Origin of ore-forming fluids in Qinggouzi stibnite deposit,NE China:Constraints from fluid inclusions and H-O-S isotopes

The Qinggouzi stibnite deposit is located in Huashan Town,Jilin Province,in the northeastern margin of North China Craton(NCC).It is controlled by fault structures,hosted within structurally controlled felsic dykes,predominantly surrounded by phyllite,schist and quartzite.This study presents the results of fluid inclusions studies,intending to determine the source of the fluid responsible for ore-formation,hence exploring its metallogenesis.The aqueous biphase inclusions are identified in the stibnite-bearing quartz veins of the deposit.Moreover,aqueous biphase inclusions are further classified into(1)biphase liquid-rich inclusions(1 a)and(2)biphase gas-rich inclusions(1 b)depending upon liquid to gas ratio trapped within the fluid inclusions.Homogenization temperatures for(1 a)and(1 b)range between 114.8℃to 422℃and 128.3℃to 267.5℃,respectively.1 a and 1 b have salinities of 0.18%to 16.14%NaCleqv and 1.22%to 12.88%NaCleqv,and density range from 0.43 to 1.02 g/cm^(3) and 0.81 to 0.98 g/cm^(3),respectively.Sulfur isotopic analysis indicatesδ34SV-CDT from 4.4×10-3 to 6.5×10^(-3),with an average of 5.2×10^(-3),whereas H isotopes values onδDV-SMOW standard are-100.8×10^(-3) and-107.5×10^(-3),while O isotopes data onδ18OV-SMOW standard range between 20.1×10^(-3) and 20.4×10-3.Fluid inclusions study,combining with sulfur and H-O isotopic data reveal that the ore-forming fluids originated from deep source and were subsequently contaminated by meteoric water.Hydrostatic pressure calculation shows that the minimum and maximum pressures are 11.65 and 42.33 MPa,and relevant depths of deposit are estimated to be 1.16 and 4.23 km.Finally,we inferred that Qinggouzi stibnite deposit is a medium-low temperature,low salinity hydrothermal deposit,which is formed by deep source and later contaminated by meteoric water,and is classified as epizonal deposit in terms of orogenic series.

Trace-element geochemistry and S–O isotopes in the fluorite-barite mineralization of Merguechoum,Moroccan eastern Meseta:insights into ore genesis to the Pangea rifting

The Merguechoum fluorite-barite mineralization,located in the Eastern Meseta of Morocco,is hosted in the Late Hercynian granite.The ore consists of fine crystals of fluorite 1,massive barite 1,euhedral crystals of fluorite 2,and barite 2 with calcite and minor quartz and sulfides.The Merguechoum ore deposits have never been investigated.This study was the first contribution that studied the genesis of fluorite and barite.The ore occurs as dissemination within granite intrusion and also fills the NE-SWtrending meter-sized fractures and faults.The values of the total Rare Earth Elements and Yttrium(REY)and the ratios of LREY/HREY,Y/Ho,Tb/Ca,and Tb/La indicate that the Merguechoum fluorite precipitated from hydrothermal fluids,likely basinal brines,which interacted with the Hercynian granite.The REY data indicate that the ore-forming fluids of the early stage have intensely interacted with the Hercynian granite compared to those of the late ore stage.The gradual decrease in the europium(Eu/Eu^(*)),yttrium(Y/Y^(*)),and cerium(Ce/Ce^(*))anomalies and a low concentration ofΣREY observed in the second ore stage compared to the first ore stage suggest an increase in p H and fO_(2)and by inference a decrease in temperature during the evolution of the hydrothermal system.This evolution could be explained by fluid mixing between the ascending basinal hydrothermal fluids and the diluted sulfate-rich meteoric water barite separates from selected samples reveal that the dissolved sulfates(SO_(4)^(2-))were derived from Permian–Triassic sulfates and/or coeval poreseawater sulfates.The proposed fluid mixing triggered the precipitation of an early-stage F-Ba assemblage followed by the second-stage F-Ba mineralization.Geologic fieldwork,REY inventories,and isotope data point to the ore genesis during the Permian–Triassic extensional tectonic activity concerning the Pangea rifting.This extensional tectonic environment is likely the driving force that mobilized a large amount of the ore-forming basinal brines along the available faults and fractures to the loci of ore deposition.

Fluid inclusion and H-O-S-Pb isotope systematics of the Chayong Cu-polymetallic deposit,Sanjiang Metallogenic Belt,Qinghai Province,China

The Chayong Cu-polymetallic deposit is a recently discovered Cu-polymetallic deposit hosted in the Sanjiang Metallogenic Belt within the Tibetan Plateau of China to the northeast of the North Qiangtang terrane.The ore body occurs in siltstone and is controlled by a northwest-trending fault structure.According to the associations,assemblages,and cutting relationships between ore veins,the hydrothermal mineralization period can be divided into three mineralization stages:(1)a molybdenite mineralization stage,(2)a Cu-polymetallic sulfide stage,and(3)a quartzcarbonate stage.Two types of fluid inclusions(FIs),namely,liquid and vapor-rich inclusions,are present in quartz as so ciated with sulfide minerals.Early-stage FIs are both iquid and vapor-rich,homogenized at temperatures ranging from 364.1 to 384.2℃,and have salinities ranging from0.70%to 9.60%NaCl equivalent(eqv).The middle-stage FIs are also both liquid-and vapor-rich,homogenized at temperatures ranging from 272.4 to 355.6℃,and have salinities ranging from 0.53%-17.10%NaCl eqv.The late-stage FIs are liquid,homogenized at temperatures ranging from 209.4to 255.3℃,and have salinities ranging from 0.35%-6.87%NaCl eqv.The samples from the deposit haveδ^(34)S values of-21.8‰to-19.2‰and-5.5‰to-6.0‰,suggesting that sulfur was derived from the host sediments and magmatic fluids,respectively.The metallic minerals within the deposit have~(206)Pb/~(204)Pb,~(207)Pb/~(204)Pb,and~(208)Pb/~(204)Pb values of 18.439-18.458,15.656-15.679,and 38.772-38.863,respectively,suggesting that the metals were derived from the upper crust and orogenic belts.The samples from the deposit haveδ^(18)O_(W)values of 2.99‰-7.99‰andδD_W values ranging from-84.4‰to-73.9‰,indicating that the pre-forming fluids were magmatic and mixed with minor amounts of meteoric water.The ore-forming fluid of the Chayong copper polymetallic deposit was a high-temperature,medium-to low-salinity H_2O-NaCl-CH_4-N_2±CO_(2)fluid system.The early high-temperature magmatic fluid,due to boiling,decreased in temperature,and via the mixing of meteoric water,gradually evolved towards the later-stage medium-to low-temperature and low-salinity fluid,causing nolybdenite mineralization and forming copper polymetallic sulfide veins and quartz carbonate veins.

Melt extraction and mineralization: A case study from the Shuangjianzishan supergiant Ag-Pb-Zn deposit(208 Mt), Inner Mongolia, NE China

The supergiant Shuangjianzishan(SJZ) Ag-Pb-Zn deposit is in the southern segment of the Great Hinggan Range(SGHR), northeast China. Previous studies suggest the ore-forming material and fluid originated from the magmatic system, and the mineralization age was consistent with the diagenetic age. However,the relationship between granitic magmatism and mineralization is still unclear in the SJZ. In this study, CH-O-He-Ar and in-situ S-Pb isotope analyses were conducted to determine the sources of ore-forming fluids and metals, which were combined with geochemistry data of SJZ granitoids from previous studies to constrain the relationship between the magmatism and the mineralization. The C-H-O-He-Ar-S-Pb isotopic compositions suggested the SJZ ore-forming material and fluids were derived from a magmatic source, which has mixed a small amount of mantle-derived materials. In addition, the disseminated sulfide from the syenogranite has comparable S-Pb isotopic composition with the sulfide minerals from ore veins,suggesting that the generation of the SJZ ore-forming fluids has a close relationship with the syenogranite magmatism. Combining with the geochemical characters of the syenogranite, the authors proposed that the mantle-derived fingerprint of the SJZ ore-forming fluid might be caused by the parent magma of the syenogranite, which was derived from partial melting of the juvenile lower crust, and underwent the residual melts segregated from a crystal mush in the shallow magma reservoir. The extraction of the syenogranite parent magma further concentrated the fertilized fluids, which was crucial to mineralization of the SJZ Ag-Pb-Zn deposit.

Provenance and salt structures of gypsum formations in Pb-Zn ore-bearing Lanping basin,Southwest China

Large-scale gypsum rocks associated with world-class Pb-Zn ore formations are widely distributed in the Lanping Basin,Sowthwest China.Geochemical studies alongside field investigations were conducted in this study to determine the source and evolutionary processes of the gypsum rocks in this area.The gypsum sequences in the Lanping Basin developed in two formations:the Triassic Sanhedong Formation and the Paleogene Yunlong Formation.The gypsum hosted in the former displays a primary thick-banded structure withδ34SV-CDT values in the range of 14.5‰−14.8‰.Combined with the 87Sr/86Sr values(0.707737−0.707783)of limestone,it can be suggested that the Sanhedong Formation is of marine origin.In contrast,the gypsum from the Paleogene Yunlong Formation is characterized by the dome,bead and diapiric salt structures,wider range of both 87Sr/86Sr(0.707695−0.708629)andδ34SV-CDT values(9.6‰−17‰),thus indicating a marine source but with the input of continental materials.The initial layered salt formations were formed by chemical deposition in a basin and were later intensely deformed by collisional orogeny during the Himalaya period.As a result,variable salt structures were formed.We hereby propose an evolutionary model to elucidate the genesis of the gypsum formations in the Lanping Basin.

Power-law patterns in the Phanerozoic sedimentary records of carbon, oxygen, sulfur,and strontium isotopes

Power-law patterns appear in a variety of natural systems on the modern Earth;nevertheless,whether such behaviors appeared in the deep-time environment has rarely been studied. Isotopic records in sedimentary rocks, which are widely used to reconstruct the geological/geochemical conditions in paleoenvironments and the evolutionary trajectories of biogeochemical cycles, offer an opportunity to investigate power laws in ancient geological systems. In this study, I focus on the Phanerozoic sedimentary records of carbon, oxygen, sulfur, and strontium isotopes, which have well documented and extraordinarily comprehensive datasets. I perform statistical analyses on these datasets and show that the variations in the sedimentary records of the four isotopes exhibit power-law behaviors. The exponents of these power laws range between 2.2 and 2.9;this narrow interval indicates that the variations in carbon, oxygen, sulfur, and strontium isotopes likely belong to the same universality class, suggesting that these systematic power-law patterns are governed by universal, scale-free mechanisms. I then derive a general form for these power laws from a minimalistic model based on basic physical principles and geosystem-specific assumptions, which provides an interpretation for the power-law patterns from the perspective of thermodynamics. The fundamental mechanisms regulating such patterns might have been ubiquitous in paleoenvironments, implying that similar power-law behaviors may exist in the sedimentary records of other isotopes.

Evidence of fluid evolution of Baoshan Cu−Pb−Zn polymetallic deposit:Constraints from in-situ sulfur isotope and trace element compositions of pyrite

In-situ LA-ICP-MS and S isotopes of pyrite from the Baoshan Cu polymetallic deposit were conducted to investigate the ore-forming process and the enrichment mechanism of elements.Three generations of pyrite (Py Ⅰ,Py Ⅱ,and Py Ⅲ) in the skarn-type ores and pyrite in the carbonate-hosted sulfide ores from central,western,and northern(C_Py,W_Py,and N_Py) mining districts are selected for comparison.Compared with Py Ⅰ and Py Ⅲ,the contents of most elements in Py Ⅱ are apparently higher.The As and Se contents are high within a wide range and are decoupled in the growth band of the C_Py.The highest As,Se,and Pb contents were found in W_Py and N_Py.These results indicate the drastic changes in the temperature and fluid mixing during the mineralization.The occurrence of fluctuation and change in temperature and f(O_(2)) was triggered by intermittent pulses of magmatic-hydrothermal fluids,mixing with meteoric water,and water-rock interactions.The sulfur isotopes of all species of pyrite indicated the magmatic source.The change in the f(O_(2)) conditions caused slight differences in the sulfur isotope compositions.Consequently,a metallogenic model was proposed to explain the ore-forming processes.

Origin of Paleofluids in Dabashan Foreland Thrust Belt:Geochemicai Evidence of ^(13)C,^(18)O and ^(87)Sr/^(86)Sr in Veins and Host Rocks

In the last ten years, with important discoveries from oil and gas exploration in the Dabashan foreland depression belt in the borderland between Shanxi and Sichuan provinces, the relationship between the formation and evolution of, and hydrocarbon accumulation in, this foreland thrust belt from the viewpoint of basin and oil and gas exploration has been studied. At the same time, there has been little research on the origin of fluids within the belt. Based on geochemical system analysis including Z values denoting salinity and research on δ13C, δ18O and S7Sr/S6Sr isotopes in the host rocks and veins, the origin of paleofluids in the foreland thrust belt is considered. There are four principal kinds of paleofluid, including deep mantle-derived, sedimentary, mixed and meteoric. For the deep mantle-derived fluid, the δ13C is generally less than -5.0‰PDB, δ18O less than -10.0‰PDB, Z value less than 110 and 87Sr/86Sr less than 0.70600; the sedimentary fluid is mainly marine carbonate- derived, with the δ13C generally more than -2.0‰PDB, 18δO less than -10.0‰PDB, Z value more than 120 and STSr/S6Sr ranging from 0.70800 to 0.71000; the mixed fluid consists mainly of marine carbonate fluid （including possibly a little mantle-derived fluid or meteoric water）, with the j13C generally ranging from -2.0‰ to -8.0‰PDB, δ18O from -10.0‰ to -18.0‰ PDB, Z value from 105 to 120 and 87Sr/86Sr from 0.70800 to 0.71000; the atmospheric fluid consists mainly of meteoric water, with the δ13C generally ranging from 0.0‰ to -10.0‰PDB, δ18O less than -8.0%rPDB, Z value less than 110 and 87Sr/86Sr more than 0.71000. The Chengkou fault belt encompasses the most complex origins, including all four types of paleofluid; the Zhenba and Pingba fault belts and stable areas contain a simple paleofluid mainly of sedimentary type; the Jimingsi fault belt contains mainly sedimentary and mixed fluids, both consisting of sedimentary fluid and meteoric water. Jurassic rocks of the foreland depression belt contain mainly meteoric fluid.

Sources of the Laoxiongdong carbonate-hosted Pb–Zn deposit in Southwest China:constraints from S–Pb–Zn isotopic compositions

The Sichuan-Yunnan-Guizhou(SYG)Pb-Zn mineral province,which has significant Pb-Zn repositories in China,is situated in the western Yangtze Block.Despite decades of research,the Pb-Zn source of deposits is still disputed between the basement rocks,sedimentary wall rocks,or the Emeishan flood basalts.The newly-discovered Laoxiongdong Pb-Zn deposit is hosted by the Late Ediacaran Dengying Formation in the SYG province.Moreover,the Laoxiongdong orebodies lie between regional deep faults and close to the Proterozoic basement and Emeishan basalts.Hence,this deposit represents a good case study on the ore-forming material source for the regional Pb-Zn mineralization.The Laoxiongdong Pb-Zn ores are massive,vein,or disseminated and have mainly sphalerite,galena,pyrite,quartz,and calcite.In this paper,we present new sulfide S-Pb-Zn isotope data of the deposit.The sulfideδ34SCDT values(+11.8 to+16.5‰)suggest that the reduced sulfur was mainly sourced from evaporites in the Late Ediacaran-Cambrian sequences.Pb isotopic ratios(206Pb/204Pb=18.004-18.107,207Pb/204Pb=15.652-15.667,and 208Pb/204Pb=38.037-38.248)suggest that the lead metal was primarily originated from the basement rocks.The sphaleriteδ66Zn values(+0.16 to+0.37‰)are also highly similar(within error)to those of basement rocks(+0.10 to+0.34‰),suggesting a basement-rocks zinc source with minor contributions from the carbonate host rocks and Emeishan flood basalts.The narrow sphalerite Zn isotopic range(0.21‰)also indicates that the Zn isotopic fractionation between the sphalerite and initial fluid was limited during the sphalerite ore precipitation.Therefore,we propose that both the Late Ediacaran Dengying Formation rocks and Proterozoic basement rocks were important ore-forming material source for the Laoxiongdong deposit,whereas the Emeishan flood basalts represent only a minor ore-material source.

Lithological and Si–O–S isotope geochemistry:constraints on the origin and genetic environment of the selenium(Se)-rich siliceous rocks in Enshi,Hubei Province,China

Se-rich black rock series of the Middle and Late Permian system is widely distributed in Enshi Prefecture with an exposed area of 850 km~2,among which the unique Yutangba black rock series independent selenium deposit with industrial mining significance in the world is produced.However,the source and metallogenic mechanisms of Se are still controversial.In general,terrestrial weathering and submarine hydrothermal processes are the main source end members of Si and Se,and the related siliceous rocks record the deposition process of Si and Se from different sources.The study of lithofacies and paleogeography shows that western Hubei belongs to the near eastwest turn of the Yangzi platform in the Middle and Late Permian and becomes an inter-platform basin with nearly north-south direction.Therefore,the comparative study of the Yutangba deposit and the selenium-rich black rock series in the northern Shadi with high selenium content is expected to reveal the provenance evolution of the two sections in space,and further restrict the Se mineralization mechanism in the Enshi basin.From the element geochemistry study,the black rock series in two study areas may have formed in a transitional position of either the continental margin or continental slope,in the process of sedimentary,more terrigenous clastic materials entered.They are rich in lithophile elements V and Cr.δU>1.0,U/Th and V/(V+Ni)ratio indicate that the Se-rich strata of black rock series in the Enshi areas occurred in an anoxic reducing environment and formed in an environment between the ocean basin and the continental margin.From Si-O isotope geochemistry,the original Si source of the study area is thought to relate to a volcanic eruption,which leads to the enrichment of Si in the seawater.The determined values of S isotope in the black rock series of the two study areas both show the characteristics related to organic reduction/biogenic.

Composition of Pancarli Magmatic Ni-Cu±(PGE) Sulfide Deposit in the Cadomian-Avalonian Belt, Eastern Turkey

Pancarli Ni-Cu±(PGE)sulfide deposit occurs in the Neoproterozoic basement complex of the Bitlis massif,which is one of the Andean-type active continental margin fragments with arc-type assemblages represented by the Cadomian orogenic belt.Pancarli sulfides are associated with quartzo-feldspathic gneisses(country rock)and mafic intrusions(host rock).Composed of only semi-massive ore,the Ni-Cu±(PGE)sulfide deposit is a small-scale deposit,and it does not contain net-textured and disseminated ore.The mineral assemblage comprises pyrrhotite,pentlandite,and chalcopyrite.The semi-massive ore samples contain 2.2 wt.%-2.9 wt.%Ni,0.8 wt.%-2.2 wt.%Cu(Cu/(Cu+Ni)=0.2-0.5)and 0.13 wt.%-0.17 wt.%Co.The Cu/Ni ratios(average 0.57)are consistent with the segregation of sulfides from a basaltic magma.Low Pt+Pd100%S values of 0.08 ppm-0.89 ppm,relatively low Pt/Pd ratios of 0.2-1.4,and Pd/Ir ratios of 4.5-39 have also been revealed.These values demonstrate that the magma reached S saturation before its emplacement and the mineralization with high Cu/Pd ratios formed by sulfides segregated from a PGE-depleted magma.δ^34S isotope values(average-3.1‰)of Pancarli sulfides are lower than mantle source.Negativeδ^34S value indicates contamination from surrounding rocks.Concerning the composition,remobilization style and magma type,the Pancarli Ni-Cu±(PGE)sulfide deposit is similar to the deposits associated with Andean-type magmatic arcs located in the convergent plate margin settings.

Genesis of the Xinfang Gold Deposit,Liaodong Peninsula:In-sights from Fluid Inclusions and S-Sr Isotopic Constraints

The North China Craton(NCC)has been continuously reactivated since the Mesozoic and this decratonization is responsible for its economically important gold mineralization in the Meso-zoic.The Early Cretaceous(110-130 Ma)gold mineralization in the NCC has been well-studied due to its significance,but little attention has been given to other episodes of gold mineralization related to polyphased reactivation of the NCC.The Xinfang mesozonal gold deposit(143 Ma)in the Liaodong Peninsula is related to the one of the episodes of the Yanshanian orogeny.The orebodies of the Xin-fang gold deposit were controlled by the low angle transpressive fault systems and hosted by the Neoarchean monzogranitic gneiss.Fluid inclusion microthermometry reveals that the mineralizing temperatures range from 220 to 280℃,with salinities from 6 wt.%NaCl eqv.to 15 wt.%NaCl eqv.,pressures from 199 to 321 Ma.The S isotopic characteristics of sulfides not only record a heterogene-ous source including magmatic or gneissic sulfur but also record inter-mineral isotope fractionation.The initial^(87)Sr/^(86)Sr values of pyrite(0.713480-0.729031)indicate a radiogenic crustal origin for the sources.The metamorphic dehydration of the underlying basement resulted in the genesis of the Xin-fang gold deposit.We summarize three episodes of gold mineralization in the Liaodong Peninsula re-lated to continuous reactivation of the NCC,which indicates a great exploration potential of this area.

Microbial communities biostimulated by ethanol during uranium （VI） bioremediation in contaminated sediment as shown by stable isotope probing

Stable isotope probing （SIP） was used to identify microbes stimulated by ethanol addition in microcosms containing two sediments collected from the bioremediation test zone at the US Department of Energy Oak Ridge site, TN, USA. One sample was highly bioreduced with ethanol while another was less reduced. Microcosms with the respective sediments were amended with ^13C labeled ethanol and incubated for 7 days for SIP. Ethanol was rapidly converted to acetate within 24h accompanied with the reduction of nitrate and sulfate. The accumulation of acetate persisted beyond the 7 d period. Aqueous U did not decline in the microcosm with the reduced sediment due to desorption of U but continuously declined in the less reduced sample. Microbial growth and concomitant 13C-DNA production was detected when ethanol was exhausted and abundant acetate had accumulated in both microcosms. This coincided with U（VI） reduction in the less reduced sample. I3C originating from ethanol was ultimately utilized for growth, either directly or indirectly, by the dominant microbial community members within 7 days of incubation. The microbial community was comprised predominantly of known denitrifiers, sulfate-reducing bacteria and iron （Ⅲ） reducing bacteria including Desulfovibrio, Sphingomonas, Ferribacterium, Rhodanobacter, Geothrix, Thiobacillus and others, including the known U（VI）-redueing bacteria Acidovorax, Anaeromyxobacter, Desulfovibrio, Geobac- ter and Desulfosporosinus. The findings suggest that ethanol biostimulates the U（VI）-reducing microbial com- munity by first serving as an electron donor for nitrate, sulfate, iron （IH） and U（VI） reduction, and acetate which then functions as electron donor for U（VI） reduction and carbon source for microbial growth.

Postherpetic Comedones in Two Chinese Han Patients

Wolf＇s postherpetic isotopic response （PHIR） describes the occurrence of a new lesion at the site of a healed herpetic lesion. It is more commonly seen alter infection by varicella-zoster virus （VZV） than herpes simplex virus. Such postherpetic lesions present with a board spectrum from inflammatory diseases to malignancies.

An isotope study of the accumulation mechanisms of high-sulfur gas from the Sichuan Basin, southwestern China

The mechanism of hydrogen sulfide(H_2S) generation plays a key role in the exploration and development of marine high-sulfur natural gas, of which the major targets are the composition and isotope characteristics of sulfur-containing compounds.Hydrocarbon source rocks, reservoir rocks, natural gases and water-soluble gases from Sichuan Basin have been analyzed with an online method for the content of H_2S and isotopic composition of different sulfur-containing compounds. The results of comparative analysis show that the sulfur-containing compounds in the source rocks are mainly formed by bacterial sulfate reduction(BSR), and the sulfur compounds in natural gas, water and reservoir are mainly formed by thermal sulfate reduction(TSR). Moreover, it has been shown that the isotopically reversion for methane and ethane in high sulfur content gas is caused by TSR. The sulfur isotopic composition of H_2S in natural gas is inherited from the gypsum or brine of the same or adjacent layer,indicating that the generation and accumulation of H_2S have the characteristics of either a self-generated source or a near-source.