Metallogenic Age and Ore-forming Material Sources of the Dahongshan Fe-Cu Deposit,Yunnan Province:Insights from Molybdenite Re-Os Dating and H-O-S-Pb Isotopes

The Dahongshan Fe-Cu(-Au)deposit is a superlarge deposit in the Kangdian metallogenic belt,southwestern China,comprising approximately 458 Mt of Fe ores(40%Fe)and 1.35 Mt Cu.Two main types of Fe-Cu(-Au)mineralization are present in the Dahongshan deposit:(1)early submarine volcanic exhalation and sedimentary mineralization characterized by strata-bound fine-grained magnetite and banded Fe-Cu sulfide(pyrite and chalcopyrite)hosted in the Na-rich metavolcanic rocks;(2)late hydrothermal(-vein)type mineralization characterized by Fe-Cu sulfide veins in the hosted strata or massive coarse-grained magnetite orebodies controlled by faults.While previous studies have focused primarily on the early submarine volcanic and sedimentary mineralization of the deposit,data related to late hydrothermal mineralization is lacking.In order to establish the metallogenic age and ore-forming material source of the late hydrothermal(-vein)type mineralization,this paper reports the Re-Os dating of molybdenite from the late hydrothermal vein Fe-Cu orebody and H,O,S,and Pb isotopic compositions of the hydrothermal quartz-sulfide veins.The primary aim of this study was to establish the metallogenic age and ore-forming material source of the hydrothermal type orebody.Results show that the molybdenite separated from quartz-sulfide veins has a Re-Os isochron age of 831±11 Ma,indicating that the Dahongshan Fe-Cu deposit experienced hydrothermal superimposed mineralization in Neoproterozoic.The molybdenite has a Re concentration of 99.7-382.4 ppm,indicating that the Re of the hydrothermal vein ores were primarily derived from the mantle.The δ^(34)S values of sulfides from the hydrothermal ores are 2‰-8‰ showing multi-peak tower distribution,suggesting that S in the ore-forming period was primarily derived from magma and partially from calcareous sedimentary rock.Furthermore,the abundance of radioactive Pb increased significantly from ore-bearing strata to layered and hydrothermal vein ores,which may be related to the later hydrothermal transformation.The composition of H and O isotopes within the hydrothermal quartz indicates that the ore-forming fluid is a mixture of magmatic water and a small quantity of water.These results further indicate that the late hydrothermal orebodies were formed by the Neoproterozoic magmatic hydrothermal event,which might be related to the breakup of the Rodinia supercontinent.Mantle derived magmatic hydrothermal fluid extracted ore-forming materials from the metavolcanic rocks of Dahongshan Group and formed the hydrothermal(-vein)type Fe-Cu orebodies by filling and metasomatism.

Origin and evolution of ore-forming fluid for the Gaosongshan gold deposit, Lesser Xing’an Range:Evidence from fluid inclusions,H-O-S-Pb isotopes

Epithermal gold deposits are typical precious metal deposits related to volcanic and subvolcanic magmatism.Due to the lack of direct geological and petrographic evidences,the origin of the ore-forming fluid is deduced from the spatial diagenesis-mineralization relationship,chronological data,physicochemical characteristics of mineral fluid inclusions,mineral or rock elements and isotopic geochemical characteristics.By objectively examining this scientific problem via a geological field survey and petrographic analysis of the Gaosongshan epithermal gold deposit,we recently discovered and verified the following points:(1) Pyrite-bearing spherical quartz aggregates (PSQA) occur in the rhyolitic porphyry;(2) the mineralization is structurally dominated by WNW- and ENE-trending systems and occurs mostly in hydrothermal breccias and pyrite-quartz veins,and the ore types are mainly hematite-crusted quartz,hydrothermal breccia,massive pyrite-quartz,etc.;(3) the alteration types consist of prevalent silicification,sericitization,propylitization and carbonation,with local adularization and illitization.The ore minerals are mainly pyrite,primary hematite,native gold,and electrum,with lesser amounts of chalcopyrite,magnetite,sphalerite,and galena,indicating a characteristic epithermal low-sulfidation deposit.The ore-forming fluid may have been primarily derived from magmatic fluid exsolved from a crystallizing rhyolitic porphyry magma.Further zircon U-Pb geochronology,fluid inclusion,physicochemical and isotopic geochemical analyses revealed that (1) rhyolitic porphyry magmatism occurred at 104.6 ± 1.0 Ma,whereas the crystallization of the PSQA occurred at 100.8 ± 2.1 Ma;(2) the hydrothermal fluid of the pre-ore stage was an exsolved CO2-bearing H2O-NaCl magmatic fluid that produced inclusions mainly composed of pure vapor (PV),vapor-rich (WV) and liquid-rich (WL) inclusions with a small number of melt-(M) and solid-bearing (S) inclusions;mineralization-stage quartz contains WL and rare PV,WV and pure liquid (PL) inclusions characterized by the H2O-NaCl system with low formation temperatures and low salinities;(3) the characteristics of hydrogen,oxygen,sulfur,and lead isotopes and those of rare earth elements (REEs) provide insight into the affinity between PSQA and orebodies resulting from juvenile crust or enriched mantle.Combined with previous research on the mineralogenetic epoch (99.32 ± 0.01 Ma),we further confirm that the mineralization of the deposit occurred in the late Early Cretaceous,which coincides with the extension of the continental margin induced by subduction of the Pacific Plate beneath the Eurasian Plate.The formation of the ore deposit was proceeded by a series of magmatic and hydrothermal events,including melting of enriched juvenile crust,upwelling,the eruption and emplacement of the rhyolitic magma,the exsolution and accumulation of magmatic hydrothermal fluid,decompression,the cooling and immiscibility/boiling of the fluid,and mixing of the magmatic fluid with meteoric water,in association with water-rock interaction.

Rising utilization of stable isotopes in tree rings for climate change and forest ecology

Analyses of stable isotopes(C,O,H)in tree rings are increasingly important cross-disciplinary programs.The rapid development in this field documented in an increasing number of publications requires a comprehensive review.This study includes a bibliometric analysis-based review to better understand research trends in tree ring stable isotope research.Overall,1475 publications were selected from the Web of Science Core Collection for 1974-2023.The findings are that:(1)numbers of annual publications and citations increased since 1974.From 1974 to 1980,there were around two relevant publications per year.However,from 2020 to 2022,this rose sharply to 109 publications per year.Likewise,average article citations were less than four per year before 1990,but were around four per article per year after 2000;(2)the major subjects using tree ring stable isotopes include forestry,geosciences,and environmental sciences,contributing to 42.5%of the total during 1974-2023;(3)the top three most productive institutions are the Chinese Academy of Sciences(423),the Swiss Federal Institute for Forest,Snow and Landscape Research(227),and the University of Arizona(204).These achievements result from strong collaborations;(4)review papers,for example,(Dawson et al.,Annu Rev Ecol Syst 33:507-559,2002)and(McCarroll and Loader,Quat Sci Rev 23:771-801,2004),are among the most cited,with more than 1000 citations;(5)tree ring stable isotope studies mainly focus on climatology and ecology,with atmospheric CO_(2) one of the most popular topics.Since 2010,precipitation and drought have received increasing attention.Based on this analysis,the research stages,key findings,debated issues,limitations and direc-tions for future research are summarized.This study serves as an important attempt to understand the progress on the use of stable isotopes in tree rings,providing scientific guid-ance for young researchers in this field.

Tracing nitrate sources in one of the world's largest eutrophicated bays(Hangzhou Bay):insights from nitrogen and oxygen isotopes

Eutrophication caused by inputs of excess nitrogen(N) has become a serious environmental problem in Hangzhou Bay(China),but the sources of this nitrogen are not well understood.In this study,the August 2019 distributions of salinity,nutrients [nitrate(NO_(3)^(-)),nitrite,ammonium,and phosphate],and the stable isotopic composition of NO_(3)^(-)(δ^(15)N and δ^(18)O) were used to investigate sources of dissolved inorganic nitrogen(DIN) to Hangzhou B ay.Spatial distributions of nitrate,salinity,and nitrate δ^(18)O indicate that the Qiantang River,the Changjiang River,and nearshore coastal waters may all contribute nitrate to the bay.Based on the isotopic compositions of nitrate in these potential source waters and conservative mixing of nitrate in our study area,we suggest that the NO_(3)^(- )in Hangzhou B ay was likely derived mainly from soils,synthetic N fertilizer,and manure and sewage.End-member modeling indicates that in the upper half of the bay,the Qiantang River was a very important DIN source,possibly contributing more than 50% of DIN in the bay head area.In the lower half of the bay,DIN was sourced mainly from strongly intruding coastal water.DIN coming directly from the Changjiang River made a relatively small contribution to Hangzhou Bay DIN in August 2019.

Source of Ore-Forming Fluid and Material in the Baiyun Gold Deposit, Liaoning Province, NE China: Constraints from H-O-S-Pb Isotopes and in-situ Analyses of Au-Bearing Pyrites

The Baiyun deposit is a large gold deposit at the western end of the Liaoji rift zone in Liaoning Province, which has produced both auriferous quartz-vein type and altered-rock type mineralization. The ore bodies are mainly hosted in schist from the Gaixian Formation of the Liaohe Group. A detailed field geological survey showed that the quartz-vein type gold ore bodies are distributed in the near EW-trending and occur in the extensional tectonic space of schist in the Gaixian Formation, and the altered-rock type gold ore bodies are distributed in the near EW-trending structural belt and occur near in the Gaixian Formation of biotite schist, biotite granulite, marble and the upper footwall of dike. To further elucidate the source of ore-forming fluid and material in the Baiyun gold deposit, the H-O isotopes for quartz, S and Pb isotopes, in-situ trace elements for sulfides from quartz-vein and altered-rock type mineralization were studied. The H-O isotopic δD_(V-SMOW) and δ^(18)O_(H2O) values of the auriferous quartz range were from-88.8‰ to-82.2‰ and-1.95‰ to 4.85‰, respectively, suggests that the ore-forming fluids were mainly magmatic water with minor meteoric water. The distribution ranges of in-situ S isotopic compositions of Au-bearing pyrite in the quartz-vein type and altered-rock type ores were-8.38‰–-10.47‰(with average values of-7.89‰) and 11.38‰– 17.52‰(with average values of 11.55‰), respectively, indicating that the S isotopic compositions of the two ore types were clearly different. The in-situ Pb isotopic ratios changed almost uniformly, which showed that they had the same lead isotopic source. Based on the analysis of S and Pb isotopic compositions, the metallogenic materials in the Baiyun gold deposit were primarily from deep magma, and some wall rock materials may have been mixed in the metallogenic process. Co/Ni diagram shows that most Au-bearing pyrites have magmatic-hydrothermal or sedimentary alteration properties, and Au/As ratios were between 0.001 and 0.828(the average value was 0.07), indicating that the ore-forming fluid in the Baiyun gold deposit may have been deep magma. Combining the geological, trace element, and isotopic data, as well as data from previous studies, we propose that the Baiyun gold deposit is a magmatic-hydrothermal ore deposit.

Geochemistry, zircon U–Pb geochronology, and Hf isotopes of S-type granite in the Baoshan block, constraints on the age and evolution of the Proto-Tethys

Geochemistry, zircon U–Pb geochronology, and Hf isotope data for the Early Paleozoic granites in the Baoshan Block reveal the Early Paleozoic tectonic evolution of the Proto-Tethys. The samples are high-K, calcalkaline, strongly peraluminous rocks with A/CNK values of 1.37–1.46, are enriched in SiO2, K2O, and Rb, and are depleted in Nb, P, Ti, Eu, and heavy rare earth elements,which indicates the crystallization fractionation of the granitic magma. Zircon U–Pb dating indicates that they formed in ca. 480 Ma. The Nansa granites have εHf(t) values ranging from-16.04 to 4.36 with corresponding TC DMages of 2.10–0.81 Ga, which suggests the magmas derived from the partial melting of ancient metasedimentary with minor involvement of mantle-derived components. A synthesis of data for the Early Paleozoic igneous rocks in the Baoshan block and adjacent(Tengchong,Qiangtang, Sibumasu, Himalaya, etc.) blocks indicates that these blocks were all aligned along the proto-Tethyan margin of East Gondwana in the Early Paleozoic. The Early Paleozoic S-type granites from Nansa were generated in a high-temperature and low-pressure(HTLP) extensional tectonic setting, which resulted from Andean-type orogeny instead of the final assembly of Gondwana or crustal extension in a non-arc environment. In certain places, an expanding environment may exist in opposition to the tectonic backdrop of the lithosphere’s thickening and shortening, leading the crust to melt and decompress,mantle-derived materials to mix, and a small quantity of peraluminous granite to emerge.

Distribution and sources of sedimentary organic matter in different aquaculture areas of northeastern Zhanjiang Bay using stable carbon and nitrogen isotopes

Zhanjiang Bay is a major aquaculture area in China with many types of mariculture products(such as oysters,fish,and shrimp).The culture area and shrimp output in Zhanjiang Bay are ranked first in China.We investigated the total organic carbon(TOC),total nitrogen(TN),TOC/TN ratio,and stable isotopes(δ^(13)C and δ^(15)N) of the fish and shrimp feed,fish and shrimp feces,and sedimentary organic matter(SOM) in and around different aquaculture areas of northeastern Zhanjiang B ay to study the impact of aquaculture activities on SOM.The average TOC contents of fish and shrimp feed were 39.20%±0.91% and 39.29%±0.21%,respectively.The average TOC content in the surface sediments of the oyster culture area,the mixed(fish and shrimp) culture area,and the cage fish farm area were 0.66%,0.88%±0.10%,and 0.58%±0.19%,respectively,which may indicate that mixed culture had a greater impact on SOM.The relatively high TOC and TN contents and relatively low TOC/TN ratios,and δ^(15)N values in the upper layer of the core sediment in the mixed culture area could also support the significant influence of mixed culture.The average δ^(13)C and δ^(15)N values of fish and shrimp feed were -20.6‰±2.2‰ and 1.8‰±1.2‰,respectively,which were different from the isotopic values of SOM in the study area.δ^(13)C and δ^(15)N values for SOM in different aquaculture areas were different from those of nearby reference stations,probably reflecting the influence of aquaculture.The δ^(13)C and δ^(15)N values in the oyster culture area(-25.9‰ and6.0‰,respectively) seemed to have reduced δ^(13)C and enriched δ^(15)N relative to those of the reference station(-24.6‰ and 5.8‰,respectively).This may reflect the influence of organic matter on oyster culture.The δ^(15)N value of the station in the mixed culture area(7.1‰±0.4‰) seemed to be relatively enriched in δ^(15)N relative to that of the reference station(6.6‰).Sedimentation and the subsequent degradation of organic matter from mixed cultures may have contributed to this phenomenon.The surface sediment at the cage fish farm area seemed to be affected by fish feces and primary production based on the indication of δ^(13)C and δ^(15)N values.The sediment core at the mixed culture region(NS6) had lower TOC/TN ratios and more positive δ^(13)C and δ^(15)N values than the sediment core at the oyster culture area,suggesting a higher proportionate contribution of marine organic matter in the mixed culture area.In summary,oyster culture,mixed culture,and cage fish culture in northeastern Zhanjiang Bay had a certain degree of impact on SOM,and mixed culture had more significant influences on SOM based on the high TOC contents and the significant vertical variations of TOC/TN ratio and δ^(15)N value in the sediment of this area.This study provides new insights into the impact of aquaculture activities on SOM content.

Fracturing timing of Jurassic reservoirs in the Dibei-Tuziluoke gas field,Kuqa foreland basin:Evidence from petrography,fluid inclusions,and clumped isotopes

Determining the timing of fracturing is crucial for understanding reservoir evolution and hydrocarbon accumulation in foreland basins.Using fracturing data from cores,borehole images,and outcrops,combined with the clumped isotope(D47)and fluid inclusion analyses of carbonate minerals filled in pores and fractures,this study ascertained the fracturing timing of the Jurassic reservoirs in the Dibei-Tuziluoke Gas Field,Kuqa Foreland Basin.Data from outcrops and borehole images show two dominant fracture sets in the study area:W-E and NE-SW striking fractures.Some W-E striking fractures are carbonate-filled,while NE-SW striking fractures lack mineral fillings.Bitumen veins,not easy to be identified in borehole images,are prevalent in cores.The petrographic analysis reveals that these bitumen veins formed before the calcite cementation in pores and display high viscosity and low maturity.Homogenization temperatures(T_(h))from primary fluid inclusion assemblages in two representative calcite vein samples were notably lower than T_(△47) values from corresponding samples.This suggests the △_(47) signature underwent alteration due to partial reordering during burial.Thus,△_(47)-derived temperatures(apparent temperatures)may not faithfully represent the mineral precipitation temperatures.When plotting these apparent temperatures vs.the burial history,only the possible latest ages of fracturing emerged.These ages were further refined by considering petroleum charging,tectonic evolution,and stress orientation.Bitumen-filled fractures likely resulted from the Late Cretaceous uplift,marking the migration of low-maturity hydrocarbons in the study area.Carbonate-filled E-W striking fractures emerged during the late Miocene(~13-6.5 Ma)alongside fold development.NE-striking fractures that crosscut W-E ones possibly formed recently due to stress reorientation.

Genesis of the Jianbeigou Gold Deposit on the Southern Margin of the North China Craton: Insights from Fluid Inclusions, H-O-S Isotopes, and Pyrite in situ Trace Element Analyses

The Jianbeigou gold deposit is a typical lode gold deposit in the Qinling metallogenic belt, located on the southern margin of the North China Craton. Three stages of the hydrothermal process can be distinguished, including the quartz ± pyrite, quartz-polymetallic sulfide, and quartz-carbonate ± pyrite stages. From the early to late stages, the homogenization temperatures of primary fluid inclusions are 281–362°C, 227–331°C, and 149–261°C, respectively. The corresponding salinities estimated for these fluids are 3.9–9.9 wt%, 0.4–9.4 wt%, and 0.7–7.2 wt% Na Cl equiv. Combined with laser Raman spectroscopy data, the ore-forming fluid belongs to a H_(2)O-CO_(2)-Na Cl ± CH_4 system with medium–low temperature and salinity. The δ~(18)Ofluid and δD values for the quartz veins are-1.0‰ to 6.0‰ and-105‰ to-84‰, respectively, which indicates that the ore-forming fluid is of mixed source, mainly derived from magma, with a contribution from meteoric water. Pyrite has been identified into three generations based on mineral paragenetic sequencing, including Py1, Py2, and Py3. The pyrites have δ~(34)S sulfur isotopic compositions from three stages between 3.7‰ and 8.4‰, indicating that sulfur mainly originated from magma. Te, Bi, Sb, and Cu contents in pyrite were all high and showed a strong correlation with Au concentrations. Native gold and the Au-Ag-Bi telluride minerals were formed concurrently, and the As concentration was low and decoupled from the Au content. Therefore, Te, Bi, Sb and other low-melting point chalcophile elements play an important role for gold mineralization in arsenic-deficient ore-forming fluid. Combined with the geological setting, evolution of pyrite, and ore-fluids geochemistry, we propose that the Jianbeigou deposit can be classified as a magmatic–hydrothermal lode gold deposit. Gold mineralization on the southern margin of the North China Craton is related to Early Cretaceous magmatism and formed in an extensional setting.

Origin of the Dashuigou independent tellurium deposit at Qinghai–Xizang Plateau: constraints from the light stable isotopes C, O, and H

By studying the light isotopic compositions of carbon,oxygen,and hydrogen,combined with previous research results on the ore-forming source of the deposit,the authors try to uncover its metallogenic origin.The δ^(18)O and δ^(13)C isotope signatures of dolomite samples vary between 10.2 and 13.0‰,and between−7.2 and−5.2‰,respectively,implying that the carbon derives from the upper mantle.δD and δ^(18) O of quartz,biotite,and muscovite from diff erent ore veins of the deposit vary between−82 and−59‰,and between 11.6 and 12.4‰,respectively,implying that the metallogenic solutions are mainly magmatic.According to the relevant research results of many isotope geologists,the fractionation degree of hydrogen isotopes increases as the depth to the Earth’s core increases,and the more diff erentiated the hydrogen isotopes are,the lower their values will be.In other words,mantle-derived solutions can have extremely low hydrogen isotope values.This means that the δD‰ value−134 of the pyrrhotite sample numbered SD-34 in this article may indicate mantle-derived oreforming fl uid of the deposit.The formation of the Dashuigou tellurium deposit occurred between 91.71 and 80.19 Ma.

Quantification of irrigation water transport processes in ZiZiphus jujuba garden using water stable isotopes

ZiZiphus jujuba,which is native to China,has become one of the main crops widely planted in the western Loess Plateau because of its drought and flood-tolerance,adaptability,and higher nutritional value of the fruit.The irrigation water infiltration in Z.jujuba gardens is complex,and understanding its mechanisms is essential for efficient water use and sustainable agriculture.This knowledge helps ensure the long-term success of jujuba cultivation.This paper describes a field experiment that investigates the infiltration process of irrigation water from Z.jujuba garden and quantifies the contribution of irrigation water to soil water at different depths using the MixSIAR model.According to the FC(Field water holding Capacity)of Z.jujuba,irrigation experiments with three volumes of 80%FC,60%FC,and 40%FC are set up in this study.The study finds that water retention is better in Z.jujuba garden soils with a higher proportion of coarse gravel in the soil particle composition.Soil water content exhibits a gradient change after irrigation,with deeper wetting front transport depth observed with increased irrigation water.Additionally,there is correlation between soil temperature and soil water content.The soil water in Z.jujuba garden generally exhibits a preferential flow signal in the 0-40 cm range.Below 40 cm,a piston flow pattern dominates.The rate of soil water infiltration increases with the amount of irrigation water.In the 0-40 cm range of the soil vertical profile,irrigation water was the main contributor to soil water.Z.jujuba demonstrated flexibility in water uptake,primarily absorbing soil water at depths of 0-40 cm.For optimal growth of Z.jujuba at this stage,40%FC irrigation is recommended.The results are expected to be valuable future irrigation practices and land use planning for Z.jujuba garden in arid zones,supporting sustainable agricultural development and water management.

Petrogenesis and Tectonic Implications of the Early Triassic Nianzi Adakitic Granite Unit in the Yanshan Fold and Thrust Belt:New Constraints from U-Pb Geochronology and Sr-Nd-Hf Isotopes

The Nianzi granite unit,which includes the Nianzi,Xiaolianghou and Xiawopu granitic intrusions,is a significant component of the northern part of the North China Craton(NCC)and is situated in the Yanshan fold and thrust belt(YFTB).However,there is still debate regarding the tectonic evolutionary history of the YFTB during the late Permian to Triassic period,specifically regarding the timing of subduction and collision between the NCC and the Paleo-Asian Ocean.The Nianzi granite unit exhibits unique petrological,geochronological and geochemical signatures that shed light on the tectonic evolutionary history of the YFTB.This study presents detailed petrology,whole-rock geochemistry,together with Sr-Nd isotopic,zircon U-Pb dating and Lu-Hf isotopic data of the granites within the Nianzi granite unit.Our findings demonstrate that the granites primarily consist of subhedral K-feldspar,plagioclase,quartz,minor biotite and hornblende,with accessory titanite,apatite,magnetite and zircon.Zircon U-Pb dating indicates that the Xiaolianghou granite was emplaced at 247.5±0.62 Ma.Additionally,the adakitic characteristics of the Nianzi,Xiawopu and Xiaolianghou granitic intrusions,such as high Sr and Ba contents and high ratios of Sr/Y and(La/Yb)N,combined with negative Sr-Nd and Lu-Hf isotopes(87Sr/86Sr)i=0.705681–0.7057433,εNd(t)=−21.98 to−20.97,zirconεHf(t)=−20.26 to−9.92,as well as the I-type granite features of high SiO_(2),Na_(2)O and K_(2)O/Na_(2)O ratios,enriched Rb,K,Sr and Ba,along with depleted Th,U,Nb,Ta,P and Ti,suggest that the Nianzi granitic unit was mainly derived from the partial melting of a thickened lower crust containing hydrous,calc-alkaline to high-K calc-alkaline,mafic to intermediate metamorphic rocks.In light of these parameters,we further integrate our data with previous studies and conclude that the Nianzi granitic unit was generated in a post-collisional extensional environment during the Early Triassic.

A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

Linkage between precipitation isotopes and water vapor sources in the monsoon margin:Evidence from arid areas of Northwest China

The isotope composition in precipitation has been widely considered as a tracer of monsoon activity.Compared with the coastal region,the monsoon margin usually has limited precipitation with large fluctuation and is usually sensitive to climate change.The water resource management in the monsoon margin should be better planned by understanding the composition of precipitation isotope and its influencing factors.In this study,the precipitation samples were collected at five sampling sites(Baiyin City,Kongtong District,Maqu County,Wudu District,and Yinchuan City)of the monsoon margin in the northwest of China in 2022 to analyze the characteristics of stable hydrogen(δD)and oxygen(δ18O)isotopes.We analyzed the impact of meteorological factors(temperature,precipitation,and relative humidity)on the composition of precipitation isotope at daily level by regression analysis,utilized the Hybrid Single-Particle Lagrangian Integrated Trajectory(HYSPLIT)-based backward trajectory model to simulate the air mass trajectory of precipitation events,and adopted the potential source contribution function(PSCF)and concentration weighted trajectory(CWT)to analyze the water vapor sources.The results showed that compared with the global meteoric water line(GMWL),the slope of the local meteoric water line(LMWL;δD=7.34δ^(18)O-1.16)was lower,indicating the existence of strong regional evaporation in the study area.Temperature significantly contributed toδ18O value,while relative humidity had a significant negative effect onδ18O value.Through the backward trajectory analysis,we found eight primary locations that were responsible for the water vapor sources of precipitation in the study area,of which moisture from the Indian Ocean to South China Sea(ITSC)and the western continental(CW)had the greatest influence on precipitation in the study area.The hydrogen and oxygen isotopes in precipitation are significantly influenced by the sources and transportation paths of air mass.In addition,the results of PSCF and CWT analysis showed that the water vapor source areas were primarily distributed in the south and northwest direction of the study area.

Genesis of the Changba–Lijiagou Giant Pb-Zn Deposit, West Qinling, Central China: Constraints from S-Pb-C-O isotopes

The extensive Changba-Lijiagou Pb-Zn deposit is located in the north of the Xihe–Chengxian ore cluster in West Qinling. The ore bodies are mainly hosted in the marble, dolomitic marble and biotite-calcite-quartz schist of the Middle Devonian Anjiacha Formation, and are structurally controlled by the fault and anticline. The ore-forming process can be divided into three main stages, based on field geological features and mineral assemblages. The mineral assemblages of hydrothermal stage I are pale-yellow coarse grain, low Fe sphalerite, pyrite with pits, barite and biotite. The mineral assemblages of hydrothermal stage II are black-brown cryptocrystalline, high Fe shalerite, pyrite without pits, marcasite or arsenopyrite replace the pyrite with pits, K-feldspar. The features of hydrothermal stage III are calcite-quartz-sulfide vein cutting the laminated, banded ore body. Forty-two sulfur isotope analyses, twenty-five lead isotope analyses and nineteen carbon and oxygen isotope analyses were determined on sphalerite, pyrite, galena and calcite. The δ34 S values of stage I(20.3 to 29.0‰) are consistent with the δ34 S of sulfate(barite) in the stratum. Combined with geological feature, inclusion characteristics and EPMA data, we propose that TSR has played a key role in the formation of the sulfides in stage I. The δ34 S values of stage II sphalerite and pyrite(15.1 to 23.0‰) are between sulfides in the host rock, magmatic sulfur and the sulfate(barite) in the stratum. This result suggests that multiple S reservoirs were the sources for S2-in stage II. The δ34 S values of stage III(13.1 to 22‰) combined with the structure of the geological and mineral features suggest a magmatic hydrothermal origin of the mineralization. The lead isotope compositions of the sulfides have 206 Pb/204 Pb ranging from 17.9480 to 17.9782, 207 Pb/204 Pb ranging from 15.611 to 15.622, and 208 Pb/204 Pb ranging from 38.1368 to 38.1691 in the three ore-forming stages. The narrow and symmetric distributions of the lead isotope values reflect homogenization of granite and mantle sources before the Pb-Zn mineralization. The δ13 CPDB and δ18 OSMOW values of stage I range from-0.1 to 2.4‰ and from 18.8 to 21.7‰. The values and inclusion data indicate that the source of fluids in stage I was the dissolution of marine carbonate. The δ13 CPDB and δ18 OSMOW values of stage II range from-4 to 1‰ and from 12.3 to 20.3‰, suggesting multiple C-O reservoirs in the Changba deposit and the addition of mantle-source fluid to the system. The values in stage III are-3.1‰ and 19.7‰, respectively. We infer that the process of mineralization involved evaporitic salt and sedimentary organic-bearing units interacting through thermochemical sulfate reduction through the isotopic, mineralogy and inclusion evidences. Subsequently, the geology feature, mineral assemblages, EPMA data and isotopic values support the conclusion that the ore-forming hydrothermal fluids were mixed with magmatic hydrothermal fluids and forming the massive dark sphalerite, then yielding the calcite-quartz-sulfide vein ore type at the last stage. The genesis of this ore deposit was epigenetic rather than the previously-proposed sedimentary-exhalative(SEDEX) type.

Sources and transformations of nitrite in the Amundsen Sea in summer 2019 and 2020 as revealed by nitrogen and oxygen isotopes

In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of nitrite in the euphotic zone of the Southern Ocean.We found that primary nitrite maxima(PNMs)are widely present in the Amundsen Sea,where the depth of occurrence deepens from east to west and nitrite concentrations increases.Evidence from dual isotopes suggests that the formation of PNMs in all regions of the Amundsen Sea is dominated by ammonia oxidation.More importantly,the nitrogen and oxygen isotope compositions of nitrite in the Amundsen Sea mixed layer are abnormal,and their depth profiles are mirror symmetrical.Isotopic anomalies exhibit spatial variations,with central surface water having the lowest nitrogen isotope composition(−89.9‰±0.2‰)and western surface water having the highest oxygen isotope composition(63.3‰±0.3‰).Isotopic exchange reaction between nitrate and nitrite is responsible for these isotope anomalies,as both nitrogen and oxygen isotopes have large isotopic fractionation and opposite enrichment effects.This proves that isotopic exchange reaction operates extensively in different regions of the Amundsen Sea.Our study highlights the unique role of dual isotopes of nitrite in deepening the understanding of nitrogen cycle.Further studies on ammonia oxidation and isotopic exchange between nitrate and nitrite are warranted in the future to understand their roles in the nitrogen cycle in the Southern Ocean.

小红石砬子铅锌(银)矿床成因:来自S-Pb同位素和元素特征的证据

小红石砬子铅锌(银)矿床是吉中-延边铜镍多金属成矿带中具有代表性的中型矿床,前人关于该矿床类型划分的观点有火山成因块状硫化物型(Volcanogenic Massive Sulfide,VMS)、中-低温热液脉型、喷流沉积-热液叠加改造型,这三种观点的争论严重制约了对该矿区及区域成矿和找矿的认识。本文选取该矿床中金属硫化物开展原位微量和S-Pb同位素分析,赋矿围岩开展全岩S同位素分析。闪锌矿Fe-Zn含量(4.48%~10.33%、53.67%~62.12%)与中温热液矿床一致(3.00%~10.00%、50.00%~60.00%,成矿温度约200℃),Zn/Cd比值(53.68~76.75)同样指示中低温成矿作用(高温:Zn/Cd>500;低温:Zn/Cd<250),Ga/Ge比值在lg(Ga/Ge)-T图解中,对应温度约为100~180℃,上述温度范围与前人测定的流体包裹体均一温度基本吻合(90~250℃)。闪锌矿Zn/Cd的比值(53.68~76.75)与Cd含量(7577×10-6~11266×10-6)特征与密西西比河谷型(Mississippi Valley-Type,MVT)矿床一致;黄铁矿Fe/S比值(0.76~1.29,平均值为0.89)接近典型MVT矿床的理论值(0.88)。金属硫化物δ34 S V-CDT值介于-9.6‰~-0.5‰之间,总体偏负;赋矿围岩δ34 S V-CDT值介于-8.5‰~4.2‰之间,两者重叠范围较大(主要集中于-9.0‰~-2.0‰),说明围岩提供了主要的还原硫,而古老基底可能提供了部分较轻的硫。金属硫化物Pb同位素比值为206 Pb/204 Pb=18.30~18.39、207 Pb/204 Pb=15.61~15.63、208 Pb/204 Pb=38.38~38.44,指示铅为混合来源,成矿物质可能主要来自上地壳和造山带,模式年龄计算显示上太古界乌拉山群变质岩可能为铅的初始来源。综上所述,小红石砬子铅锌(银)矿床地球化学特征与MVT型矿床基本一致,地质特征略有差别,因此推测其为类MVT型矿床。

Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate:Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic(2.22-2.06 Ga).Theδ^(13)C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05‰-4.95‰(V-PDB;maximum:4.95‰)in this study,which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group.They are much higher than theδ^(13)C values of marine carbonates(-1.16‰on average).Theδ^(13)C values of other formations in the Paleoproterozoic Yimen Group are negative.The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block,which is reported for the first time.Furthermore,they are comparable to theδ^(13)C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton,the Wuzhiling Formation of the Songshan Group in the Xiong'er area,Henan Province,and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area,Liaoning Province.Therefore,it can be further concluded that the LJE is a global event.This study reveals that LJE occurred in Central Yunnan at 2.15-2.10 Ga,lasting for about 50 Ma.The macro-columnar,bean-shaped,and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group.They are the direct cause for the LJE and are also the oldest paleontological fossils ever found.The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event(first occurrence),the global Superiortype banded iron formations(BIFs),the Huronian glaciation,the Great Oxygenation Event(second occurrence),the explosion of multicellular eukaryotes,the positive carbon isotope excursion,and the global anoxic and selenium-rich sedimentary event.The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.

Zircon U-Pb geochronology,Hf isotopes,and geochemistry constraints on the age and tectonic affinity of the basement granitoids from the Qiongdongnan Basin,northern South China Sea

Studies in the northern South China Sea(SCS)basement remain important for understanding the evolution of the Southeast Asian continental margin.Due to a thick cover of sediments and scarce borehole penetration,little is known about the age and tectonic affinity of this basement.In this study,an integrated study of zircon U-Pb geochronology,Hf isotopes,and whole-rock major and trace elements on seven basement granitoids from seven boreholes of Qiongdongnan Basin has been carried out.New zircon U-Pb results for these granitoids present middle-late Permian((270.0±1.2)Ma;(253±3.4)Ma),middle to late Triassic((246.2±3.4)Ma;(239.3±0.96)Ma;(237.9±0.99)Ma;(228.9±1.0)Ma)and Late Cretaceous ages((120.6±0.6)Ma).New data from this study,in combination with the previous dataset,indicates that granitoid ages in northern SCS basement vary from 270 Ma to 70.5 Ma,with three age groups of 270–196 Ma,162–142 Ma,and 137–71 Ma,respectively.Except for the late Paleozoic-Mesozoic rocks in the basement of the northern SCS,a few old zircon grains with the age of(2708.1±17)Ma to(2166.6±19)Ma provide clues to the existence of the pre-Proterozoic components.The geochemical signatures indicate that the middle Permian-early Cretaceous granitoids from the Qiongdongnan Basin are I-type granites formed in a volcanic arc environment,which were probably related to the subduction of the Paleo-Pacific Plate.

北山成矿带老硐沟金多金属矿床S-Pb-C-O同位素特征及其对矿床成因的约束

老硐沟金多金属矿床是北山成矿带内蒙古段最为典型的金矿床之一,其矿床成因存在较多争议,矿床成矿物质来源方面的研究几近空白。文章基于详细的野外实地调查,选取不同成矿阶段的硫化物和方解石,开展原位S-Pb同位素和C-O同位素测试。研究结果表明,老硐沟金多金属矿床δ34S值为-0.56‰~5.54‰,^(206)Pb/^(204)Pb比值为18.326~18.390,207Pb/^(204)Pb比值为15.563~15.645,^(208)Pb/^(204)Pb比值为38.226~38.390,铅同位素μ值变化范围为9.40~9.55,ω值变化范围为35.77~36.85,方铅矿二阶段模式年龄为232~270 Ma,δ^(13)C值介于-0.04‰~2.93‰之间,表明老硐沟金多金属矿床成矿物质具有岩浆和地层混合来源性质,成矿流体以岩浆来源为主,成矿作用晚期流体中混入了地层变质水。文章从矿床稳定同位素研究方面,结合前人对北山造山带构造演化的认识,提出老硐沟金多金属矿床成因为岩浆热液型。