers. There are three distinctive sedimentary facies BIFs, the oxide, silicate–carbonate–oxide and carbonate (being subdivided into ankerite and siderite facies BIFs) in the Dahongliutan BIF. They demonstrate lateral and vertical zonation from south to north and from bottom to top: the carbonate facies BIF through a majority of the oxide facies BIF into the silicate–carbonate–oxide facies BIF and a small proportion of the oxide facies BIF.The positive correlations between Al₂O₃ and TiO₂, Sc, V, Cr, Rb, Cs, Th and ∑REE (total rare earth element) for various facies of BIFs indicate these chemical sediments incorporate terrigenous detrital components. Low contents of Al₂O₃ (<3 wt%), TiO₂ (<0.15 wt%), ∑REE (5.06–39.6 ppm) and incompatible HFSEs (high field strength elements, e.g., Zr, Hf, Th and Sc) (<10 ppm), and high Fe/Ti ratios (254–4115) for a majority of the oxide and carbonate facies BIFs suggest a small clastic input (<20% clastic materials) admixtured with their original chemical precipitates. The higher abundances of Al₂O₃ (>3 wt%), TiO₂, Zr, Th, Cs, Sc, Cr and ∑REE (31.2–62.9 ppm), and low Fe/Ti ratios (95.2–236) of the silicate–carbonate–oxide facies BIF are consistent with incorporation of higher amounts of clastic components (20%–40% clastic materials). The HREE (heavy rare earth element) enrichment pattern in PAAS-normalized REE diagrams exhibited by a majority of the oxide and carbonate facies BIFs shows a modern seawater REE signature overprinted by high-T (temperature) hydrothermal fluids marked by strong positive Eu anomalies (Eu/Eu¹_PAAS = 2.37–5.23). The low Eu/Sm ratios, small positive Eu anomaly (Eu/Eu¹_PAAS = 1.10–1.58) and slightly MREE (middle rare earth element) enrichment relative to HREE in the silicate–carbonate–oxide facies BIF and some oxide and carbonate facies BIFs indicate higher contributions from low-T hydrothermal sources. The absence of negative Ce anomalies and the high Fe³⁺/(Fe³⁺/Fe²⁺) ratios (0.98–1.00) for the oxide and silicate–carbonate–oxide BIFs do not support ocean anoxia. The δ¹³C_V-PDB (−4.0‰ to −6.6‰) and δ¹⁸O_V-PDB (−14.0‰ to −11.5‰) values for siderite and ankerite in the carbonate facies BIF are, on average, ∼6‰ and ∼5‰ lower than those (δ¹³C_V-PDB = −0.8‰ to + 3.1‰ and δ¹⁸O_V-PDB = −8.2‰ to −6.3‰) of Ca–Mg carbonates from the silicate–carbonate–oxide facies BIF. This feature, coupled with the negative correlations between FeO, Eu/Eu¹_PAAS and δ¹³C_V-PDB, imply that a water column stratified with regard to the isotopic omposition of total dissolved CO₂, with the deeper water, from which the carbonate facies BIF formed, depleted in δ¹³C that may have been derive from hydrothermal activity.Integration of petrographic, geochemical, and isotopic data indicates that the silicate–carbonate–oxide facies BIF and part of the oxide facies BIF precipitated in a near-shore, oxic and shallow water environment, whereas a majority of the oxide and carbonate facies BIFs deposited in anoxic but Fe²⁺-rich deeper waters, closer to submarine hydrothermal vents. High-T hydrothermal solutions, with infusions of some low-T hydrothermal fluids, brought Fe and Si onto a shallow marine, variably mixed with detrital components from seawaters and fresh waters carrying continental landmass and finally led to the alternating deposition of the Dahongliutan BIF during regression–transgression cycles.The Dahongliutan BIF is more akin to Superior-type rather than Algoma-type and Rapitan-type BIF, and constitutes an additional line of evidence for the widespread return of BIFs in the Cryogenian and Ediacaran reflecting the recurrence of anoxic ferruginous deep sea and anoxia/reoxygenation cycles in the Neoproterozoic. In combination with previous studies on other Fe deposits in the Tianshuihai terrane, we propose that a Fe²⁺-rich anoxic basin or deep sea probably existed from the Neoproterozoic to the Early Cambrian in this area.     

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.