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.

Genesis of the Weiquan Ag-Polymetallic Deposit in East Tianshan, China： Evidence from Zircon U-Pb Geochronology and C-H-O-S-Pb Isotope Systematics

The Weiquan Ag-polymetallic deposit is located on the southern margin of the Central Asian Orogenic Belt and in the western segment of the Aqishan-Yamansu arc belt in East Tianshan,northwestern China. Its orebodies, controlled by faults, occur in the lower Carboniferous volcanosedimentary rocks of the Yamansu Formation as irregular veins and lenses. Four stages of mineralization have been recognized on the basis of mineral assemblages, ore fabrics, and crosscutting relationships among the ore veins. Stage I is the skarn stage(garnet + pyroxene), Stage Ⅱ is the retrograde alteration stage(epidote + chlorite + magnetite ± hematite 士 actinolite ± quartz),Stage Ⅲ is the sulfide stage(Ag and Bi minerals + pyrite + chalcopyrite + galena + sphalerite + quartz ± calcite ± tetrahedrite),and Stage IV is the carbonate stage(quartz + calcite ± pyrite). Skarnization,silicification, carbonatization,epidotization,chloritization, sericitization, and actinolitization are the principal types of hydrothermal alteration. LAICP-MS U-Pb dating yielded ages of 326.5±4.5 and 298.5±1.5 Ma for zircons from the tuff and diorite porphyry, respectively. Given that the tuff is wall rock and that the orebodies are cut by a late diorite porphyry dike, the ages of the tuff and the diorite porphyry provide lower and upper time limits on the age of ore formation. The δ13C values of the calcite samples range from-2.5‰ to 2.3‰, the δ18OH2 Oand δDVSMOWvalues of the sulfide stage(Stage Ⅲ) vary from 1.1‰ to 5.2‰ and-111.7‰ to-66.1‰, respectively,and the δ13C, δ18OH2 Oand δDV-SMOWvalues of calcite in one Stage IV sample are 1.5‰,-0.3‰, and-115.6‰, respectively. Carbon, hydrogen, and oxygen isotopic compositions indicate that the ore-forming fluids evolved gradually from magmatic to meteoric sources. The δ34SV-CDTvalues of the sulfides have a large range from-6.9‰ to 1.4‰, with an average of-2.2‰, indicating a magmatic source, possibly with sedimentary contributions. The206Pb/204Pb,207Pb/204Pb, and208Pb/204Pb ratios of the sulfides are 17.9848-18.2785,15.5188-15.6536, and 37.8125-38.4650, respectively, and one whole-rock sample at Weiquan yields206Pb/204Pb,207Pb/204Pb, and208Pb/204Pb ratios of 18.2060, 15.5674, and 38.0511,respectively. Lead isotopic systems suggest that the ore-forming materials of the Weiquan deposit were derived from a mixed source involving mantle and crustal components. Based on geological features, zircon U-Pb dating, and C-H-OS-Pb isotopic data, it can be concluded that the Weiquan polymetallic deposit is a skarn type that formed in a tectonic setting spanning a period from subduction to post-collision. The ore materials were sourced from magmatic ore-forming fluids that mixed with components derived from host rocks during their ascent, and a gradual mixing with meteoric water took place in the later stages.

Fluid inclusions,C-H-O-S-Pb isotope systematics,geochronology and geochemistry of the Budunhua Cu deposit,northeast China:Implications for ore genesis

The Budunhua Cu deposit is located in the Tuquan ore-concentrated area of the southern Great Xing’an Range,NE China.This deposit includes the southern Jinjiling and northern Kongqueshan ore blocks,separated by the Budunhua granitic pluton.Cu mineralization occurs mainly as stockworks or veins in the outer contact zone between tonalite porphyry and Permian metasandstone.The ore-forming process can be divided into four stages involving stage Ⅰ quartz-pyrite-arsenopyrite;stage Ⅱ quartz-pyrite-chalcopyrite-pyrrhotite;stage Ⅲ quartz--polynetallic sulfides;and stage IV quartz-calcite.Three types of fluid inclusions(FIs) can be distinguished in the Budunhua deposit:liquid-rich two-phase aqueous FIs(L-type),vapour-rich aqueous FIs(V-type),and daughter mineral-bearing multi-phase FIs(S-type).Quartz of stages Ⅰ-Ⅲ contains all types of FIs,whereas only L-type FIs are evident in stage Ⅳ veins.The coexisting V-and S-type FIs of stages Ⅰ-Ⅲ have similar homogenization temperatures but contrasting salinities,which indicates that fluid boiling occurred.The FIs of stages Ⅰ,Ⅱ,Ⅲ,and Ⅳyield homogenization temperatures of 265-396℃,245-350℃,200-300℃,and 90-228℃ with salinities of3.4-44.3 wt.%,2.9-40.2 wt.%,1.4-38.2 wt.%,and 0.9-9.2 wt.% NaCl eqv.,respectively.Ore-forming fluids of the Budunhua deposit are characterized by high temperatures,moderate salinities,and relatively oxidizing conditions typical of an H2 O-NaCl fluid system.Mineralization in the Budunhua deposit occurred at a depth of0.3-1.5 km,with fluid boiling and mixing likely being responsible for ore precipitation.C-H-O-S-Pb isotope studies indicate a predominantly magmatic origin for the ore-forming fluids and materials.LA-ICP-MS zircon U-Pb analyses indicate that ore-forming tonalite porphyry and post-ore dioritic porphyrite were formed at 151.1±1.1 Ma and 129.9±1.9 Ma,respectively.Geochemical data imply that the primary magma of the tonalite porphyry formed through partial melting of Neoproterozoic lower crust.On the basis of available evidence,we suggest that the Budunhua deposit is a porphyry ore system that is spatially,temporally,and genetically associated with tonalite porphyry and formed in a post-collision extensional setting following closure of the Mongol-Okhotsk Ocean.

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.

Determination of Carbon and Nitrogen Isotope Fractions in Asparagine, Aspartic Acid, Threonine and Methionine

The nomenclature for compounds that are modified with isotopes is growing every day. Compounds can be modified with isotopes either individually, in a functional group or groups, or completely with all atomic centers of the element. This diversity of isotope-modified compounds increases the range of researches that can be studied using them. Compounds modified with isotopes of carbon-13 or nitrogen-15 can be converted into carbon monoxide, carbon dioxide and molecular nitrogen. Currently, only the average value of carbon-13 or nitrogen-15 isotopes can be determined. However, by directly determining the atomic share of these isotopes in organic compounds modified with isotopes, information about the isotopic centers of the element can be obtained. The atomic fraction of an element is defined as a single carbon or nitrogen isotope-modified center or centers, or all centers that are isotope-modified with that element at the same time. Carbon-13 or nitrogen-15 isotopes’ atomic fraction can be determined molecularly or with fragment ions of different elemental content, or both. This makes the method self-verifying, increasing the accuracy and reliability of the results obtained. Amino acids, such as asparagine, aspartic acid, methionine, and threonine, are essential for the human body. This proposed method of isotopic analysis will increase the possibilities for scientific research using these compounds.

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.

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.

Geochemical modeling to aid experimental design for multiple isotope tracer studies of coupled dissolution and precipitation reaction kinetics

It is a challenge to make thorough but efficient experimental designs for the coupled mineral dissolution and precipitation studies in a multi-mineral system, because it is difficult to speculate the best experimental duration, optimal sampling schedule, effects of different experimental conditions, and how to maximize the experimental outputs prior to the actual experiments. Geochemical modeling is an efficient and effective tool to assist the experimental design by virtually running all scenarios of interest for the studied system and predicting the experimental outcomes. Here we demonstrated an example of geochemical modeling assisted experimental design of coupled labradorite dissolution and calcite and clayey mineral precipitation using multiple isotope tracers. In this study, labradorite(plagioclase) was chosen as the reactant because it is both a major component and one of the most reactive minerals in basalt. Following our isotope doping studies of single minerals in the last ten years, initial solutions in the simulations were doped withmultiple isotopes(e.g., Ca and Si). Geochemical modeling results show that the use of isotope tracers gives us orders of magnitude more sensitivity than the conventional method based on concentrations and allows us to decouple dissolution and precipitation reactions at near-equilibrium condition. The simulations suggest that the precise unidirectional dissolution rates can inform us which rate laws plagioclase dissolution has followed. Calcite precipitation occurred at near-equilibrium and the multiple isotope tracer experiments would provide near-equilibrium precipitation rates, which was a challenge for the conventional concentration-based experiments. In addition, whether the precipitation of clayey phases is the rate-limiting step in some multi-mineral systems will be revealed. Overall, the modeling results of multimineral reaction kinetics will improve the understanding of the coupled dissolution–precipitation in the multi-mineral systems and the quality of geochemical modeling prediction of CO_(2) removal and storage efficacy in the basalt systems.

Nuclear volume effects in kinetic isotope fractionation:A case study of mercury oxidation by chlorine species

It is well-known that the equilibrium isotope fractionation of mercury(Hg)includes classical massdependent fractionations(MDFs)and nuclear volume effect(NVE)induced mass-independent fractionations(MIFs).However,the effect of the NVE on these kinetic processes is not known.The total fractionations(MDFs+NVEinduced MIFs)of several representative Hg-incorporated substances were selected and calculated with ab initio calculations in this work for both equilibrium and kinetic processes.NVE-induced MIFs were calculated with scaled contact electron densities at the nucleus through systematic evaluations of their accuracy and errors using the Gaussian09 and DIRAC19 packages(named the electron density scaling method).Additionally,the NVE-induced kinetic isotope effect(KIE)of Hg isotopes are also calculated with this method for several representative Hg oxidation reactions by chlorine species.Total KIEs for 202 Hg/^(198)Hg ranging from−2.27‰to 0.96‰are obtained.Three anomalous^(202)Hg-enriched KIEs(δ^(202)Hg/^(198)Hg=0.83‰,0.94‰,and 0.96‰,)caused by the NVE are observed,which are quite different from the classical view(i.e.,light isotopes react faster than the heavy ones).The electron density scaling method we developed in this study can provide an easier way to calculate the NVE-induced KIEs for heavy isotopes and serve to better understand the fractionation mechanisms of mercury isotope systems.

Comparison of isotope-based linear and Bayesian mixing models in determining moisture recycling ratio

Stable water isotopes are natural tracers quantifying the contribution of moisture recycling to local precipitation,i.e.,the moisture recycling ratio,but various isotope-based models usually lead to different results,which affects the accuracy of local moisture recycling.In this study,a total of 18 stations from four typical areas in China were selected to compare the performance of isotope-based linear and Bayesian mixing models and to determine local moisture recycling ratio.Among the three vapor sources including advection,transpiration,and surface evaporation,the advection vapor usually played a dominant role,and the contribution of surface evaporation was less than that of transpiration.When the abnormal values were ignored,the arithmetic averages of differences between isotope-based linear and the Bayesian mixing models were 0.9%for transpiration,0.2%for surface evaporation,and–1.1%for advection,respectively,and the medians were 0.5%,0.2%,and–0.8%,respectively.The importance of transpiration was slightly less for most cases when the Bayesian mixing model was applied,and the contribution of advection was relatively larger.The Bayesian mixing model was found to perform better in determining an efficient solution since linear model sometimes resulted in negative contribution ratios.Sensitivity test with two isotope scenarios indicated that the Bayesian model had a relatively low sensitivity to the changes in isotope input,and it was important to accurately estimate the isotopes in precipitation vapor.Generally,the Bayesian mixing model should be recommended instead of a linear model.The findings are useful for understanding the performance of isotope-based linear and Bayesian mixing models under various climate backgrounds.

Effects of thinning and understory removal on water use efficiency of Pinus massoniana:evidence from photosynthetic capacity and stable carbon isotope analyses

Understanding the relationship between forest management and water use efficiency(WUE)is important for evaluating forest adaptability to climate change.However,the effects of thinning and understory removal on WUE and its key controlling processes are not well understood,which limits our comprehension of the physiological mechanisms of various management practices.In this study,four forest management measures(no thinning:NT;understory removal:UR;light thinning:LT;and heavy thinning:HT)were carried out in Pinus massoniana plantations in a subtropical region of China.Photosynthetic capacity and needle stable carbon isotope composition(δ^(13)C)were measured to assess instantaneous water use efficiency(WUE_(inst))and long-term water use efficiency(WUE_(i)).Multiple regression models and structural equation modelling(SEM)identified the effects of soil properties and physiological performances on WUE_(inst)and WUE_(i).The results show that WUE_(inst)values among the four treatments were insignificant.However,compared with the NT stand(35.8μmol·mol^(-1)),WUE_(i)values significantly increased to 41.7μmol·mol^(-1)in the UR,50.1μmol·mol^(-1)in the LT and 46.6μmol·mol^(-1)in HT treatments,largely explained by photosynthetic capacity and soil water content.Understory removal did not change physiological performance(needle water potential and photosynthetic capacity).Thinning increased the net photosynthetic rate(A_n)but not stomatal conductance(g_s)or predawn needle water potential(ψ_(pd)),implying that the improvement in water use efficiency for thinned stands was largely driven by radiation interception than by soil water availability.In general,thinning may be an appropriate management measure to promote P.massoniana WUE to cope with seasonal droughts under future extreme climates.

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.

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.

Origin of the Yueguang gold deposit in Xinhua, Hunan Province, South China: insights from fl uid inclusion and hydrogen–oxygen stable isotope analysis

The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,west of the Baimashan granitic batholith.In order to discern the characteristics of the ore-formingfluids,the underlying mineralization processes,and establish a foundation for the origin of the Yueguang gold depositfluid inclusion micro-thermometry,as well as quartz hydrogen and oxygen isotope analysis,have been carried out on samples obtained from various stages of mineralization.The hydrothermal miner-alization stages within the Yueguang gold deposit can be categorized into three stages:(i)the barren,pre-ore quartz-pyrite stage(Stage Ⅰ),the quartz-pyrite-gold stage(Stage Ⅱ),and the post-ore quartz-carbonate stage(Stage Ⅲ),with the second stage being the main mineralization stage.Thefluid inclusions identified in samples from the main min-eralization stage can predominantly be described with the NaCl–H_(2)O and CO_(2)–NaCl–H_(2)O systems.These inclusions display homogenization temperatures ranging from 158.8 to 334.9℃,and thefluid salinity ranges from 0.3%to 4.0%(wt.%NaCl equiv.).Laser Raman spectroscopy analysis of individual inclusions further reveals the presence of gas-phases such as CO_(2),CH_(4),and N_(2).Isotopic analysis indicatesδ^(18)Ofluid values ranging from 3.95 to 6.7‰ and δDH_(2)O values ranging from-71.9 to-55.7‰.These results indi-cate that the ore-formingfluid of the Yueguang gold deposit belongs to metamorphic hydrothermalfluids of middle-low temperature and low salinity.In the process of ore formation,gold is transported in the form of Au(HS)2-complexes,with gold deposition being driven byfluid immiscibility.Therefore,the Yueguang gold deposit is categorized as an orogenic gold deposit dominated by metamorphic hydrother-malfluid.It may become a new target for gold exploration in the Baimashan region,central Hunan Province.

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.

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.

Variation of soil-plant-atmosphere continuum stable isotope and water source in Qinghai spruce forest of the eastern Qilian Mountains

Understanding the hydrogen and oxygen stable isotope composition and characteristics of different water bodies in soil-plant-atmosphere continuum is of significance for revealing regional hydrological processes and water cycle mechanisms.In this study,we analyzed the stable isotopic composition,relationship and indicative significance of precipitation,soil water(0~100 cm depth)and xylem water of Qinghai spruce(Picea crassifolia)forest in the eastern Qilian Mountains,and explored the circulation process among different water bodies.The results show that the stable isotopes of precipitation vary greatly during the entire observation period.The values ofδ2H andδ^(18)O in the precipitation in the warm season are richer than those in the cold season,and the slope and intercept of local meteoric water line(LMWL,δ2H=6.79δ18O+7.13)are both smaller than global meteoric water line(GMWL,δ2H=8.17δ18O+10.56).The stable isotopes of soil water at different depths underwent different degrees of evaporative fractionation,and theδ18O andδ2H of shallow soil water varied greatly,while the deep soil water tended to be similar.The topsoil(0~10 cm)can respond quickly to precipitation,and the response of the deep soil has a time lag.In the whole growing season,0~30 cm and 60~100 cm soil water are the main water sources of Qinghai spruce.The water source of Qinghai spruce was from all soil layers in May and September,mainly from the shallow soil layer(0~30 cm)in August and October,and mainly from the deep soil layer(60~100 cm)in June and July.

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。