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
Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can...Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth.In this study,an improved approach of adsorbed hydrocarbons extraction from sediments was established.The improved thermal desorption approach,compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The isotopic compositions of the terminal position carbon of propane(δ^(13)C_(terminal))serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins.The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter(typeⅢkerogen)at an early mature stage.δ^(13)C_(terminal)values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks,suggesting their genetic relationship.Overall,the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.展开更多
The Metal Stable Isotope Geochemistry Laboratory(MSIGL)at the University of Science and Technology of China has developed state-of-the-art analytical methods for twelve stable isotope systems,including Mg,Si,V,Fe,Cu,Z...The Metal Stable Isotope Geochemistry Laboratory(MSIGL)at the University of Science and Technology of China has developed state-of-the-art analytical methods for twelve stable isotope systems,including Mg,Si,V,Fe,Cu,Zn,Rb,Sr,Ag,Cd,Ba,and U.Geological and biological samples were first digested by acid dissolution or alkali dissolution.The target element was subsequently purified by the column chromatography method.A Neptune Plus MC-ICP-MS was used to measure isotope compositions and the isotope bias caused during measurements was calibrated by standard bracketing and/or the double spike method.The analytical procedure was carefully checked to ensure the high precision and accuracy of the data.Here,we summarized the protocol of these established methods and compiled the standard data measured at our lab as well as those reported in literature.This comprehensive dataset can serve as a reliable benchmark for calibration,method validation,and quality assurance in metal stable isotope analyses.展开更多
Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable S...Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.展开更多
Medical isotopes are the foundation material for nuclear medicine and are primarily produced through in-reactor irradia-tion.Neutron spectrum regulation is the main technical approach for enhancing the production of m...Medical isotopes are the foundation material for nuclear medicine and are primarily produced through in-reactor irradia-tion.Neutron spectrum regulation is the main technical approach for enhancing the production of medical isotopes,and it requires determining the optimal neutron spectrum and quantifying the values of neutrons in different energy regions.We calculated the neutron energy region values for 20 medical isotopes(^(14)C,^(32)P,^(47)Sc,^(60)Co,^(64)Cu,^(67)Cu,^(89)Sr,^(90)Y,^(99)Mo,^(125)I,^(131)I,^(153)Sm,^(161)Tb,^(166)Ho,^(177)Lu,^(186)Re,^(188)Re,^(92)Ir,^(225)Ac,and ^(252)Cf).The entire energy range was divided into 238 energy regions to improve the energy spectrum resolution,and both fast and thermal reactors were simulated to enhance universal applicability.A dataset of neutron energy region values across the entire energy range was built,which identifies the positive and negative-energy regions and guides the neutron spectrum regulation process during in-reactor medical isotope produc-tion.We conducted neutron spectrum regulation based on this dataset,which effectively improved the production efficiency of medical isotopes and demonstrated the correctness and feasibility of the dataset.展开更多
Although the demand of ^(10)B separation has arisen in the 1930s,^(10)B/^(11)B are among the most difficult isotopes to separate due to the extremely similar relative atomic mass.Herein,we report an efficient separati...Although the demand of ^(10)B separation has arisen in the 1930s,^(10)B/^(11)B are among the most difficult isotopes to separate due to the extremely similar relative atomic mass.Herein,we report an efficient separation of ^(10)B isotopologue by engineering amino-galloyl synergistic materials via a selective adsorption and isotope exchange reaction,achieving a record-high single-stage separation factor of 1.048 with ^(10)B abundance up to 21.42%.^(11)B MAS NMR results and DFT calculations reveal that the galloyl groups exhibit inherent high affinity for B(OH)4-,forming tetrahedral sp^(3) B-galloyl complexes.The relatively higher ^(10)B–O bond energy of ^(10)B-galloyl complexes facilitates the isotope exchange between11B in B-galloyl complexes and ^(10)B in B(OH)_(3).Flowthrough dynamic separation in fixed-bed demonstrates the feasibility and potential of large-scale deployment of this method in real-world,suggesting a promising avenue for the exploitation of more efficient enrichment of ^(10)B for the sustainable nuclear energy and biomedical research.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
Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some sho...Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.展开更多
Sulfur isotopes of S-bearing materials are powerful tools to trace various geological processes and sulfur sources in earth sciences,especially in ore deposits where sulfide-sulfate pair coprecipitates widely.However,...Sulfur isotopes of S-bearing materials are powerful tools to trace various geological processes and sulfur sources in earth sciences,especially in ore deposits where sulfide-sulfate pair coprecipitates widely.However,in-situ S isotope determination of barite is challenging without natural matrix-matched reference material.In this study,we present two natural barite reference materials(1-YS and 294-YS)for in-situ sulfur isotopic analysis.Independent LA-MC-ICP-MS laboratories were utilized to test theδ34S micron-scale homogeneity of 1-YS and 294-YS barites that have 2s repeatabilities of better than±0.45‰and±0.41‰,respectively.Meanwhile,the in-situ analysis results are consistent with the results of the bulk analysis by GS-IRMS within uncertainty.The grand meanδ~(34)S values of 1-YS(13.37‰±0.42‰,2s)and 294-YS(14.38‰±0.44‰,2s)are the final recommended values obtained from four independent laboratories.All the results confirm the suitability of 1-YS and 294-YS barite used as calibration materials with respect to in-situ S isotopic analysis.Moreover,the new developed barite reference materials were used as matrix-matched standard to calibrate the barite samples from the Huayangchuan carbonatite-hosted U-polymetallic deposit(Qinling orogenic belt,western China)to obtainδ34S values.Utilizing the temperaturedependentδ34S fractionation of barite-pyrite pair,we calculate the formation temperature of barite(i.e.,506 to 537°C)and theδ34S value of mineralizing fluid(i.e.,-7.11‰to-7.59‰)in the Huayangchuan deposit.The results indicate an involvement of sedimentary sulfur,presumably acting as a potential uranium source(e.g.,upper crustal materials)for the giant Huayangchuan deposit.展开更多
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
The Cretaceous Koum Basin is a rift-related half-graben in northern Cameroon,which constitutes a portion of the Yola Arm of the Upper Benue Trough.This study presents the first comprehensive dataset combining mineral-...The Cretaceous Koum Basin is a rift-related half-graben in northern Cameroon,which constitutes a portion of the Yola Arm of the Upper Benue Trough.This study presents the first comprehensive dataset combining mineral-ogical,bulk-rock geochemical,and stable C-H-O isotopic data for dark-gray,finegrained mudstones from the basin,providing new insights into its sediment source,paleoenvironment,and geodynamic setting.The mudstones primarily consist of phyllosilicates(~8.6%),feldspars(~30.5%),carbonates(~13.7%),and minor iron oxides(~2.7%),with vermiculite,illite,and kaolinite as the main clay minerals.The presence of analcime,ankerite,and dolomite suggests low-grade metamorphism and/or hydrothermal alteration.Fe_(2)O_(3)/K_(2)O(1.52-6.40)and SiO_(2)/Al_(2)O_(3)(2.97-4.68)ratios classify the mudstones as compositionally immature shales(ICV~1.64)with low-moderate chemical weathering(CIA~56.35;PIA~59.74;R^(3+)/R^(3+)+R^(2+)+M^(+)~0.51).Trace element ratios(Th/Sc~1.70,Zr/Sc~1.33,La/Sc~6.30,La/Th~4.14)indicate an intermediate igneous provenance from a continental crustal source.Paleoenviron-mental proxies suggest deposition in a dynamic basin environment marked by fluctuating redox(C org/P:0.21-178.34)and salinity(Sr/Ba:0.34-3.25;N-values:48-35.92)conditions,ranging from oxic to anoxic and brackish to saline.Major element data(SiO_(2) vs.Al_(2)O_(3)+K_(2)O+Na_(2)O)indicate a semi-arid regime,while Paleoclimatic indicators such as Sr/Cu(1.88-37.47)and C-values(0.12-0.93)suggests alter-nating humid and arid conditions.Notably,stable isotope data,reported here for the first time in the Koum Basin,reveal a predominantly terrestrial,fluvial-deltaic C_(3) plant source for organic carbon(δ^(13)C-25.2‰ to -35.2‰)and complex fluid-rock interactions involving meteoric and magmatic-metamorphic fluids under a warm,equatorial climate(δ^(18)O+3.6‰to +24.9‰,δ^(2)H-104‰ to-50‰).The combined mineralogical,geochemical,and isotopic data point to deposition in a tectonically active continental arc setting,with contributions from ocean island arc and passive margin sources.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
0 INTRODUCTION Tin(Sn)deposits are genetically associated with reduced,crust-derived magmas where Sn is incompatible(as Sn^(2+))and tends to enrich in residual melts during magma evolution(e.g.,Lehmann,2021;Linnen et ...0 INTRODUCTION Tin(Sn)deposits are genetically associated with reduced,crust-derived magmas where Sn is incompatible(as Sn^(2+))and tends to enrich in residual melts during magma evolution(e.g.,Lehmann,2021;Linnen et al.,1995).In contrast,copper(Cu)deposits are typically related to oxidized,mantle-derived magmas where Cu is incompatible because sulfur(S)occurs as sulfate(e.g.,Deng et al.,2023;Sillitoe and Lehmann,2022;Jugo,2009).Thus,Sn and Cu mineralization are rarely coexisting in a single magmatic-hydrothermal deposit(Sillitoe and Lehmann,2022).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
Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress.Both reversible and irreversible covalent inhibitors are developed for targeting lysin...Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress.Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues.The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity.For covalent inhibitors,the pull down-based methods including activity-based protein profiling(ABPP)are commonly used to profile their target proteins.For covalent reversible inhibitors,it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner.Here,we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules.This pair of isotopic probes consists of a lysinereactive warhead,a desthiobiotin moiety and isotopicable linker.This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process.To demonstrate the feasibility of our newly-developed probes for the protein target identification,we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner.Finally,we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol.Interestingly,pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins.Together,our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.展开更多
Extraterrestrial dust exhibits a wide range of textural,chemical and oxygen isotopic compositions due to the heterogeneity of their precursors and modification during atmospheric entry.Experimental heating provides an...Extraterrestrial dust exhibits a wide range of textural,chemical and oxygen isotopic compositions due to the heterogeneity of their precursors and modification during atmospheric entry.Experimental heating provides an opportunity to investigate the relationship between thermal processing and micrometeorite composition for a known precursor material.We conducted experiments to simulate the atmospheric entry of micrometeorites(MMs)using controlled,short-duration(10-50 s)flash heating(400-1600℃)of CI chondrite chips(<1500µm)in atmospheric air(1 bar,21%O2)combined with microanalysis(textures,chemical and isotopic compositions)of the experimental products.The heated chips closely resemble natural samples,with materials similar to unmelted MMs,partially melted(scoriaceous)MMs and fully melted cosmic spherules produced.We reproduced several key features such as dehydration cracks,magnetite rims,volatile gas release,vesicle formation and coalescence,melting and quench cooling.Our parameter space allows for discriminating peak temperature and heating duration effects.Peak temperature is the first-order control on MM mineralogy,while heating duration controls vesicle coalescence and homogenization.When compared against previous heating experiments,our data demonstrates that CI chondrite dust is more thermally resistant,relative to CM chondrite dust,by approximately+200℃.The 207 measurement of O-isotopes allows,for the first time,petrographic effects(such as volatile degassing and melting)to be correlated against bulk O-isotope evolution.Our results demonstrate findings applicable to CI chondrites and potentially to all fine-grained hydrated carbonaceous chondrite dust grains:(1)O-isotope variations arising during sub-solidus heating are dominated by the release of water from phyllosilicates,forcing the residual MM composition towards its anhydrous precursor composition.(2)Oxygen isotope compositions undergo the most significant changes at supra-solidus temperatures.As previously demonstrated and now empirically confirmed,most of these changes are driven by a mass-dependent fractionation effect caused by evaporation,which shifts residual rock compositions toward heavier values.Mixing with atmospheric air alters compositions toward the terrestrial fractionation line.Notably,these two processes do not begin simultaneously.Our data indicate that at 1200℃,isotopic evolution is dominated by evaporative mass loss.However,at higher temperatures(1400-1600℃),both pronounced evaporation and mixing with atmospheric oxygen become active,resulting in a more complex isotopic signature.(3)The total change in Δ17O during heating up to 1600℃is<3‰and in most scenarios<2‰.展开更多
Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not y...Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.展开更多
Microwave digestion-inductively coupled plasma mass spectrometry(ICP-MS)was used to analyze the sources of lead in farmland soil and rice in the Jiulongjiang River Basin.The results suggested that the source of lead i...Microwave digestion-inductively coupled plasma mass spectrometry(ICP-MS)was used to analyze the sources of lead in farmland soil and rice in the Jiulongjiang River Basin.The results suggested that the source of lead in rice was differ from that in soil.There were four main sources of lead in farmland soil:natural source,agricultural source,industrial source and fossil fuel source,among which natural source,agricultural source and industrial source contributed more.There were four main sources of lead in rice:natural,agricultural,industrial and fossil fuel sources,and more importantly,fossil fuel sources.The comparison of lead isotope composition with potential sources(^(206)Pb/^(207)Pb,^(208)Pb/^(206)Pb,^(208)Pb/^(207)Pb)can provide a scientific basis for the identification and treatment of heavy metal lead pollution sources in farmland soil and rice in the Jiulong River Basin.展开更多
The tectonic evolution of Borneo and the affiliation between Southern and Northern Borneo remains unclear.The Rajang and Crocker Fan sediments,as one of the largest ancient submarine fans in Southeast Asia have witnes...The tectonic evolution of Borneo and the affiliation between Southern and Northern Borneo remains unclear.The Rajang and Crocker Fan sediments,as one of the largest ancient submarine fans in Southeast Asia have witnessed the tectonic evolution of Borneo since at least the late Mesozoic.In this study,we present laser ablation inductively coupled plasma mass spectrometer(LA-ICP-MS)U-Pb dating and Hf isotopic results of detrital zircons from the Trusmadi and Crocker formations within the Crocker Fan of Sabah,Northern Borneo.Our results,coupled with previous data,show that the Crocker Fan sediments in Sabah of Northern Borneo display similar age spectra to the Rajang Fan sediments in Sarawak of Central Borneo,with two major age clusters at 130-80 and 280-200 Ma.Further provenance analysis based on mineral shape with a prismatic characteristic and similar detrital zircon Hf isotopes of the two formations illustrates that the Jurassic-Cretaceous and partly Triassic detrital zircons of the Crocker and Rajang Fan sediments were derived from the erosion of contemporaneous magmatic rocks;part of Permian-Triassic ones could be the recycling of the Jurassic deposits in SW Borneo.The initial provenance of these Permian-Triassic detritus could be synchronous magmatic rocks in the Tin belt of the Malay Peninsula.Combining with previous data,we propose that the entire Borneo continent,including both Southern and Northern Borneo,developed a common Mesozoic continental magmatic arc.Moreover,we postulate that the Rajang and Crocker fans formed in a fore-arc extensional rift basin related to the retreat of the subducted Paleo-Pacific Plate beneath the Northern Borneo margin.展开更多
The pervasively distributed granitoids in South China contributed greatly to regional polymetallic mineralization,including tungsten,tin,copper,gold,rare metals,and rare earth elements(REEs).To ascertain the dynamic b...The pervasively distributed granitoids in South China contributed greatly to regional polymetallic mineralization,including tungsten,tin,copper,gold,rare metals,and rare earth elements(REEs).To ascertain the dynamic backgrounds,rock types and genesis of the parent rocks related to the Early-Middle Jurassic ionic rare earth mineralization,typical deposits at Muzishan,Xiahu,and Zudong were investigated by conducting petrographic,geochronologic,whole-rock geochemical,and Sr-Nd-Pb isotope analyses,which found that the parent rocks from the Muzishan deposit were the A1-type K-feldspar granite(~195 Ma),from the Zudong deposit were the A2-type monzogranite(~171 Ma),and from the Xiahu deposit were the I-type monzogranite(~167 Ma).All the three granitic rocks underwent different degrees of fractionation,with the Xiahu granite experiencing the highest degree,followed by the Zudong granite,and the Muzishan granite undergoing the lowest degree.The Muzishan granite was concluded to be formed under an intraplate extensional tectonic regime influenced by the hotspots or the mantle plume.The Zudong granite was formed in a post-arc extensional setting related to subduction-collision-rollback of the paleo-Pacific Plate,which caused upwelling of the asthenosphere,thinning of the lithosphere,and partial melting of crustal materials.The Xiahu granite was generated under a transitional tectonic setting of extension and compression,triggered by delamination and rollback of the paleo-Pacific Plate.展开更多
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financially supported by the National Natural Science Foundation of China(Grant No.42102202)U.S.Department of Energy Geosciences program(DE-SC0016271)。
文摘Hydrocarbons are one of the important fluids within the Earth's crust,and different biotic and abitoic processes can generate hydrocarbon during geological periods.Tracing the sources and sinks of hydrocarbons can help us better understand the carbon cycle of the earth.In this study,an improved approach of adsorbed hydrocarbons extraction from sediments was established.The improved thermal desorption approach,compound-specific isotope analysis and position-specific isotope analysis were integrated to investigate the molecular and intramolecular isotope fractionation between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The isotopic compositions of the terminal position carbon of propane(δ^(13)C_(terminal))serves as a correlation indicator between trace hydrocarbon gases within sediments and geological hydrocarbon deposits.The tight sandstone gas from the Turpan-Hami Basin is a first case study for the application of this novel method to trace hydrocarbon origins.The results showed that the hydrocarbons in the tight sandstone gases in the study area most likely originated from humic organic matter(typeⅢkerogen)at an early mature stage.δ^(13)C_(terminal)values of the thermally desorbed propane gases from different source rocks were distinguishable and the values of the tight sandstone gases significantly overlap with those of the Lower Jurassic Sangonghe source rocks,suggesting their genetic relationship.Overall,the results provided novel position-specific carbon isotopic constraints on origins of hydrocarbons.
基金the National Science Foundation of China(Nos.42273007 and 42473008)the Distinguished Young Scholars of Anhui,China(No.2408085J021)。
文摘The Metal Stable Isotope Geochemistry Laboratory(MSIGL)at the University of Science and Technology of China has developed state-of-the-art analytical methods for twelve stable isotope systems,including Mg,Si,V,Fe,Cu,Zn,Rb,Sr,Ag,Cd,Ba,and U.Geological and biological samples were first digested by acid dissolution or alkali dissolution.The target element was subsequently purified by the column chromatography method.A Neptune Plus MC-ICP-MS was used to measure isotope compositions and the isotope bias caused during measurements was calibrated by standard bracketing and/or the double spike method.The analytical procedure was carefully checked to ensure the high precision and accuracy of the data.Here,we summarized the protocol of these established methods and compiled the standard data measured at our lab as well as those reported in literature.This comprehensive dataset can serve as a reliable benchmark for calibration,method validation,and quality assurance in metal stable isotope analyses.
基金supported by National Natural Science Foundation of China(42473009).
文摘Stable Sr isotopic composition(δ^(88/86)Sr)can be used to study magmatic processes,but their fractionation mechanism during magmatic evolution remains unclear.To understand the fractionation behaviors of the stable Sr isotopes during magmatism,we report theδ^(88/86)Sr values of the Huili granitic pluton,which was subjected to intensive crystal-melt separation.The Huili pluton consists of K-feldspar granite and more evolved albite granite,and the albite granite exhibits significantly higherδ^(88/86)Sr values(+0.36‰to+0.52‰)than that of K-feldspar granite(+0.11‰to+0.25‰).K-feldspar,which contributes most of the Sr budget of the K-feldspar granite,has slightly lowerδ^(88/86)Sr values(−0.01‰to+0.17‰)than the whole rock.Theδ^(88/86)Sr variation of the Huili granites can be explained by separation of melt from K-feldspar-dominated crystals,because crystallization of K-feldspar can result in heavy Sr isotopic composition of the extracted interstitial melt.Stable Sr and Ba isotopic ratios in the Huili granites are highly coupled toward the heavy direction,refl ecting their similar element partitioning and isotope fractionation behaviors between the crystalline K-feldspar and melt.This study indicates that melt extraction plays a key role in granitic magma evolution.
基金sponsored by the National Natural Science Foundation of China(No.12305190)Lingchuang Research Project of China National Nuclear Corporation(CNNC).
文摘Medical isotopes are the foundation material for nuclear medicine and are primarily produced through in-reactor irradia-tion.Neutron spectrum regulation is the main technical approach for enhancing the production of medical isotopes,and it requires determining the optimal neutron spectrum and quantifying the values of neutrons in different energy regions.We calculated the neutron energy region values for 20 medical isotopes(^(14)C,^(32)P,^(47)Sc,^(60)Co,^(64)Cu,^(67)Cu,^(89)Sr,^(90)Y,^(99)Mo,^(125)I,^(131)I,^(153)Sm,^(161)Tb,^(166)Ho,^(177)Lu,^(186)Re,^(188)Re,^(92)Ir,^(225)Ac,and ^(252)Cf).The entire energy range was divided into 238 energy regions to improve the energy spectrum resolution,and both fast and thermal reactors were simulated to enhance universal applicability.A dataset of neutron energy region values across the entire energy range was built,which identifies the positive and negative-energy regions and guides the neutron spectrum regulation process during in-reactor medical isotope produc-tion.We conducted neutron spectrum regulation based on this dataset,which effectively improved the production efficiency of medical isotopes and demonstrated the correctness and feasibility of the dataset.
基金supported by the National Natural Science Foundation of China(Nos.22108181,22178233)the Fund of Science and Technology on Reactor Fuel and Materials Laboratory(No.6142A06190601)+6 种基金the National Excellent Young Scientists Fund(No.00308054A1045)the National Key R&D Program of China(No.2022YFA0912800)the Talents Program of Sichuan ProvinceDouble First Class University Plan of Sichuan Universitythe State Key Laboratory of Polymer Materials Engineering(No.sklpme 2020–03–01)the Tianfu Emei Program of Sichuan Province(No.2022EC02–00073-CG)Ministry of Education Key Laboratory of Leather Chemistry and Engineering(Sichuan University)。
文摘Although the demand of ^(10)B separation has arisen in the 1930s,^(10)B/^(11)B are among the most difficult isotopes to separate due to the extremely similar relative atomic mass.Herein,we report an efficient separation of ^(10)B isotopologue by engineering amino-galloyl synergistic materials via a selective adsorption and isotope exchange reaction,achieving a record-high single-stage separation factor of 1.048 with ^(10)B abundance up to 21.42%.^(11)B MAS NMR results and DFT calculations reveal that the galloyl groups exhibit inherent high affinity for B(OH)4-,forming tetrahedral sp^(3) B-galloyl complexes.The relatively higher ^(10)B–O bond energy of ^(10)B-galloyl complexes facilitates the isotope exchange between11B in B-galloyl complexes and ^(10)B in B(OH)_(3).Flowthrough dynamic separation in fixed-bed demonstrates the feasibility and potential of large-scale deployment of this method in real-world,suggesting a promising avenue for the exploitation of more efficient enrichment of ^(10)B for the sustainable nuclear energy and biomedical research.
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supported by the Natural Science Foundation of China(Grant No.42302170)National Postdoctoral Innovative Talent Support Program(Grant No.BX20220062)+3 种基金CNPC Innovation Found(Grant No.2022DQ02-0104)National Science Foundation of Heilongjiang Province of China(Grant No.YQ2023D001)Postdoctoral Science Foundation of Heilongjiang Province of China(Grant No.LBH-Z22091)the Natural Science Foundation of Shandong Province(Grant No.ZR2022YQ30).
文摘Prediction of production decline and evaluation of the adsorbed/free gas ratio are critical for determining the lifespan and production status of shale gas wells.Traditional production prediction methods have some shortcomings because of the low permeability and tightness of shale,complex gas flow behavior of multi-scale gas transport regions and multiple gas transport mechanism superpositions,and complex and variable production regimes of shale gas wells.Recent research has demonstrated the existence of a multi-stage isotope fractionation phenomenon during shale gas production,with the fractionation characteristics of each stage associated with the pore structure,gas in place(GIP),adsorption/desorption,and gas production process.This study presents a new approach for estimating shale gas well production and evaluating the adsorbed/free gas ratio throughout production using isotope fractionation techniques.A reservoir-scale carbon isotope fractionation(CIF)model applicable to the production process of shale gas wells was developed for the first time in this research.In contrast to the traditional model,this model improves production prediction accuracy by simultaneously fitting the gas production rate and δ^(13)C_(1) data and provides a new evaluation method of the adsorbed/free gas ratio during shale gas production.The results indicate that the diffusion and adsorption/desorption properties of rock,bottom-hole flowing pressure(BHP)of gas well,and multi-scale gas transport regions of the reservoir all affect isotope fractionation,with the diffusion and adsorption/desorption parameters of rock having the greatest effect on isotope fractionation being D∗/D,PL,VL,α,and others in that order.We effectively tested the universality of the four-stage isotope fractionation feature and revealed a unique isotope fractionation mechanism caused by the superimposed coupling of multi-scale gas transport regions during shale gas well production.Finally,we applied the established CIF model to a shale gas well in the Sichuan Basin,China,and calculated the estimated ultimate recovery(EUR)of the well to be 3.33×10^(8) m^(3);the adsorbed gas ratio during shale gas production was 1.65%,10.03%,and 23.44%in the first,fifth,and tenth years,respectively.The findings are significant for understanding the isotope fractionation mechanism during natural gas transport in complex systems and for formulating and optimizing unconventional natural gas development strategies.
基金supported by the National Natural Science Foundation of China(Nos.42003014,42363004,42073051,42303023)Jiangxi Provincial Natural Science Foundation(No.20232BAB213070)the Natural Science Foundation of Shandong Province(No.ZR2022QD050)。
文摘Sulfur isotopes of S-bearing materials are powerful tools to trace various geological processes and sulfur sources in earth sciences,especially in ore deposits where sulfide-sulfate pair coprecipitates widely.However,in-situ S isotope determination of barite is challenging without natural matrix-matched reference material.In this study,we present two natural barite reference materials(1-YS and 294-YS)for in-situ sulfur isotopic analysis.Independent LA-MC-ICP-MS laboratories were utilized to test theδ34S micron-scale homogeneity of 1-YS and 294-YS barites that have 2s repeatabilities of better than±0.45‰and±0.41‰,respectively.Meanwhile,the in-situ analysis results are consistent with the results of the bulk analysis by GS-IRMS within uncertainty.The grand meanδ~(34)S values of 1-YS(13.37‰±0.42‰,2s)and 294-YS(14.38‰±0.44‰,2s)are the final recommended values obtained from four independent laboratories.All the results confirm the suitability of 1-YS and 294-YS barite used as calibration materials with respect to in-situ S isotopic analysis.Moreover,the new developed barite reference materials were used as matrix-matched standard to calibrate the barite samples from the Huayangchuan carbonatite-hosted U-polymetallic deposit(Qinling orogenic belt,western China)to obtainδ34S values.Utilizing the temperaturedependentδ34S fractionation of barite-pyrite pair,we calculate the formation temperature of barite(i.e.,506 to 537°C)and theδ34S value of mineralizing fluid(i.e.,-7.11‰to-7.59‰)in the Huayangchuan deposit.The results indicate an involvement of sedimentary sulfur,presumably acting as a potential uranium source(e.g.,upper crustal materials)for the giant Huayangchuan deposit.
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.
文摘The Cretaceous Koum Basin is a rift-related half-graben in northern Cameroon,which constitutes a portion of the Yola Arm of the Upper Benue Trough.This study presents the first comprehensive dataset combining mineral-ogical,bulk-rock geochemical,and stable C-H-O isotopic data for dark-gray,finegrained mudstones from the basin,providing new insights into its sediment source,paleoenvironment,and geodynamic setting.The mudstones primarily consist of phyllosilicates(~8.6%),feldspars(~30.5%),carbonates(~13.7%),and minor iron oxides(~2.7%),with vermiculite,illite,and kaolinite as the main clay minerals.The presence of analcime,ankerite,and dolomite suggests low-grade metamorphism and/or hydrothermal alteration.Fe_(2)O_(3)/K_(2)O(1.52-6.40)and SiO_(2)/Al_(2)O_(3)(2.97-4.68)ratios classify the mudstones as compositionally immature shales(ICV~1.64)with low-moderate chemical weathering(CIA~56.35;PIA~59.74;R^(3+)/R^(3+)+R^(2+)+M^(+)~0.51).Trace element ratios(Th/Sc~1.70,Zr/Sc~1.33,La/Sc~6.30,La/Th~4.14)indicate an intermediate igneous provenance from a continental crustal source.Paleoenviron-mental proxies suggest deposition in a dynamic basin environment marked by fluctuating redox(C org/P:0.21-178.34)and salinity(Sr/Ba:0.34-3.25;N-values:48-35.92)conditions,ranging from oxic to anoxic and brackish to saline.Major element data(SiO_(2) vs.Al_(2)O_(3)+K_(2)O+Na_(2)O)indicate a semi-arid regime,while Paleoclimatic indicators such as Sr/Cu(1.88-37.47)and C-values(0.12-0.93)suggests alter-nating humid and arid conditions.Notably,stable isotope data,reported here for the first time in the Koum Basin,reveal a predominantly terrestrial,fluvial-deltaic C_(3) plant source for organic carbon(δ^(13)C-25.2‰ to -35.2‰)and complex fluid-rock interactions involving meteoric and magmatic-metamorphic fluids under a warm,equatorial climate(δ^(18)O+3.6‰to +24.9‰,δ^(2)H-104‰ to-50‰).The combined mineralogical,geochemical,and isotopic data point to deposition in a tectonically active continental arc setting,with contributions from ocean island arc and passive margin sources.
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 National Natural Science Foundation of China(Nos.42002080,42302092)the Guangxi Technology Base and Talent Project(No.Guike AD20238013)the Provincial Natural Science Foundation of Hunan(No.2024JJ5394)。
文摘0 INTRODUCTION Tin(Sn)deposits are genetically associated with reduced,crust-derived magmas where Sn is incompatible(as Sn^(2+))and tends to enrich in residual melts during magma evolution(e.g.,Lehmann,2021;Linnen et al.,1995).In contrast,copper(Cu)deposits are typically related to oxidized,mantle-derived magmas where Cu is incompatible because sulfur(S)occurs as sulfate(e.g.,Deng et al.,2023;Sillitoe and Lehmann,2022;Jugo,2009).Thus,Sn and Cu mineralization are rarely coexisting in a single magmatic-hydrothermal deposit(Sillitoe and Lehmann,2022).
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 funding from The National Natural Science Foundation of China(No.22177136)the CAMS Innovation Fund for Medical Sciences(CIFMS)(No.2022-I2M-2-002).
文摘Recent advances in drug development and bioactive molecules that covalently target lysine residues have shown substantial progress.Both reversible and irreversible covalent inhibitors are developed for targeting lysine residues.The identification of protein targets and binding sites of these lysine-targeting molecules in the whole proteome is crucial to understand their proteome-wide selectivity.For covalent inhibitors,the pull down-based methods including activity-based protein profiling(ABPP)are commonly used to profile their target proteins.For covalent reversible inhibitors,it is not easy to pull down the potential protein targets as the captured proteins may get off beads because of the reversible manner.Here,we report a pair of isotope-labelled click-free probes to competitively identify the protein targets of lysine-targeting covalent reversible small molecules.This pair of isotopic probes consists of a lysinereactive warhead,a desthiobiotin moiety and isotopicable linker.This integrated probe could eliminate the background proteins induced by the click chemistry during the pull-down process.To demonstrate the feasibility of our newly-developed probes for the protein target identification,we selected the natural product Gossypol in that we proved for the first time that it could modify the lysine residue in a covalent reversible manner.Finally,we confirmed that this pair of integrated probes can be used in a competitive manner to precisely identify the protein target as well as binding sites of Gossypol.Interestingly,pretreatment of Gossypol could stop the antibody from recognizing Gossypol-binding proteins.Together,our isotope-labeled click-free probes could be used for whole-proteome profiling of lysine-targeting covalent reversible small molecules.
基金ISRO-RESPOND GAP3332 and PMN-MOES GAP2175 Project support this work.
文摘Extraterrestrial dust exhibits a wide range of textural,chemical and oxygen isotopic compositions due to the heterogeneity of their precursors and modification during atmospheric entry.Experimental heating provides an opportunity to investigate the relationship between thermal processing and micrometeorite composition for a known precursor material.We conducted experiments to simulate the atmospheric entry of micrometeorites(MMs)using controlled,short-duration(10-50 s)flash heating(400-1600℃)of CI chondrite chips(<1500µm)in atmospheric air(1 bar,21%O2)combined with microanalysis(textures,chemical and isotopic compositions)of the experimental products.The heated chips closely resemble natural samples,with materials similar to unmelted MMs,partially melted(scoriaceous)MMs and fully melted cosmic spherules produced.We reproduced several key features such as dehydration cracks,magnetite rims,volatile gas release,vesicle formation and coalescence,melting and quench cooling.Our parameter space allows for discriminating peak temperature and heating duration effects.Peak temperature is the first-order control on MM mineralogy,while heating duration controls vesicle coalescence and homogenization.When compared against previous heating experiments,our data demonstrates that CI chondrite dust is more thermally resistant,relative to CM chondrite dust,by approximately+200℃.The 207 measurement of O-isotopes allows,for the first time,petrographic effects(such as volatile degassing and melting)to be correlated against bulk O-isotope evolution.Our results demonstrate findings applicable to CI chondrites and potentially to all fine-grained hydrated carbonaceous chondrite dust grains:(1)O-isotope variations arising during sub-solidus heating are dominated by the release of water from phyllosilicates,forcing the residual MM composition towards its anhydrous precursor composition.(2)Oxygen isotope compositions undergo the most significant changes at supra-solidus temperatures.As previously demonstrated and now empirically confirmed,most of these changes are driven by a mass-dependent fractionation effect caused by evaporation,which shifts residual rock compositions toward heavier values.Mixing with atmospheric air alters compositions toward the terrestrial fractionation line.Notably,these two processes do not begin simultaneously.Our data indicate that at 1200℃,isotopic evolution is dominated by evaporative mass loss.However,at higher temperatures(1400-1600℃),both pronounced evaporation and mixing with atmospheric oxygen become active,resulting in a more complex isotopic signature.(3)The total change in Δ17O during heating up to 1600℃is<3‰and in most scenarios<2‰.
基金supported by the National Natural Science Foundation of China(U21A2033)the Fundamental Research Funds for the Central Universities(2652022103).
文摘Microbial vanadate(V(V))reduction is a key process for environmental geochemistry and detoxification of vanadium(V).However,the electron transfer pathways and V isotope fractionation involved in this process are not yet fully understood.In this study,the V(V)reduction mechanisms with concomitant V isotope fractionation by the Gram-positive bacterium Bacillus subtilis(B.subtilis)and the Gramnegative bacterium Thauera humireducens(T.humireducens)were investigated.Both strains could effectively reduce V(V),removing(90.5%±1.6%)and(93.0%±1.8%)of V(V)respectively from an initial concentration of 50 mg L^(-1) during a 10-day incubation period.V(V)was bioreduced to insoluble vanadium(IV),which was distributed both inside and outside the cells.Electron transfer via cytochrome C,nicotinamide adenine dinucleotide,and glutathione played critical roles in V(V)reduction.Metabolomic analysis showed that differentially enriched metabolites(quinone,biotin,and riboflavin)mediated electron transfer in both strains.The aqueous V in the remaining solution became isotopically heavier as V(V)bioreduction proceeded.The obtained V isotope composition dynamics followed a Rayleigh fractionation model,and the isotope enrichment factor(e)was(–0.54‰±0.04‰)for B.subtilis and(–0.32‰±0.03‰)for T.humireducens,with an insignificant difference.This study provides molecular insights into electron transfer for V(V)bioreduction and reveals V isotope fractionation during this bioprocess,which is helpful for understanding V biogeochemistry and developing novel strategies for V remediation.
基金Supported by Natural Science Foundation of Fujian Province(2023J011667)Natural Science Foundation of Xiamen(3502Z202374084).
文摘Microwave digestion-inductively coupled plasma mass spectrometry(ICP-MS)was used to analyze the sources of lead in farmland soil and rice in the Jiulongjiang River Basin.The results suggested that the source of lead in rice was differ from that in soil.There were four main sources of lead in farmland soil:natural source,agricultural source,industrial source and fossil fuel source,among which natural source,agricultural source and industrial source contributed more.There were four main sources of lead in rice:natural,agricultural,industrial and fossil fuel sources,and more importantly,fossil fuel sources.The comparison of lead isotope composition with potential sources(^(206)Pb/^(207)Pb,^(208)Pb/^(206)Pb,^(208)Pb/^(207)Pb)can provide a scientific basis for the identification and treatment of heavy metal lead pollution sources in farmland soil and rice in the Jiulong River Basin.
基金jointly supported by the Scientific Research Foundation of Third Institute of Oceanography,Ministry of Natural Resources,Xiamen(No.2018002)the Guangxi Natural Science Fundation(No.2022GXNSFBA035588)+1 种基金the National Natural Science Foundation of China(Nos.41506050,41402193)the Scientific Research Foundation of Guangxi Key Laboratory of Hidden Metallic Ore Deposits Exploration(No.19-185-17-09)。
文摘The tectonic evolution of Borneo and the affiliation between Southern and Northern Borneo remains unclear.The Rajang and Crocker Fan sediments,as one of the largest ancient submarine fans in Southeast Asia have witnessed the tectonic evolution of Borneo since at least the late Mesozoic.In this study,we present laser ablation inductively coupled plasma mass spectrometer(LA-ICP-MS)U-Pb dating and Hf isotopic results of detrital zircons from the Trusmadi and Crocker formations within the Crocker Fan of Sabah,Northern Borneo.Our results,coupled with previous data,show that the Crocker Fan sediments in Sabah of Northern Borneo display similar age spectra to the Rajang Fan sediments in Sarawak of Central Borneo,with two major age clusters at 130-80 and 280-200 Ma.Further provenance analysis based on mineral shape with a prismatic characteristic and similar detrital zircon Hf isotopes of the two formations illustrates that the Jurassic-Cretaceous and partly Triassic detrital zircons of the Crocker and Rajang Fan sediments were derived from the erosion of contemporaneous magmatic rocks;part of Permian-Triassic ones could be the recycling of the Jurassic deposits in SW Borneo.The initial provenance of these Permian-Triassic detritus could be synchronous magmatic rocks in the Tin belt of the Malay Peninsula.Combining with previous data,we propose that the entire Borneo continent,including both Southern and Northern Borneo,developed a common Mesozoic continental magmatic arc.Moreover,we postulate that the Rajang and Crocker fans formed in a fore-arc extensional rift basin related to the retreat of the subducted Paleo-Pacific Plate beneath the Northern Borneo margin.
基金supported by the Open Fund Project of the Key Laboratory of Ionic Rare Earth Resources and Environment,Ministry of Natural Resources(Grant No.2022IREE101)the Young Elite Scientists Sponsorship Program by CAST(Grant No.2022QNRC001)the Geological Investigation Project(Grant Nos.DD20243483,DD20221643).
文摘The pervasively distributed granitoids in South China contributed greatly to regional polymetallic mineralization,including tungsten,tin,copper,gold,rare metals,and rare earth elements(REEs).To ascertain the dynamic backgrounds,rock types and genesis of the parent rocks related to the Early-Middle Jurassic ionic rare earth mineralization,typical deposits at Muzishan,Xiahu,and Zudong were investigated by conducting petrographic,geochronologic,whole-rock geochemical,and Sr-Nd-Pb isotope analyses,which found that the parent rocks from the Muzishan deposit were the A1-type K-feldspar granite(~195 Ma),from the Zudong deposit were the A2-type monzogranite(~171 Ma),and from the Xiahu deposit were the I-type monzogranite(~167 Ma).All the three granitic rocks underwent different degrees of fractionation,with the Xiahu granite experiencing the highest degree,followed by the Zudong granite,and the Muzishan granite undergoing the lowest degree.The Muzishan granite was concluded to be formed under an intraplate extensional tectonic regime influenced by the hotspots or the mantle plume.The Zudong granite was formed in a post-arc extensional setting related to subduction-collision-rollback of the paleo-Pacific Plate,which caused upwelling of the asthenosphere,thinning of the lithosphere,and partial melting of crustal materials.The Xiahu granite was generated under a transitional tectonic setting of extension and compression,triggered by delamination and rollback of the paleo-Pacific Plate.
