The growth trajectory of hailstones within clouds has remained elusive due to the inability to trace them directly,impeding the comprehension of their underlying growth mechanisms.This study investigated hailstone ver...The growth trajectory of hailstones within clouds has remained elusive due to the inability to trace them directly,impeding the comprehension of their underlying growth mechanisms.This study investigated hailstone vertical growth trajectories by detecting the stable isotope signatures(2H and 18O compositions)of different shells in 27 hailstones from 9hailstorms,which allowed us to capture the ambient temperature during hailstone growth.The vertical growth trajectories were obtained by comparing the isotopic compositions of water condensate in clouds,derived from the Adiabatic Model,with those measured in hailstones.Although hailstone growth was primarily observed in the–10°C to–30°C temperature layer,the embryo formation height and subsequent growth trajectories significantly varied among hailstones.Embryos formed over a wide range of temperatures(–8.7°C to–33.4°C);four originated at temperatures above–15°C and 16originated at temperatures below–20°C,suggesting ice nuclei composed of bioproteins and mineral dust,respectively.Among the 27 measured hailstones,3 exhibited minimal vertical movement,16 exhibited a monotonic rise or fall,and the remaining 8 exhibited alternating up-down trajectories;only one experienced“recycling”during up-down drifting.Trajectory analysis revealed that similar-sized hailstones from a single storm tended to form at similar heights,whereas those larger than 25 mm in diameter exhibited at least one period of upward growth.Vertical trajectories derived from isotopic analysis were corroborated by radar hydrometeor observations.展开更多
Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geoc...Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.展开更多
Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehens...Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehensive understanding of reservoir evolution and have constrained integrated resource development.This study involved a 28-h desorption experiment in which gases released from shales of the Dalong and Gufeng Formations were systematically collected for compositional and carbon—hydrogen isotope analyses.Comparing the compositional and geochemical characteristics of the desorbed gases and investigating their genetic origins resulted in four main findings:(1)Gas composition during the middle stage of desorption,excluding H_(2)S,best represents the original reservoir fluid,with component variations linked to adsorption and diffusion capacities.(2)Both shales display similar gas compositions with trace H_(2)S;the Dalong shale contains lower CH_(4),CO_(2),and H_(2)S but higher C_(2)H_(6)and N_(2).(3)Carbon and hydrogen isotopes indicate oil-type thermogenic gases,with carbon isotope reversal reflecting tectonic uplift,depressurization,and the mixing of primary kerogen-derived and secondary oil-/condensate-derived gases.(4)N_(2)likely originates from ammonium-bearing silicate decomposition,CO_(2)is mainly inorganic,from thermal carbonate decomposition with minor organic contribution,and H_(2)S may result from oil cracking or thermochemical sulfate reduction.This study provides a comprehensive record of the fluid characteristics of middle-upper Permian shale gas reservoirs and enhances the understanding of their formation and evolution.展开更多
0 INTRODUCTION Uraninite and pitchblende are the most important ore minerals in nearly all types of uranium deposits.Therefore,the U-Pb isotopic system of uraninite and pitchblende are widely used in dating uranium de...0 INTRODUCTION Uraninite and pitchblende are the most important ore minerals in nearly all types of uranium deposits.Therefore,the U-Pb isotopic system of uraninite and pitchblende are widely used in dating uranium deposits.展开更多
The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coin...The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.展开更多
Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)ste...Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)sterane ratio value range(0.72 to 0.83)of bitumen samples from the formation suggests that they were likely formed during phytoplankton blooms.Sterane,hopane,and isoprenoid/n-alkane ratios indicate that the formation's organic matter predominantly consists of algae,and bacteria,accompanied by some reworked material derived from higher plants.Due to the predominance of anoxic conditions and the actions of sulfate-reducing bacteria,the bitumen present is enriched with sulfur compounds.The percentages of saturates,aromatics,and nitrogen-sulfuroxygen(NSO)fractions in the bitumen samples classify them as naphthenic oils.Isotope analysis reveals that biodegradation and water-washing have reduced the concentrations of some volatile saturates and low molecular weight aromatics in the bitumen samples.These actions have resulted in distinctiveδ^(13)C values for the formation's kerogen and bitumen fractions.The formation's organic matter has been subjected to high-temperature thermal regimes and has entered the oil-generation window at the sampled localities,with vitrinite reflectance(%R_(C))varying between 0.7%and 0.75%.展开更多
The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified i...The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified in the region via exploration.However,metallogenic sources and evolution of W remain unclear,and the existing metallogenic model has to be updated to guide further ore prospecting.Elemental and Sr-Nd isotopic data for scheelites assist in the determination of sources and evolution of the W-mineralizing fluids and metals in the district.Based on field geological survey,the scheelites in the Gejiu district can be categorized into three types:altered granite(Type Ⅰ),quartz vein(Type Ⅱ)from the Laochang deposit,and skarn(Type Ⅲ)from the Kafang deposit.Types Ⅰ and Ⅱ scheelites have low molybdenum(Mo)and strontium(Sr)contents,and Type Ⅱ scheelite has lower Sr contents than Type Ⅰ as well as higher Mo and Sr contents than Type Ⅲ scheelites.Varying Mo contents across the scheelite types suggests that the oxygen fugacity varied during ore accumulation.Type Ⅰ and Type Ⅱ scheelites exhibit similar rare earth elements(REE)patterns;Type Ⅲ scheelite contains lower REE content,particularly HREE,compared with the other scheelites.All scheelites exhibit negative Eu anomalies in the chondrite-normalized REE patterns.As the W-mineralization and two-mica granite share close spatial and temporal relationships,the negative Eu anomalies were likely inherited from the two-mica granite.Type Ⅰ and Type Ⅱ scheelites display varied(^(87)Sr/^(86)Sr)_(82 Ma)(0.7090-0.7141)andε_(Nd)(82 Ma)(from−9.9 to−5.4)values,similar to those of granite.However,Type Ⅲ scheelite exhibits lower(^(87)Sr/^(86)Sr)_(82 Ma)(0.7083-0.7087)and lowerε_(Nd)(82 Ma)(from−10.5 to−6.9)values than the two-mica granite.This indicates that the two-mica granite alone did not provide the ore-forming fluids and metals and that the Type Ⅲ scheelite ore-forming fluids likely involved external fluids that were probably derived from carbonate rocks.The implication is that highly differentiated two-mica granites were the source of primary W-bearing metals and fluids,which is consistent with earlier research on the origin of Sn ore-forming materials.展开更多
The widespread dolomite of the Sinian Dengying Formation in the Sichuan Basin(China)serves as one of the most important oil and gas reservoir rocks of the basin.Well WT1,as an exploration well,is recently drilled in t...The widespread dolomite of the Sinian Dengying Formation in the Sichuan Basin(China)serves as one of the most important oil and gas reservoir rocks of the basin.Well WT1,as an exploration well,is recently drilled in the Kaijiang County,northeastern Sichuan Basin(SW China),and it drills through the Dengying Formation dolomite at the depth interval of 7500–7580 m.In this study,samples are systematically collected from the cores of that interval,followed by new analyses of carbon-oxygen isotope,major elements,trace elements,rare earth elements(REEs)and EP-MA.The Dengying Formation dolomites of Well WT1 haveδ13C values of 0.37‰to 2.91‰andδ18O values of-5.72‰to-2.73‰,indicating that the dolomitization fluid is derived from contemporary seawater in the near-surface environment,rather than the burial environment.Based on the REE patterns of EPMA-based in-situ data,we recognized the seawater-sourced components,the mixedsourced components and the terrigenous-sourced components,indicating the marine origin of the dolomite with detrital contamination and diagenetic alteration.Moreover,high Al,Th,and Zr contents indicate significant detrital contamination derived from clay and quartz minerals,and high Sr/Ba and Sr/Cu ratios imply a relatively dry depositional environment with extremely high seawater salinity,intensive evaporation,and strong influences of terrigenous sediment.展开更多
The End-Permian mass extinction(EPME),Earth’s most severe biocrisis,occurred proximal to the Permian-Triassic Boundary(PTB),with marine ecosystems experiencing catastrophic collapse.This study employs stable carbon(...The End-Permian mass extinction(EPME),Earth’s most severe biocrisis,occurred proximal to the Permian-Triassic Boundary(PTB),with marine ecosystems experiencing catastrophic collapse.This study employs stable carbon(δ^(13)C)and oxygen isotopes from marine carbonates in the Haidai Section(Xuanwei,northeastern Yunnan)to decipher paleoenvironmental drivers.The well-preserved stratigraphic sequence encompasses the Upper Permian(Yangxin and Xuanwei Formations)transitioning into the Lower Triassic(Feixianguan and Jialingjiang Formations),providing a continuous marine sedimentary archive.A marked negativeδ^(13)C excursion(-9.66‰V-PDB)occurs at the PTB,initiating from+0.82‰with subsequent gradual recovery.This geochemical signature correlates with:90%reduction in primary productivity Biodiversity collapse exhibiting cluster extinction patterns Prolonged suppression of ecological recovery Concurrently,reconstructed seawater temperatures reveal extreme thermal fluctuations,surging from 23℃to 32℃at the PTB before precipitously declining to 16℃.These perturbations demonstrate coupled biogeochemical dynamics wherein:•Carbon cycle destabilization disrupted nutrient fluxes.•Temperature oscillations exceeded marine taxa thermal tolerances.•Synergistic environmental stresses amplified extinction selectivity.Theδ^(13)C-temperature covariance(r^(2)=0.085)establishes mechanistic linkages between physicochemical perturbations and biotic responses.Our findings demonstrate that the EPME was driven by positive feedback loops in which:Volcanic CO₂emissions triggered carbonate saturation decline Thermal stratification exacerbated anoxia Biogeochemical cycling perturbations suppressed primary producers This integrated geochemical record from the Haidai Section provides critical insights into environment-organism coevolution during Phanerozoic Earth’s most profound mass extinction.展开更多
To investigate the stable chromium(Cr)isotope variations during melt percolation in the mantle,we ana-lyzed the Cr isotopic compositions of fresh ultramafic rocks from the Balmuccia and Baldissero peridotite massifs l...To investigate the stable chromium(Cr)isotope variations during melt percolation in the mantle,we ana-lyzed the Cr isotopic compositions of fresh ultramafic rocks from the Balmuccia and Baldissero peridotite massifs located in the Italian Alps.These massifs represent fragments of the subcontinental lithospheric mantle.The samples collected included lherzolites,harzburgites,dunites,and pyroxenites.Lherzolites,formed through 5%-15%fractional melting of a primitive mantle source,exhibited δ^(53)Crvalues ranging from−0.13‰±0.03‰to−0.03‰±0.03‰.These values correlated negatively with Al_(2)O_(3)content,sug-gesting that partial melting induces Cr isotopic fractionation between the melts and residual peridotites.Harzburgites and dunites,influenced by the silicate melt percolation,displayed distinctδ^(53)Cr values.Notably,dunites not spatially associated with the pyroxenite veins exhibited slightly elevatedδ^(53)Cr val-ues(−0.05‰±0.03‰to 0.10‰±0.03‰)relative to lherzolites.This difference likely resulted from pyroxene dissolution and olivine precipitation during melt percolation processes.However,one dunite sample in direct contact with pyroxenite veins showed lowerδ^(53)Cr values(−0.26‰±0.03‰),possibly owing to the kinetic effects during silicate melt percolation.Pyroxenites are formed through the interac-tion of basaltic melts with the surrounding peridotite via a metasomatic reaction or crystallization in a vein.Most of theirδ^(53)Cr values(−0.26‰±0.03‰to−0.13‰±0.03‰)are positively correlated with MgO contents,suggesting that they were influenced by magmatic differentiation.However,two subsam-ples from a single clinopyroxenite vein exhibit anomalously lowδ^(53)Crvalues(−0.30‰±0.03‰and−0.43‰±0.03‰),which are attributed to kinetic isotopic fractionation during melt-percolation pro-cesses.Our findings suggest that melt percolation processes in the mantle contribute to the Cr isotopic heterogeneity observed within the Earth’s mantle.展开更多
The Xingyuan large fluorite deposit in Fengning,Hebei Province,China,is a significant deposit in the North Hebei-West Liaoning fluorite mineralization belt.The ore bodies are structurally controlled and occur in fault...The Xingyuan large fluorite deposit in Fengning,Hebei Province,China,is a significant deposit in the North Hebei-West Liaoning fluorite mineralization belt.The ore bodies are structurally controlled and occur in fault zones near granitic porphyry veins.Previous studies have focused on the geology and ore-controlling factors,whereas the general features of the hydrothermal systems that contributed to the formation of the deposit remain unclear.This study investigated the nature,origin,and evolution of mineralizing fluids in the Fengning deposit,based on fluid inclusion and H-O isotope data.The fluid inclusions in fluorite are mostly H2O-rich,gas-liquid,two-phase inclusions,along with a few three-phase inclusions containing halite daughter crystals and CO_(2)gas.The ore-forming fluid was variable in homogenization temperature(108-388°C),salinity(0.2-47.4 wt%NaCl equivalent),and density(0.58-1.11 g/cm^(3)),which indicate it was a H2O-NaCl-CO_(2)system of moderate-low temperature,low salinity,and low density.Fluorite H-O isotopes(δD_(V-SMOW)=−123.5‰to−111.8‰;δ^(18)O_(V-SMOW)=−10.3‰to−6.5‰),temperature data,and fluid compositions indicate the mineralizing fluid was initially dominated by magmatic waters,but then experienced a large influx of meteoric waters.The fluid temperature and salinity decreased and the density increased from the early to late stages of mineralization.The main mechanisms of fluorite precipitation were water-rock reactions and fluid cooling.The Xingyuan fluorite deposit is a post-magmatic hydrothermal deposit.展开更多
The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambigu...The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambiguous,leading to controversy regarding its genesis.This study conducted a detailed field geological survey,with systematic sampling of the KT6 orebody,to delineate mineralization stages.Fine mineralogy work,including the use of CL images of scheelite,in-situ LA-ICP-MS trace elements,and Sr isotopes,was carried out on diff erent generations of scheelite formed in various stages.The findings identified the evolution of fluids in the mineralization process,shedding light on the genesis of the deposit.The study revealed four mineralization stages at the Guanfang W deposit:prograde skarn stage,retrograde skarn stage,quartz-sulfide stage,and carbonate-fluorite stage.Diff erent generations of scheelite(Sch I,Sch II,Sch III)were observed in the first three stages,displaying distinct chondrite-normalized REE patterns.The REE of Sch I mainly substituted into the Ca site by REE^(3+)+□_(Ca),and there may be a similar substitution of Nb for REE,whereas it is not the main substitution method.The REE of Sch II mainly enter the scheelite lattice in the form of REE 3++Na+,and there may be a substitution of Nb for REE isomorphism.In the early stage,The REE of Sch III was mainly replaced by Nb for REE isomorphism,while in the later stage,the replacement mode of REE^(3+)+□_(Ca)coexisted with it.The Mo content in scheelite,along with the corresponding Eu anomalies in both scheelite and garnet,collectively imply that the ore-forming fluids during various mineralization stages were predominantly oxidizing,with only slight reducibility observed in Sch II.The in-situ Sr isotope ratios of scheelite concentrates ranged from 0.7093 to 0.7153,resembling those of the Bozhushan granite,indicating a relationship between W mineralization and granite.In addition,the Y/Ho ratios of scheelite from various mineralization stages exhibit a narrow range(19-31),with a pronounced correlation between the contents of Y and Ho and a similar trend in their variation.This consistency suggests that the Guanfang deposit has undergone a uniform or comparable evolutionary process,implying a stable ore-forming fluid across diff erent mineralization stages.展开更多
The method of LA-MC-ICP-MS has become one choice for the analysis of many isotopic systems due to its relatively low cost,high analysis speed,high spatial resolution,and low matrix effect.However,there are still many ...The method of LA-MC-ICP-MS has become one choice for the analysis of many isotopic systems due to its relatively low cost,high analysis speed,high spatial resolution,and low matrix effect.However,there are still many challenges in the accuracy,precision,and spatial resolution of in situ isotopic composition determination by LA-MC-ICP-MS,which mainly include:(1)how to improve instrument sensitivity,further improve the spatial resolution,and achieve simultaneous determination of isotopes,multiple isotopes,or isotopes with trace elements in low-content samples?(2)how to deduct and correct interference to improve the accuracy of isotopic determination?(3)how to correct isotope fractionation?(4)how to reduce the matrix effect of isotopes?how to develop matrix-matched reference materials?and(5)how to achieve non-matrix-matched correction of isotopes?The high-sensitivity cone combinations,gas mixture,shield torch,and reasonable detector array can be applied to improve the elemental sensitivity.The interferences include the background interference and the interferences from the matrix elements(the isobaric interference,the polyatomic interference,and doubly charged ions interference).To reduce or even eliminate the interference,commonly used methods including interference elimination,background correction,and interference correction by evaluating with an interference-free isotope.Isotopic fractionation correction mainly involves external standard calibration and internal and pseudo-internal standard normalization.For non-matrix matched calibration,many methods can be applied,such as the femtosecond laser,line scan,low laser energy,wet plasma condition,optical setup below the sample surface,and matching the intensity of the sample and standard.In this review,we systematically summarized the above challenges and solutions to promote the study and application of LA-MC-ICP-MS in isotopic determination.展开更多
Objective In recent years, a series of tungsten prospecting breakthroughs have been made in the southern Qinling Mountains. Especially, a new deposit type with a scheelite -beryl-molybdenite assemblage in the Zhen＇a...Objective In recent years, a series of tungsten prospecting breakthroughs have been made in the southern Qinling Mountains. Especially, a new deposit type with a scheelite -beryl-molybdenite assemblage in the Zhen＇an area of Shaanxi Province was firstly discovered. This deposit is currently in a detailed investigation stage, and no detailed study has been yet conducted. This work selected one molybdenite sample from the Be （W） ores in this deposit for Re-Os isotope measurements to define the time limit of tungsten and beryllium mineralization, and to further reveal the ore-forming geological setting of rare metals in the southern Qinling region.展开更多
The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction...The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction. The distributions of P（θr）, P（Фr） and the PDDCSs of （2π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dωt）, （2π/σ）（dσ22＋/dωt）, （2π/σ）（dσ21-/dωt） have been calculated based on the surface. The remarkable isotopic effects in the reactions are observed, and the mechanism which may be ascribed to different mass factors is discussed.展开更多
Developing mathematical models for high Knudsen number(Kn)flow for isotopic gas fractionation in tight sedimentary rocks is still challenging.In this study,carbon isotopic reversals(δ^(13)C_(1)>δ^(13)C_(2))were f...Developing mathematical models for high Knudsen number(Kn)flow for isotopic gas fractionation in tight sedimentary rocks is still challenging.In this study,carbon isotopic reversals(δ^(13)C_(1)>δ^(13)C_(2))were found for four Longmaxi shale samples based on gas degassing experiments.Gas in shale with higher gas content exhibits larger reversal.Then,a mathematical model was developed to simulate the carbon isotopic reversals of methane and ethane.This model is based on these hypotheses:(i)diffusion flow is dominating during gas transport process;(ii)diffusion coefficients are nonlinear depending on concentration gradient.Our model not only shows a good agreement with isotopic reversals,but also well predicts gas production rates by selecting appropriate exponents m and m^(*) of gas pressure gradient,where m is for ^(12)C and m^(*)is for ^(13)C.Moreover,the(m−m^(*))value has a positive correlation with fractionation level.(m1−m1^(*))of methane are much higher than that of ethane.Finally,the predicted carbon isotopic reversal magnitude(δ^(13)C_(1)−δ^(13)C_(2))exhibits a positive relationship with total gas content since gas in shale with higher gas content experiences a more extensive high Kn number diffusion flow.As a result,our model demonstrates an impressive agreement with the experimental carbon isotopic reversal data.展开更多
Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availabil...Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availability of inexpensive and simple isotope analysis methods. The present article is an attempt to determine the nitrogen-15 isotope content directly in organic compounds without their conversion. The general principle of possibility of determination of the isotopes of nitrogen directly in organic compounds is proposed. Based on the study of mass-spectra of Carbamide Carbonyldiamide, isocyanic acid and nitrobenzene the mass peaks are selected, by which it is possible to determine the atomic fraction of the isotopes of nitrogen. The respective formulas are proposed.展开更多
South Qinling Tectonic Belt（SQTB）is located between the Shangzhou-Danfeng and Mianxian-Lueyang sutures.There are a lot of early Mesozoic granitoid plutons in its middle segment, comprising the Dongjiangkou-Zhashui g...South Qinling Tectonic Belt（SQTB）is located between the Shangzhou-Danfeng and Mianxian-Lueyang sutures.There are a lot of early Mesozoic granitoid plutons in its middle segment, comprising the Dongjiangkou-Zhashui granitoid plutons at the northeast,Huayang-Wulong-Laocheng granitoid plutons at the central part,Xiba granitoid pluton at the northwest and Guangtoushan-Liuba granitoid plutons at the southwest.These Indonisian granitoids contain a mass of various scale mafic enclaves,which show sometimes clear boundaries and sometimes transitional boundaries with their host granitoids.These granitoids also exhibit metaluminous to peraluminous series,commonly higher Mg# and a wide range of petrochemistry from low-K tholeiite series,through mid-K and high-K calc-alkaline series to shoshonite series and predominated samples are attributed to mid-K and high-K calc-alkaline series.Detailed analyses in Sr-Nd isotopic systematics and petrochemistry reveal that there may be regionally initial granitoid magma of the Indonisian granitoid plutons,comprising Dongjiangkou-Zhashui,Huayang-Wulong-Laocheng,Xiba,and Guangtoushan-Liuba granitoid plutons,which were produced by hybrids of magmas in various degrees,and the initial magmas were derived from both the mantle and the lower continental crust（LCC）sources in the SQTB.The initial granitoid magma further did the magma hybrid with the magmas from the LCC,crystallization fractionation,and assimilation with upper crustal materials during their emplacement to produce these granitoid plutons in the SQTB.These magmatism processes are most likely to occur under continent marginal arc and syn-collision to post-collision tectonic backgrounds.展开更多
Surface lake sediments, 28 from Hoh XU, 24 from northeastern China, 99 from Lake Bosten, 31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values. Considering the impact factors, conductiv...Surface lake sediments, 28 from Hoh XU, 24 from northeastern China, 99 from Lake Bosten, 31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values. Considering the impact factors, conductivity, alkalinity, pH, TOC, C/N and carbonate-content in the sediments, CI, P, S, and metal element ratios of Mg/Ca, Sr/Ca, Fe/Mn of bulk sediments as environmental variables enable evaluation of their influences on δ13C and δ18O using principal component analysis （PCA） method. The closure and residence time of lakes can influence the correlation between δ13C and δ18O. Lake water will change from fresh to brackish with increasing reduction and eutrophication effects. Mg/Ca in the bulk sediment indicates the characteristic of residence time, Sr/Ca and Fe/Mn infer the salinity of lakes. Carbonate formation processes and types can influence the 6~3C--~1So correlation. ~180 will be heavier from Mg-calcite and aragonite formed in a high-salinity water body than calcite formed in freshwater conditions. When carbonate content is less than 30%, there is no relationship with either 613C or 6180, and also none between δ13C and δ18O. More than 30%, carbonate content, however, co-varies highly to δ13C and δ18O, and there is also a high correlation between δ13C and δ18O. Vegetation conditions and primary productivity of lakes can influence the characteristics of δ13C and δ18O, and their co-variance. Total organic matter content （TOC） in the sediments is higher with more terrestrial and submerged plants infilling. In northeastern and northwestern China, when organic matter in the lake sediments comes from endogenous floating organisms and algae, the δ13C value is high. δ13C is in the range of-4‰ to 0‰ when organic matter comes mainly from floating organisms （C/N〈6）; in the range of-4‰ to 8‰ when organic matter comes from diatoms （C/N=6 to 8）; and -8‰ to -4‰ when organic matter comes from aquatic and terrestrial plants （C/N〉8）.展开更多
He-Ar isotopic compositions of fluid inclusions trapped in pyrites from some representative PGE-polymetallic deposits in Lower Cambrian black rock series in South China were analyzed by using an inert gas isotopic mas...He-Ar isotopic compositions of fluid inclusions trapped in pyrites from some representative PGE-polymetallic deposits in Lower Cambrian black rock series in South China were analyzed by using an inert gas isotopic mass spectrometer. The results show that the ore-forming fluids possess a low 3He/4He ratio, varying from 0.43×10-8 to 26.39×10-8, with corresponding R/Ra value of 0.003-0.189. The 40Ar/36Ar ratios are 258-287, close to those of air saturated water (ASW). He-Ar isotopic indicator studies show that the ore-forming fluids were mainly derived from the formation water or basinal hot brine and sea water, while the content of mantle-derived fluid or deep-derived magmatic water might be negligible. The PGE-polymetallic mineralization might be related to the evolution of the Caledonian miogeosynclines distributed along the southern margin of the Yangtze Craton. During the Early Cambrian, the formation water or basinal hot brine trapped in Caledonian basins which accumulated giant thick sediments was expelled and migrated laterally along strata because of the pressure generated by overlying sediments. The basinal hot brine ascended along faults, mixed with sea water and finally deposited ore minerals.展开更多
基金supported by the National Natural Science Foundation of China(Grant No.42030607)the Beijing Municipal Science and Technology Commission(Grant No.Z251100004525005)the National Science Foundation/National Center for Atmospheric Research,and NASA(Grant No.80NSSC22M0129)。
文摘The growth trajectory of hailstones within clouds has remained elusive due to the inability to trace them directly,impeding the comprehension of their underlying growth mechanisms.This study investigated hailstone vertical growth trajectories by detecting the stable isotope signatures(2H and 18O compositions)of different shells in 27 hailstones from 9hailstorms,which allowed us to capture the ambient temperature during hailstone growth.The vertical growth trajectories were obtained by comparing the isotopic compositions of water condensate in clouds,derived from the Adiabatic Model,with those measured in hailstones.Although hailstone growth was primarily observed in the–10°C to–30°C temperature layer,the embryo formation height and subsequent growth trajectories significantly varied among hailstones.Embryos formed over a wide range of temperatures(–8.7°C to–33.4°C);four originated at temperatures above–15°C and 16originated at temperatures below–20°C,suggesting ice nuclei composed of bioproteins and mineral dust,respectively.Among the 27 measured hailstones,3 exhibited minimal vertical movement,16 exhibited a monotonic rise or fall,and the remaining 8 exhibited alternating up-down trajectories;only one experienced“recycling”during up-down drifting.Trajectory analysis revealed that similar-sized hailstones from a single storm tended to form at similar heights,whereas those larger than 25 mm in diameter exhibited at least one period of upward growth.Vertical trajectories derived from isotopic analysis were corroborated by radar hydrometeor observations.
基金Supported by PetroChina Science and Technology Research and Technology Development Project(2021DJ0502)Open Research Project of Key Laboratory of Shale Gas Resources Exploration,Ministry of Natural Resources(Chongqing Institute of Geology and Mineral Resources)(KLSGE-2023).
文摘Based on geochemical data from natural gas samples across spring water systems and sedimentary basins,including Songliao,Bohai Bay,Sanshui,Sichuan,Ordos,Tarim and Ying-Qiong,this paper systematically compares the geochemical compositions of abiogenic versus biogenic gases.Emphasis is placed on the diagnostic signatures of abiogenic gases in terms of gas composition,and carbon,hydrogen and helium isotopes.The main findings are as follows.(1)In hydrothermal spring systems,abiogenic alkane gases are extremely scarce.Methane concentrations are typically less than 1%,with almost no detectable C^(2+)hydrocarbons.The gas is dominantly composed of CO_(2),while N_(2)is the major component in a few samples.(2)Abiogenic alkane gases display distinct isotopic signatures,including enriched methane carbon isotopic compositions(δ^(13)C_(1)>-25‰generally),complete carbon isotopic reversal(δ^(13)C_(1)>δ^(13)C_(2)>δ^(13)C_(3)>δ^(13)C_(4)),and enriched helium isotope(R/Ra>0.5,CH_(4)/^(3)He≤10^(6)generally).(3)The hydrogen isotopic composition of abiogenic alkane gases may be characterized by a positive sequence(δD_(1)<δD_(2)<δD_(3)),or a complete reversal(δD_(1)>δD_(2)>δD_(3)),or a V-shaped distribution(δD_(1)>δD_(2),δD_(2)<δD_(3)).The hydrogen isotopic compositions of methane generally show limited variation(about 9‰),possibly due to hydrogen isotopic exchange with connate water.(4)In terms of identifying gas origin,CH_(4)/^(3)He-R/Ra andδ^(13)CCO_(2)-R/Ra charts are more effective than CO_(2)/^(3)He-R/Ra chart.These new geological insights provide theoretical clues and diagnostic charts for the genetic identification of natural gas and further research on abiogenic gases.
基金supported by the Hubei Provincial Natural Science Foundation of China(Grant No.2022CFB490,2024AFD381)Science and Technology Project of Hubei Geological Bureau(Grant No.KJ2024-2,KJ2025-14)Open Fund of Technology Innovation Center for Shale oil and Gas Accumulation Theory and Engineering in Southern Complex Structural Area,China Geological Survey(Grant No.SOG-202410).
文摘Significant progress has been made in exploring shale gas resources in the middle-upper Permian strata of western Hubei.However,the unclear geochemical characteristics and origins of the gas have hindered a comprehensive understanding of reservoir evolution and have constrained integrated resource development.This study involved a 28-h desorption experiment in which gases released from shales of the Dalong and Gufeng Formations were systematically collected for compositional and carbon—hydrogen isotope analyses.Comparing the compositional and geochemical characteristics of the desorbed gases and investigating their genetic origins resulted in four main findings:(1)Gas composition during the middle stage of desorption,excluding H_(2)S,best represents the original reservoir fluid,with component variations linked to adsorption and diffusion capacities.(2)Both shales display similar gas compositions with trace H_(2)S;the Dalong shale contains lower CH_(4),CO_(2),and H_(2)S but higher C_(2)H_(6)and N_(2).(3)Carbon and hydrogen isotopes indicate oil-type thermogenic gases,with carbon isotope reversal reflecting tectonic uplift,depressurization,and the mixing of primary kerogen-derived and secondary oil-/condensate-derived gases.(4)N_(2)likely originates from ammonium-bearing silicate decomposition,CO_(2)is mainly inorganic,from thermal carbonate decomposition with minor organic contribution,and H_(2)S may result from oil cracking or thermochemical sulfate reduction.This study provides a comprehensive record of the fluid characteristics of middle-upper Permian shale gas reservoirs and enhances the understanding of their formation and evolution.
文摘0 INTRODUCTION Uraninite and pitchblende are the most important ore minerals in nearly all types of uranium deposits.Therefore,the U-Pb isotopic system of uraninite and pitchblende are widely used in dating uranium deposits.
基金Project supported by the National Natural Science Foundation of China(Grant Nos.12325406,92261201,12404305,11974272)the Shannxi Province Natural Science Fundamental Research Project(Grant Nos.2023JC-XJ-03 and 23JSQ013)the Fundamental Research Funds for the Central Universities(Grant No.xzy022024040)。
文摘The two-body fragmentation dynamics of water isotopologues dications(H_(2)O^(2+),HOD^(2+),and D_(2)O^(2+))induced by200 eV electron impact is investigated.Two fragment ions and an emitted electron are detected in coincidence,and their momentum vectors are determined by employing a reaction microscope.The complete kinematical information of four two-body fragmentation channels of H^(+)+OH+,H^(+)+OD^(+),D^(+)+OH^(+),and D^(+)+OD+is obtained.By analyzing the projectile energy-loss spectrum,the initial electronic state of the two-body dissociation channel is determined.Upon examining the kinetic energy release(KER)distributions of the four fragmentation channels,a clear difference is found between the two-body fragmentation channel H^(+)+OD+and the other three channels.The isotopic effect in the two-body fragmentation is demonstrated by the analysis of the relative yields of the two-body fragmentation channels originating from different isotopologues,which shows preferential cleavage of the O-H bond over the O-D bond.These results provide deeper insight into the microscopic dynamic mechanisms in water radiolysis.
文摘Biomarker and stable carbon isotope analyses are presented for the Garau Formation of the Cretaceous Age,an important source rock in western Iran,to reveal its potential as an oilprone source rock.The C_(28)/C_(29)sterane ratio value range(0.72 to 0.83)of bitumen samples from the formation suggests that they were likely formed during phytoplankton blooms.Sterane,hopane,and isoprenoid/n-alkane ratios indicate that the formation's organic matter predominantly consists of algae,and bacteria,accompanied by some reworked material derived from higher plants.Due to the predominance of anoxic conditions and the actions of sulfate-reducing bacteria,the bitumen present is enriched with sulfur compounds.The percentages of saturates,aromatics,and nitrogen-sulfuroxygen(NSO)fractions in the bitumen samples classify them as naphthenic oils.Isotope analysis reveals that biodegradation and water-washing have reduced the concentrations of some volatile saturates and low molecular weight aromatics in the bitumen samples.These actions have resulted in distinctiveδ^(13)C values for the formation's kerogen and bitumen fractions.The formation's organic matter has been subjected to high-temperature thermal regimes and has entered the oil-generation window at the sampled localities,with vitrinite reflectance(%R_(C))varying between 0.7%and 0.75%.
基金financed by Yunnan Major Scientific and Technological Projects(Grant No.202202AG050006)the National Natural Science Foundation of China(Grant No.42462011)Projects of Yunnan Province Technology Hall(Grant No.202305AT350004).
文摘The Gejiu tin-copper-(tungsten)(Sn-Cu-(W))polymetallic district is located in the southwest of the W-Sn metallogenic belt in the western Youjiang Basin,Yunnan,Southwest China.Abundant W minerals have been identified in the region via exploration.However,metallogenic sources and evolution of W remain unclear,and the existing metallogenic model has to be updated to guide further ore prospecting.Elemental and Sr-Nd isotopic data for scheelites assist in the determination of sources and evolution of the W-mineralizing fluids and metals in the district.Based on field geological survey,the scheelites in the Gejiu district can be categorized into three types:altered granite(Type Ⅰ),quartz vein(Type Ⅱ)from the Laochang deposit,and skarn(Type Ⅲ)from the Kafang deposit.Types Ⅰ and Ⅱ scheelites have low molybdenum(Mo)and strontium(Sr)contents,and Type Ⅱ scheelite has lower Sr contents than Type Ⅰ as well as higher Mo and Sr contents than Type Ⅲ scheelites.Varying Mo contents across the scheelite types suggests that the oxygen fugacity varied during ore accumulation.Type Ⅰ and Type Ⅱ scheelites exhibit similar rare earth elements(REE)patterns;Type Ⅲ scheelite contains lower REE content,particularly HREE,compared with the other scheelites.All scheelites exhibit negative Eu anomalies in the chondrite-normalized REE patterns.As the W-mineralization and two-mica granite share close spatial and temporal relationships,the negative Eu anomalies were likely inherited from the two-mica granite.Type Ⅰ and Type Ⅱ scheelites display varied(^(87)Sr/^(86)Sr)_(82 Ma)(0.7090-0.7141)andε_(Nd)(82 Ma)(from−9.9 to−5.4)values,similar to those of granite.However,Type Ⅲ scheelite exhibits lower(^(87)Sr/^(86)Sr)_(82 Ma)(0.7083-0.7087)and lowerε_(Nd)(82 Ma)(from−10.5 to−6.9)values than the two-mica granite.This indicates that the two-mica granite alone did not provide the ore-forming fluids and metals and that the Type Ⅲ scheelite ore-forming fluids likely involved external fluids that were probably derived from carbonate rocks.The implication is that highly differentiated two-mica granites were the source of primary W-bearing metals and fluids,which is consistent with earlier research on the origin of Sn ore-forming materials.
基金financially supported by the Science Foundation of China University of Petroleum,Beijing(Nos.2462018YJRC030 and 2462020YXZZ020)the China Sponsorship Council(No.202306440071)。
文摘The widespread dolomite of the Sinian Dengying Formation in the Sichuan Basin(China)serves as one of the most important oil and gas reservoir rocks of the basin.Well WT1,as an exploration well,is recently drilled in the Kaijiang County,northeastern Sichuan Basin(SW China),and it drills through the Dengying Formation dolomite at the depth interval of 7500–7580 m.In this study,samples are systematically collected from the cores of that interval,followed by new analyses of carbon-oxygen isotope,major elements,trace elements,rare earth elements(REEs)and EP-MA.The Dengying Formation dolomites of Well WT1 haveδ13C values of 0.37‰to 2.91‰andδ18O values of-5.72‰to-2.73‰,indicating that the dolomitization fluid is derived from contemporary seawater in the near-surface environment,rather than the burial environment.Based on the REE patterns of EPMA-based in-situ data,we recognized the seawater-sourced components,the mixedsourced components and the terrigenous-sourced components,indicating the marine origin of the dolomite with detrital contamination and diagenetic alteration.Moreover,high Al,Th,and Zr contents indicate significant detrital contamination derived from clay and quartz minerals,and high Sr/Ba and Sr/Cu ratios imply a relatively dry depositional environment with extremely high seawater salinity,intensive evaporation,and strong influences of terrigenous sediment.
基金supported by the Scientific Research Fund of the Education Department of Yunnan Province(Grant Number:2019J0488).
文摘The End-Permian mass extinction(EPME),Earth’s most severe biocrisis,occurred proximal to the Permian-Triassic Boundary(PTB),with marine ecosystems experiencing catastrophic collapse.This study employs stable carbon(δ^(13)C)and oxygen isotopes from marine carbonates in the Haidai Section(Xuanwei,northeastern Yunnan)to decipher paleoenvironmental drivers.The well-preserved stratigraphic sequence encompasses the Upper Permian(Yangxin and Xuanwei Formations)transitioning into the Lower Triassic(Feixianguan and Jialingjiang Formations),providing a continuous marine sedimentary archive.A marked negativeδ^(13)C excursion(-9.66‰V-PDB)occurs at the PTB,initiating from+0.82‰with subsequent gradual recovery.This geochemical signature correlates with:90%reduction in primary productivity Biodiversity collapse exhibiting cluster extinction patterns Prolonged suppression of ecological recovery Concurrently,reconstructed seawater temperatures reveal extreme thermal fluctuations,surging from 23℃to 32℃at the PTB before precipitously declining to 16℃.These perturbations demonstrate coupled biogeochemical dynamics wherein:•Carbon cycle destabilization disrupted nutrient fluxes.•Temperature oscillations exceeded marine taxa thermal tolerances.•Synergistic environmental stresses amplified extinction selectivity.Theδ^(13)C-temperature covariance(r^(2)=0.085)establishes mechanistic linkages between physicochemical perturbations and biotic responses.Our findings demonstrate that the EPME was driven by positive feedback loops in which:Volcanic CO₂emissions triggered carbonate saturation decline Thermal stratification exacerbated anoxia Biogeochemical cycling perturbations suppressed primary producers This integrated geochemical record from the Haidai Section provides critical insights into environment-organism coevolution during Phanerozoic Earth’s most profound mass extinction.
基金supported by National Natural Science Foundation of China(Grant No.42473017)Hong Kong RGC grants(JLFS/P-702/24 and 17308023)China Geological Survey project(Grant No.DD20242037).
文摘To investigate the stable chromium(Cr)isotope variations during melt percolation in the mantle,we ana-lyzed the Cr isotopic compositions of fresh ultramafic rocks from the Balmuccia and Baldissero peridotite massifs located in the Italian Alps.These massifs represent fragments of the subcontinental lithospheric mantle.The samples collected included lherzolites,harzburgites,dunites,and pyroxenites.Lherzolites,formed through 5%-15%fractional melting of a primitive mantle source,exhibited δ^(53)Crvalues ranging from−0.13‰±0.03‰to−0.03‰±0.03‰.These values correlated negatively with Al_(2)O_(3)content,sug-gesting that partial melting induces Cr isotopic fractionation between the melts and residual peridotites.Harzburgites and dunites,influenced by the silicate melt percolation,displayed distinctδ^(53)Cr values.Notably,dunites not spatially associated with the pyroxenite veins exhibited slightly elevatedδ^(53)Cr val-ues(−0.05‰±0.03‰to 0.10‰±0.03‰)relative to lherzolites.This difference likely resulted from pyroxene dissolution and olivine precipitation during melt percolation processes.However,one dunite sample in direct contact with pyroxenite veins showed lowerδ^(53)Cr values(−0.26‰±0.03‰),possibly owing to the kinetic effects during silicate melt percolation.Pyroxenites are formed through the interac-tion of basaltic melts with the surrounding peridotite via a metasomatic reaction or crystallization in a vein.Most of theirδ^(53)Cr values(−0.26‰±0.03‰to−0.13‰±0.03‰)are positively correlated with MgO contents,suggesting that they were influenced by magmatic differentiation.However,two subsam-ples from a single clinopyroxenite vein exhibit anomalously lowδ^(53)Crvalues(−0.30‰±0.03‰and−0.43‰±0.03‰),which are attributed to kinetic isotopic fractionation during melt-percolation pro-cesses.Our findings suggest that melt percolation processes in the mantle contribute to the Cr isotopic heterogeneity observed within the Earth’s mantle.
基金supported by the National Natural Science Foundation of China(Grant No.41872219).
文摘The Xingyuan large fluorite deposit in Fengning,Hebei Province,China,is a significant deposit in the North Hebei-West Liaoning fluorite mineralization belt.The ore bodies are structurally controlled and occur in fault zones near granitic porphyry veins.Previous studies have focused on the geology and ore-controlling factors,whereas the general features of the hydrothermal systems that contributed to the formation of the deposit remain unclear.This study investigated the nature,origin,and evolution of mineralizing fluids in the Fengning deposit,based on fluid inclusion and H-O isotope data.The fluid inclusions in fluorite are mostly H2O-rich,gas-liquid,two-phase inclusions,along with a few three-phase inclusions containing halite daughter crystals and CO_(2)gas.The ore-forming fluid was variable in homogenization temperature(108-388°C),salinity(0.2-47.4 wt%NaCl equivalent),and density(0.58-1.11 g/cm^(3)),which indicate it was a H2O-NaCl-CO_(2)system of moderate-low temperature,low salinity,and low density.Fluorite H-O isotopes(δD_(V-SMOW)=−123.5‰to−111.8‰;δ^(18)O_(V-SMOW)=−10.3‰to−6.5‰),temperature data,and fluid compositions indicate the mineralizing fluid was initially dominated by magmatic waters,but then experienced a large influx of meteoric waters.The fluid temperature and salinity decreased and the density increased from the early to late stages of mineralization.The main mechanisms of fluorite precipitation were water-rock reactions and fluid cooling.The Xingyuan fluorite deposit is a post-magmatic hydrothermal deposit.
基金suppor ted by Yunnan Major Scientific and Technological Projects(Grant No.202202AG050006)the Personnel Training Project of Kunming University of Science and Technology(Grant No.KKZ3202221022)。
文摘The Guanfang large-scale W deposit is located in the W polymetallic ore concentration area of Bozhushan in southeastern Yunnan,China.Despite extensive research,the fluid evolution process of the deposit remains ambiguous,leading to controversy regarding its genesis.This study conducted a detailed field geological survey,with systematic sampling of the KT6 orebody,to delineate mineralization stages.Fine mineralogy work,including the use of CL images of scheelite,in-situ LA-ICP-MS trace elements,and Sr isotopes,was carried out on diff erent generations of scheelite formed in various stages.The findings identified the evolution of fluids in the mineralization process,shedding light on the genesis of the deposit.The study revealed four mineralization stages at the Guanfang W deposit:prograde skarn stage,retrograde skarn stage,quartz-sulfide stage,and carbonate-fluorite stage.Diff erent generations of scheelite(Sch I,Sch II,Sch III)were observed in the first three stages,displaying distinct chondrite-normalized REE patterns.The REE of Sch I mainly substituted into the Ca site by REE^(3+)+□_(Ca),and there may be a similar substitution of Nb for REE,whereas it is not the main substitution method.The REE of Sch II mainly enter the scheelite lattice in the form of REE 3++Na+,and there may be a substitution of Nb for REE isomorphism.In the early stage,The REE of Sch III was mainly replaced by Nb for REE isomorphism,while in the later stage,the replacement mode of REE^(3+)+□_(Ca)coexisted with it.The Mo content in scheelite,along with the corresponding Eu anomalies in both scheelite and garnet,collectively imply that the ore-forming fluids during various mineralization stages were predominantly oxidizing,with only slight reducibility observed in Sch II.The in-situ Sr isotope ratios of scheelite concentrates ranged from 0.7093 to 0.7153,resembling those of the Bozhushan granite,indicating a relationship between W mineralization and granite.In addition,the Y/Ho ratios of scheelite from various mineralization stages exhibit a narrow range(19-31),with a pronounced correlation between the contents of Y and Ho and a similar trend in their variation.This consistency suggests that the Guanfang deposit has undergone a uniform or comparable evolutionary process,implying a stable ore-forming fluid across diff erent mineralization stages.
基金funded by the National Key R&D Program of China (No. 2019YFA0708400)the National Natural Science Foundation of China (No. 41927803)+2 种基金the MOST (Ministry of Science and Technology) Special Fund from the State Key Laboratory of Geological Processes and Mineral Resources (No. MSFGPMR01)the Natural Science Foundation of Hubei Province (No. 2020CFA045)the Fundamental Research Funds for the Central Universities,China University of Geosciences (Wuhan).
文摘The method of LA-MC-ICP-MS has become one choice for the analysis of many isotopic systems due to its relatively low cost,high analysis speed,high spatial resolution,and low matrix effect.However,there are still many challenges in the accuracy,precision,and spatial resolution of in situ isotopic composition determination by LA-MC-ICP-MS,which mainly include:(1)how to improve instrument sensitivity,further improve the spatial resolution,and achieve simultaneous determination of isotopes,multiple isotopes,or isotopes with trace elements in low-content samples?(2)how to deduct and correct interference to improve the accuracy of isotopic determination?(3)how to correct isotope fractionation?(4)how to reduce the matrix effect of isotopes?how to develop matrix-matched reference materials?and(5)how to achieve non-matrix-matched correction of isotopes?The high-sensitivity cone combinations,gas mixture,shield torch,and reasonable detector array can be applied to improve the elemental sensitivity.The interferences include the background interference and the interferences from the matrix elements(the isobaric interference,the polyatomic interference,and doubly charged ions interference).To reduce or even eliminate the interference,commonly used methods including interference elimination,background correction,and interference correction by evaluating with an interference-free isotope.Isotopic fractionation correction mainly involves external standard calibration and internal and pseudo-internal standard normalization.For non-matrix matched calibration,many methods can be applied,such as the femtosecond laser,line scan,low laser energy,wet plasma condition,optical setup below the sample surface,and matching the intensity of the sample and standard.In this review,we systematically summarized the above challenges and solutions to promote the study and application of LA-MC-ICP-MS in isotopic determination.
基金financially supported by the China Postdoctoral Science Foundation(grant 2017M610960)China Geological Survey(grants No.DD20160346 and DD20160055)
文摘Objective In recent years, a series of tungsten prospecting breakthroughs have been made in the southern Qinling Mountains. Especially, a new deposit type with a scheelite -beryl-molybdenite assemblage in the Zhen＇an area of Shaanxi Province was firstly discovered. This deposit is currently in a detailed investigation stage, and no detailed study has been yet conducted. This work selected one molybdenite sample from the Be （W） ores in this deposit for Re-Os isotope measurements to define the time limit of tungsten and beryllium mineralization, and to further reveal the ore-forming geological setting of rare metals in the southern Qinling region.
基金This work was supported by the National Natural Science Foundation of China （No. 10974078, No. 11174117,No. 10674114, and No. 10874104） and the Research Fund for the Doctoral Program of Higher Education of China （No.20093704110001）.
文摘The vector correlations in Ca＋HCl, Ca＋DCl, and Ca＋TCl reactions have been investigated by means of the quasi-classical trajectory calculations on PES constructed by means of multireference configuration interaction. The distributions of P（θr）, P（Фr） and the PDDCSs of （2π/σ）（dσ00/dωt）, （2π/σ）（dσ20/dωt）, （2π/σ）（dσ22＋/dωt）, （2π/σ）（dσ21-/dωt） have been calculated based on the surface. The remarkable isotopic effects in the reactions are observed, and the mechanism which may be ascribed to different mass factors is discussed.
基金support from Enterprise Innovation and Development Joint Fund of National Natural Science Foundation of China"Enrichment regularity and development mechanism of deep marine shale gas(U19B600303)"SINOPEC Science and Technology Department Project"Research on Precision Characterization of Shale Pore and Fluid Dynamic Monitoring Technology(P20059-8)"。
文摘Developing mathematical models for high Knudsen number(Kn)flow for isotopic gas fractionation in tight sedimentary rocks is still challenging.In this study,carbon isotopic reversals(δ^(13)C_(1)>δ^(13)C_(2))were found for four Longmaxi shale samples based on gas degassing experiments.Gas in shale with higher gas content exhibits larger reversal.Then,a mathematical model was developed to simulate the carbon isotopic reversals of methane and ethane.This model is based on these hypotheses:(i)diffusion flow is dominating during gas transport process;(ii)diffusion coefficients are nonlinear depending on concentration gradient.Our model not only shows a good agreement with isotopic reversals,but also well predicts gas production rates by selecting appropriate exponents m and m^(*) of gas pressure gradient,where m is for ^(12)C and m^(*)is for ^(13)C.Moreover,the(m−m^(*))value has a positive correlation with fractionation level.(m1−m1^(*))of methane are much higher than that of ethane.Finally,the predicted carbon isotopic reversal magnitude(δ^(13)C_(1)−δ^(13)C_(2))exhibits a positive relationship with total gas content since gas in shale with higher gas content experiences a more extensive high Kn number diffusion flow.As a result,our model demonstrates an impressive agreement with the experimental carbon isotopic reversal data.
文摘Nitrogen-15 isotope-modified compounds are widely used in medicine, pharmacology, agriculture and various fields of science and their nomenclature is gradually increasing. Their widespread use depends on the availability of inexpensive and simple isotope analysis methods. The present article is an attempt to determine the nitrogen-15 isotope content directly in organic compounds without their conversion. The general principle of possibility of determination of the isotopes of nitrogen directly in organic compounds is proposed. Based on the study of mass-spectra of Carbamide Carbonyldiamide, isocyanic acid and nitrobenzene the mass peaks are selected, by which it is possible to determine the atomic fraction of the isotopes of nitrogen. The respective formulas are proposed.
基金provided by the National Scientific and Tecnological Support Program of China(Grant No:2006BAB01A11)
文摘South Qinling Tectonic Belt（SQTB）is located between the Shangzhou-Danfeng and Mianxian-Lueyang sutures.There are a lot of early Mesozoic granitoid plutons in its middle segment, comprising the Dongjiangkou-Zhashui granitoid plutons at the northeast,Huayang-Wulong-Laocheng granitoid plutons at the central part,Xiba granitoid pluton at the northwest and Guangtoushan-Liuba granitoid plutons at the southwest.These Indonisian granitoids contain a mass of various scale mafic enclaves,which show sometimes clear boundaries and sometimes transitional boundaries with their host granitoids.These granitoids also exhibit metaluminous to peraluminous series,commonly higher Mg# and a wide range of petrochemistry from low-K tholeiite series,through mid-K and high-K calc-alkaline series to shoshonite series and predominated samples are attributed to mid-K and high-K calc-alkaline series.Detailed analyses in Sr-Nd isotopic systematics and petrochemistry reveal that there may be regionally initial granitoid magma of the Indonisian granitoid plutons,comprising Dongjiangkou-Zhashui,Huayang-Wulong-Laocheng,Xiba,and Guangtoushan-Liuba granitoid plutons,which were produced by hybrids of magmas in various degrees,and the initial magmas were derived from both the mantle and the lower continental crust（LCC）sources in the SQTB.The initial granitoid magma further did the magma hybrid with the magmas from the LCC,crystallization fractionation,and assimilation with upper crustal materials during their emplacement to produce these granitoid plutons in the SQTB.These magmatism processes are most likely to occur under continent marginal arc and syn-collision to post-collision tectonic backgrounds.
基金provided by China NSFC grant (41173015, 41202093)the Chinese Ministry of Education Supervision of Ph.D. Degree Fund (20100211110020)
文摘Surface lake sediments, 28 from Hoh XU, 24 from northeastern China, 99 from Lake Bosten, 31 from Ulungur and 26 from Heihai were collected to determine δ13C and δ18O values. Considering the impact factors, conductivity, alkalinity, pH, TOC, C/N and carbonate-content in the sediments, CI, P, S, and metal element ratios of Mg/Ca, Sr/Ca, Fe/Mn of bulk sediments as environmental variables enable evaluation of their influences on δ13C and δ18O using principal component analysis （PCA） method. The closure and residence time of lakes can influence the correlation between δ13C and δ18O. Lake water will change from fresh to brackish with increasing reduction and eutrophication effects. Mg/Ca in the bulk sediment indicates the characteristic of residence time, Sr/Ca and Fe/Mn infer the salinity of lakes. Carbonate formation processes and types can influence the 6~3C--~1So correlation. ~180 will be heavier from Mg-calcite and aragonite formed in a high-salinity water body than calcite formed in freshwater conditions. When carbonate content is less than 30%, there is no relationship with either 613C or 6180, and also none between δ13C and δ18O. More than 30%, carbonate content, however, co-varies highly to δ13C and δ18O, and there is also a high correlation between δ13C and δ18O. Vegetation conditions and primary productivity of lakes can influence the characteristics of δ13C and δ18O, and their co-variance. Total organic matter content （TOC） in the sediments is higher with more terrestrial and submerged plants infilling. In northeastern and northwestern China, when organic matter in the lake sediments comes from endogenous floating organisms and algae, the δ13C value is high. δ13C is in the range of-4‰ to 0‰ when organic matter comes mainly from floating organisms （C/N〈6）; in the range of-4‰ to 8‰ when organic matter comes from diatoms （C/N=6 to 8）; and -8‰ to -4‰ when organic matter comes from aquatic and terrestrial plants （C/N〉8）.
基金the National Natural Sciences Foundation of China(grants40173025,49928201)Trans-century Training Program Foundation for the Talents by the Ministry of Education the Visiting Scholar Foundation of Labs in Universities.
文摘He-Ar isotopic compositions of fluid inclusions trapped in pyrites from some representative PGE-polymetallic deposits in Lower Cambrian black rock series in South China were analyzed by using an inert gas isotopic mass spectrometer. The results show that the ore-forming fluids possess a low 3He/4He ratio, varying from 0.43×10-8 to 26.39×10-8, with corresponding R/Ra value of 0.003-0.189. The 40Ar/36Ar ratios are 258-287, close to those of air saturated water (ASW). He-Ar isotopic indicator studies show that the ore-forming fluids were mainly derived from the formation water or basinal hot brine and sea water, while the content of mantle-derived fluid or deep-derived magmatic water might be negligible. The PGE-polymetallic mineralization might be related to the evolution of the Caledonian miogeosynclines distributed along the southern margin of the Yangtze Craton. During the Early Cambrian, the formation water or basinal hot brine trapped in Caledonian basins which accumulated giant thick sediments was expelled and migrated laterally along strata because of the pressure generated by overlying sediments. The basinal hot brine ascended along faults, mixed with sea water and finally deposited ore minerals.
