Petrogenesis and Tectonic Significance of Shenxianshui Alkaline Granite in Gejiu,Yunnan Province,China

The Shenxianshui granites in the western Gejiu area were formed in the Late Cretaceous.Laser ablation inductively coupled plasma mass spectrometry indicates zircon U-Pb ages ranging from 90.67±0.7 to 85.97±0.6 Ma.The intrusive rocks are peraluminous(A/CNK=1.03 to 1.33)and calc-alkaline,showing an affinity towards I-type granite.Large ion lithophilic elements are enriched in K and Rb,while high field strength elements are depleted.Moreover,light rare earth elements are significantly enriched,showing a slight negative Eu anomaly(Eu/Eu^(*)=0.39 to 0.58).Shenxianshui granite has a relatively high initial Sr isotope ratio(^(87)Sr/^(86)Sr)_(i)(0.7098-0.7105),negative ε_(Nd)(t)values(−7.99 to−7.44)and negative ε_(Hf)(t)values(−8.37 to−2.58).Combined with previous studies,these characteristics suggest that the Shenxianshui alkaline granites were formed in a post-collision extensional environment.The alkaline granitic magma possibly originated from the partial melting of the lower crust during the Mesoproterozoic era and may have contained mantle source materials.Shenxianshui alkaline granite was formed from mixed magma with a high degree of crystal differentiation.The abundance of ore-forming elements indicates that Shenxianshui granite has the potential to mineralize key metals and rare earth elements.

Extensive Resetting of Feldspar Pb Isotopic Composition in Archean–Paleoproterozoic Granitic Rocks from the Kongling Terrane,South China:Implications for Tracing Thermal Evolutionary History

Feldspar Pb isotopes have been widely used to trace magmatic formation and evolution processes.However,it remains unclear whether post-magmatic thermal events can affect feldspar Pb isotopic ratios.Here,the in situ Pb isotopic composition of feldspar hosted in granitic rocks(thirteen Archean and one Paleoproterozoic)from the northern Kongling terrane,Yangtze Craton,South China,is analyzed.The samples reveal a substantial variation in their Pb isotopic composition,spanning the gap between the 1.9 Ga and present-day geochrons,which indicates extensive resetting by later tectonothermal events.This resetting was interpreted to have likely resulted from Paleoproterozoic and Neoproterozoic tectonothermal events related to the assembly and breakup of the Columbia and Rodinia supercontinents.These results suggest that Pb isotopes should be used cautiously when tracing magma sources and petrogenesis in magmatic rocks that have experienced post-magmatic reworking.However,the in situ Pb isotopic composition of feldspar in ancient granitoids may also potentially be used to reveal later tectonothermal events.The extensive resetting of the Pb isotopic composition in feldspar by regional thermal events may also provide new insights into our understanding of the Pb isotope paradox.

Geology and Geochemistry of K-feldspar Veins in Lamprophyre at the Zhenyuan Gold Deposit,Yunnan,Southwest China:Implications for Gold Mineralization

Lamprophyres typically appear in hydrothermal gold deposits.The relationship between lamprophyres and gold deposits is investigated widely.Some researchers suggest that the emplacement of lamprophyres triggers gold mineralization,whereas others hypothesize that the formation of lamprophyres increases the fertility of mantle sources and ore-forming fluids.K-feldspar veins,with ages between those of lamprophyres and gold deposits,appear in lamprophyres in Zhenyuan.Therefore,K-feldspar veins are ideal for investigating the relationship between lamprophyres and gold deposits.Phlogopite in K-feldspar veins has lower Mg#,Ni,and Cr contents and higher TiO2,Li,Ba,Sr,Sc,Zr,Nb,and Cs contents than phlogopite in lamprophyres.The in-situ Sr isotopic values of apatites(0.7063–0.7066)in K-feldspar veins are within the range for apatites(0.7064–0.7078)from lamprophyres.High large-ion lithophile element concentrations and low Nb and Ta concentrations in phlogopite from lamprophyres,in addition to high(87Sr/86Sr)i values of apatite(0.7064–0.7078),indicate that the magma parental to these phlogopite and apatite crystals is derived from an enriched mantle.Kfeldspar veins are genetically correlated with lamprophyres,whereas sulfide mineral assemblage and trace element compositions of pyrite in K-feldspar veins suggest that K-feldspar veins in lamprophyres are not directly related to gold mineralization of the Zhenyuan deposit.

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

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

The organic geochemistry of crude oil in the Saltpond Basin(Ghana):Organic source input,depositional environment,and thermal maturity

The Saltpond Basin,situated within the South Atlantic margin of Ghana,is a significant area for petro-leum exploration but has received relatively limited research attention.Previous studies have examined source rock com-position,but data on crude oil organic chemistry are lack-ing,hindering understanding of the basin’s petroleum system and evolution.To address this gap,we analyzed biomarkers and stable carbon-isotope ratios in Saltpond Basin crude oil using gas chromatography–mass spectrometry and gas chromatography–isotope ratio mass spectrometry to eluci-date organic matter source,depositional environment,and thermal maturity.Findings were compared with oils from the West African segment of the South Atlantic margin,namely the Tano Basin and the Niger Delta Basin,to iden-tify potential correlations and gain insights into regional variations.Molecular and isotopic results unveiled a sig-nificant prevalence of organic matter derived from lower marine organisms.Patterns of organic matter deposition and preservation in Saltpond oil samples suggested a suboxic marine transitional environment,contradicting conventional understanding of terrestrial dominance in such settings.Moreover,the potential for degradation processes to obscure differentiation between terrestrial and marine organic mat-ter origins underscores the complex nature of organic mat-ter dynamics in transitional marine environments.Analysis of molecular thermal maturity indices suggested Saltpond oils were expelled from source rocks exhibiting thermal maturity at the early maturity stage.Correlation analysis unveiled genetic disparities among crude oils sourced from the Saltpond Basin and those from the Tano and Niger Delta Basin,primarily due to variations in source input and depo-sitional environment conditions.Saltpond oil exhibits lower terrestrial organic input than Tano Basin’s crude oils,which also have less terrestrial input than Niger Delta Basin crude oils.Additionally,its paleodepositional environment nota-bly differs from oils in the Tano Basin(anoxic transitional marine-lacustrine settings)and the Niger Delta Basin(sub-oxic–oxic terrigenous deltaic or marine or lacustrine envi-ronments).Thermal maturity range of Saltpond oil is com-parable to oils in the Tano Basin but lower than oils in the Niger Delta Basin.Thesefindings provide valuable insights into petroleum generation history and unique organic geo-chemical characteristics within the Saltpond Basin,essen-tial for exploration,production,and environmental manage-ment efforts in the region.Furthermore,correlation studies provide evidence that distinct biological,geological,and paleoenvironmental conditions shaped various oil types in the West African segment of the South Atlantic margin.

Morphological and Sulfur-Isotopic Characteristics of Pyrites in the Deep Sediments from Xisha Trough,South China Sea

Pyrite is one of the common authigenic minerals in marine sediments.Previous studies have shown that the morphological and isotopic characteristics of pyrite are closely related to the geochemical environment where it is formed.To better understand the for-mation mechanism of authigenic pyrite,we analyzed the isotopic composition,morphology,and distribution of pyrite in the sediment at 500m below the seafloor from Xisha Trough,South China Sea.Mineral morphologies were observed by scanning electron micros-copy and Raman spectrography.X-Ray computed tomography was applied to measure the particle size of pyrite.The size of pyrite crystals in the matrix sediment mainly ranged between 25 and 65µm(av.ca.40µm),although crystals were larger(av.ca.50μm)in the veins.The pyrites had a fine-grained truncated octahedral shape with occasionally well-developed growth steps,which implies the low growth rate and weak anaerobic oxidation of methane-sulfate reduction when pyrite was formed.Theδ^(34)S values of pyrites ranged from+20.8‰Vienna-defined Canyon Diablo Troilite(V-CDT)to+33.2‰V-CDT and from+44.8‰V-CDT to+48.9‰,which suggest two growth stages.In the first stage,with the continuous low methane flux,the pyrite possibly formed in an environment with good access to seawater.In the second stage,the pyrites mainly developed in sediment fractures and appeared in veins,probably due to the limited availability of sulfate.The less exposure of pyrite to the environment in the second stage was probably caused by sediment accumulation or perturbation.In this study,an episodic pyritization process was identified,and the paleoenvironment was reconstructed for the sediment investigated.

The late Early-Paleozoic granitic magmatism in Northwestern Fujian, China: constraints on intraplate orogeny in the South China block

The Early Paleozoic tectono-thermal event was a significant orogenic activity during the Phanerozoic era,which had a profound impact on the early crust of the South China Block(SCB) and established the foundation for later tectonic activity.The Wuyi-Yunkai orogenic belt in Southeastern China was extensively exposed to Early Paleozoic magmatism,the genetic mechanism of which remains controversial.To shed light on this issue,detailed petrological,geochemical,and zircon U-Pb-Hf isotopic studies were carried out on two granitoids,namely the Yuntongshan pluton and the Gaoqiao pluton,identified in the central Wuyishan.Zircon U-Pb chronology of the Yuntongshan and Gaoqiao bodies yielded ages of437±4 Ma(MSWD=2.2) and 404±2 Ma(MSWD=12),respectively,indicating that they were emplaced during the Early Silurian and Early Devonian periods.These granitoids are primarily composed of biotite-granite and biotite-monzonitic-granites,with high concentrations of S_(i)O_(2)(73.59-75.91 wt%),K_(2)O+Na_(2)O(8.31-8.73wt%),and low contents of MgO,CaO,Cr,Ni.They are classified as high-K calc-alkaline and weakly metaluminous-strongly peraluminous S-type granites.These granitoids are enriched in light rare earth elements(LREEs) and large ion lithophile elements(LILEs) and depleted in heavy rare earth elements(HREEs) and high field strength elements(HFSEs) with arc affinity.The εHf(t) values of-3.3 to-15.4 with two-stage Hf model ages ranging from 2829 to 1644 Ma,combined with the presence of Neoproterozoic inherited zircons,suggest that the primary magma of these granitoids was derived from the partial melting of Neoproterozoic crust with a Paleoproterozoic crustal model age.These findings,combined with the spatio-temporal distribution of regional magmatism,reveal that the late Early-Paleozoic granitoids formed in the intraplate orogenic background originating from the subduction of the proto-Tethys Ocean and proto-Pacific Ocean around the margin of the east Gondwana supercontinent.

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

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

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

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

Vibronic effect study of ^(1)A_(2) state of H_(2)O and D_(2)O

The generalized oscillator strengths of the dipole-forbidden excitations of the ^(1)A_(2) of H_(2)O and D_(2)O were calculated with the time dependent density functional theory,by taking into account the vibronic effect.It is found that the vibronic effect converts the dipole-forbidden excitation of the ^(1)A_(2) into a dipole-allowed one,which enhances the intensities of the corresponding generalized oscillator strength in the small squared momentum transfer region.The present investigation shows that the vibronic effect of H_(2)O is slightly stronger than that of D_(2)O,which exhibits a clear isotopic effect.

Early Neoproterozoic Granite-Gneisses of the Junggar Alataw(Southeastern Kazakhstan):Age,Petrogenesis and Tectonic Implications

The combined petrographic,petrological,geochemical and geochronological study of the Neoproterozoic gneisses of the Sarychabyn and Baskan complexes of the Junggar Alataw of South Kazakhstan elucidate the Precambrian tectonic evolution of the Aktau–Yili terrane.It is one of the largest Precambrian crustal blocks in the western Central Asian orogenic belt.The U-Pb single-grain zircon ages indicate that granite-gneisses formed from the same source and crystallised in the early Neoproterozoic ca.930–920 Ma.The chemical composition of gneisses corresponds to A2-type granites.The whole-rock Nd isotopic characteristics(εNd(t)=−4.9 to−1.0 and TNd(DM-2st)=1.9 to 1.7 Ga)indicate the involvement of Paleoproterozoic crustal rocks in magma generation.Early Neoproterozoic ca.930–920 Ma A-type granitoids in the Aktau–Yili terrane of South and Central Kazakhstan might reflect within-plate magmatism adjacent to the collisional belt or a local extension setting in back-arc areas of the continental arc.

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

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

Genesis of the Nuri Cu-W-Mo Deposit,Tibet,China:Constraints from in situ Trace Elements and Sr Isotopic Analysis of Scheelite

The Nuri deposit is the only Cu-W-Mo polymetallic deposit with large-scale WO3 resources in the eastern section of the Gangdese metallogenic belt,Tibet,China.However,the genetic type of this deposit has been controversial since its discovery.Based on a study of the geological characteristics of the deposit,this study presents mineralization stages,focusing on the oxide stage and the quartz-sulfide stage where scheelite is mainly formed,referred to as Sch-A and Sch-B,respectively.Through LA-ICP-MS trace element and Sr isotope analyses,the origin,evolutionary process of the oreforming fluid and genesis of the ore deposit are investigated.Scanning Electron Microscope-Cathodoluminescence(SEMCL)observations reveal that Sch-A consists of three generations,with dark gray homogenous Sch-A1 being replaced by relatively lighter and homogeneous Sch-A2 and Sch-A3,with Sch-A2 displaying a gray CL image color with vague and uneven growth bands and Sch-A3 has a light gray CL image color with hardly any growth band.In contrast,Sch-B exhibits a‘core-rim’structure,with the core part(Sch-B1)being dark gray and displaying a uniform growth band,while the rim part(Sch-B2)is light gray and homogeneous.The normalized distribution pattern of rare earth elements in scheelite and Sr isotope data suggest that the early ore-forming fluid in the Nuri deposit originated from granodiorite porphyry and,later on,some country rock material was mixed in,due to strong water-rock interaction.Combining the O-H isotope data further indicates that the ore-forming fluid in the Nuri deposit originated from magmatic-hydrothermal sources,with contributions from metamorphic water caused by water-rock interaction during the mineralization process,as well as later meteoric water.The intense water-rock interaction likely played a crucial role in the precipitation of scheelite,leading to varying Eu anomalies in different generations of scheelite from the oxide stage to the quartz-sulfide stage,while also causing a gradual decrease in oxygen fugacity(fO2)and a slow rise in pH value.Additionally,the high Mo and low Sr contents in the scheelite are consistent with typical characteristics of magmatic-hydrothermal scheelite.Therefore,considering the geological features of the deposit,the geochemical characteristics of scheelite and the O-H isotope data published previously,it can be concluded that the genesis of the Nuri deposit belongs to porphyry-skarn deposit.

Hydraulic properties and drought response of a tropical bamboo (Cephalostachyum pergracile)

Bamboo plants are an essential component of tropical ecosystems,yet their vulnerability to climate extremes,such as drought,is poorly understood due to limited knowledge of their hydraulic properties.Cephalostachyum pergracile,a commonly used tropical bamboo species,exhibited a substantially higher mortality rate than other co-occurring bamboos during a severe drought event in 2019,but the underlying mechanisms remain unclear.This study investigated the leaf and stem hydraulic traits related to drought responses,including leaf-stem embolism resistance(P50leaf;P50stem) estimated using optical and X-ray microtomography methods,leaf pressure-volume and water-releasing curves.Additionally,we investigated the seasonal water potentials,native embolism level(PLC) and xylem water source using stable isotope.We found that C.pergracile exhibited strong resistance to embolism,showing low P50leaf,P50stem,and turgor loss point,despite its rapid leaf water loss.Interestingly,its leaves displayed greater resistance to embolism than its stem,suggesting a lack of effective hydraulic vulnerability segmentation(HVS) to protect the stem from excessive xylem tension.During the dry season,approximately 49% of the water was absorbed from the upper 20-cm-deep soil layer.Consequently,significant diurnal variation in leaf water potentials and an increase in midday PLC from 5.87±2.33% in the wet season to 12.87±4.09%in the dry season were observed.In summary,this study demonstrated that the rapid leaf water loss,high reliance on surface water,and a lack of effective HVS in C.pergracile accelerated water depletion and increased xylem embolism even in the typical dry season,which may explain its high mortality rate during extreme drought events in 2019.

The photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis

Photosynthesis is the most important biochemical reaction on Earth. It has co-evolved and developed with the Earth, driving the biogeochemical cycle of all elements on the planet and serving as the only chemical process in nature that can convert light energy into chemical energy. Some heavy oxygen isotopic(^(18)O) labeling experiments have"conclusively" demonstrated that the oxygen released by photosynthesis comes only from water and are written into textbooks. However, it is not difficult to find that bicarbonate has never been excluded from the direct substrate of photosynthesis from beginning to end during the history of photosynthesis research. No convincing mechanism can be used to explain photosynthetic oxygen evolution solely from water photolysis. The bicarbonate effect, the Dole effect, the thermodynamic convenience of bicarbonate photolysis, the crystal structure characteristics of photosystem Ⅱ, and the reinterpretation of heavy oxygen isotopic labeling(^(18)O)experiments all indicate that the photosynthetic oxygen evolution does not exclude the important role and contribution of bicarbonate photolysis. The recently proposed view that bicarbonate photolysis is the premise of water photolysis, bicarbonate photolysis and water photolysis work together with a 1:1(mol/mol) stoichiometric relationship, and the stoichiometric relationship between oxygen and carbon dioxide released during photosynthetic oxygen evolution is also 1:1, has excellent applicability and objectivity, which can logically and reasonably explain the precise coordination between light and dark reactions during photosynthesis, the bicarbonate effect, the Dole effect, the Kok cycle and the neutrality of water and carbon in nature.This is of great significance for constructing the bionic artificial photosynthetic reactors and scientifically answering the question of the source of elemental stoichiometric relationships in nature.

Fe-N-C core-shell catalysts with single low-spin Fe(Ⅱ)-N_(4)species for oxygen reduction reaction and high-performance proton exchange membrane fuel cells

Fe-N-doped carbon materials(Fe-N-C)are promising candidates for oxygen reduction reaction(ORR)relative to Pt-based catalysts in proton exchange membrane fuel cells(PEMFCs).However,the intrinsic contributions of Fe-N_(4)moiety with different chemical/spin states(e.g.D1,D2,D3)to ORR are unclear since various states coexist inevitably.In the present work,Fe-N-C core-shell nanocatalyst with single lowspin Fe(Ⅱ)-N_(4)species(D1)is synthesized and identified with ex-situ ultralow temperature Mossbauer spectroscopy(T=1.6 K)that could essentially differentiate various Fe-N_(4)states and invisible Fe-O species.By quantifying with CO-pulse chemisorption,site density and turnover frequency of Fe-N-C catalysts reach 2.4×10^(-9)site g^(-1)and 23 e site~(-1)s^(-1)during the ORR,respectively.Half-wave potential(0.915V_(RHE))of the Fe-N-C catalyst is more positive(approximately 54 mV)than that of Pt/C.Moreover,we observe that the performance of PEMFCs on Fe-N-C almost achieves the 2025 target of the US Department of Energy by demonstrating a current density of 1.037 A cm^(-2)combined with the peak power density of 0,685 W cm^(-2),suggesting the critical role of Fe(Ⅱ)-N_(4)site(D1).After 500 h of running,PEMFCs still deliver a power density of 1.26 W cm^(-2)at 1.0 bar H_(2)-O_(2),An unexpected rate-determining step is figured out by isotopic labelling experiment and theoretical calculation.This work not only offers valuable insights regarding the intrinsic contribution of Fe-N_(4)with a single spin state to alkaline/acidic ORR,but also provides great opportunities for developing high-performance stable PEMFCs.

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

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

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

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

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

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

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

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