A bulk extraction method to determine the stable isotope ratios of iron,nickel,copper,zinc,and cadmium in seawater using multi-collector inductively coupled plasma mass spectrometry

The oceanic trace metals iron(Fe),nickel(Ni),copper(Cu),zinc(Zn),and cadmium(Cd)are crucial to marine phytoplankton growth and global carbon cycle,and the analysis of their stable isotopes can provide valuable insights into their biogeochemical cycles within the ocean.However,the simultaneous isotopic analysis of multiple elements present in seawater is challenging because of their low concentrations,limited volumes of the test samples,and high salt matrix.In this study,we present the novel method developed for the simultaneous analysis of five isotope systems by 1 L seawater sample.In the developed method,the NOBIAS Chelate-PA1 resin was used to extract metals from seawater,the AG MP-1M anion-exchange resin to purify Cu,Fe,Zn,Cd,and the NOBIAS Chelate-PA1 resin to further extract Ni from the matrix elements.Finally,a multi-collector inductively coupled plasma mass spectroscope(MC-ICPMS)was employed for the isotopic measurements using a doublespike technique or sample-standard bracketing combined with internal normalization.This method exhibited low total procedural blanks(0.04 pg,0.04 pg,0.21 pg,0.15 pg,and 3 pg for Ni,Cu,Fe,Zn,and Cd,respectively)and high extraction efficiencies(100.5%±0.3%,100.2%±0.5%,97.8%±1.4%,99.9%±0.8%,and 100.1%±0.2%for Ni,Cu,Fe,Zn,and Cd,respectively).The external errors and external precisions of this method could be considered negligible.The proposed method was further tested on the seawater samples obtained from the whole vertical profile of a water column during the Chinese GEOTRACES GP09 cruise in the Northwest Pacific,and the results showed good agreement with previous related data.This innovative method will contribute to the advancement of isotope research and enhance our understanding of the marine biogeochemical cycling of Fe,Ni,Cu,Zn,and Cd.

Precise and accurate Ga isotope ratio measurements of geological samples by multi-collector inductively coupled plasma mass spectrometry

Gallium isotope is a potential geochemical tool for understanding planetary processes,environmental pollution,and ore deposit formation.The reported Ga isotope compositions(δ^(71)Ga NIST994 values)of some international geological standards,such as BCR-2 and BHVO-2 basalts,exhibit inconsistencies between diff erent laboratories.During mass spectrometry analysis,we found thatδ^(71)Ga NIST994 values of geological standards with or without the correction of the interference of^(138)Ba^(2+)(mass/charge ratio=69)on 69 Ga show signifi cant isotope off sets,and thus effi cient separation of Ba and correcting the interference of^(138)Ba^(2+)are both crucial to obtain accurateδ^(71)Ga values.By comparingδ^(71)Ga NIST994 values(relative to NIST SRM 994 Ga)of the same geostandards from diff erent laboratories,we suggest that the isotopic heterogeneity from NIST SRM 994 Ga is one of the key reasons for the inconsistencies inδ^(71)Ga NIST994 values of BCR-2 and BHVO-2.To facilitate inter-laboratory comparisons,we measured the Ga isotopic compositions of 11 geological reference materials(including Pb-Zn ore,bauxite,igneous rocks,and loess)and two Ga solution standards(NIST SRM 3119a and Alfa Aesar).Theδ^(71)Ga NIST994 andδ^(71)Ga IPGP values of these reference materials vary from 1.12‰to 2.63‰and−0.13‰to 1.38‰,respectively,and can be used to evaluate the precision and accuracy of Ga isotope data from diff erent laboratories.

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.

The Deconvolution Method for Obtaining Correspondence in Data-Independent Acquisition Mass Spectrometry Data

Although data-independent acquisition (DIA) shows powerful potential in achieving comprehensive peptide information acquisition, the difficulty in determining the precursor m/z and distinguishing fragment ions has posed challenges in DIA data analysis. To address this challenge, a common approach is to recover the correspondence between precursor ions and fragment ions, followed by peptide identification using traditional data-dependent acquisition (DDA) database searching. In this study, we propose a cosine similarity-based deconvolution method that rapidly establishes the correspondence between chromatographic profiles of precursor ions and fragment ions through matrix calculations. Experimental results demonstrate that our method, referred to as CosDIA, yields a peptide identification count close to that of DIA-umpire. However, compared to DIA-umpire, we can establish the correspondence between original MS/MS spectra and pseudo-MS/MS spectra. Furthermore, compared to the CorrDIA method, our approach achieves higher efficiency in terms of time, reducing the time cost of the analysis process. These results highlight the potential advantages of the CosDIA method in DIA data analysis, providing a powerful tool and method for large-scale proteomics research.

Separation and Precise Measurement of Lithium Isotopes in Three Reference Materials Using Multi Collector-Inductively Coupled Plasma Mass Spectrometry

Lithium separation technique for three reference materials has been established together with precise determination of lithium isotope using a Neptune multi collector-inductively coupled plasma mass spectrometry （MC-ICP-MS）. The solutions of lithium element standard reference materials, potassium, calcium, sodium, magnesium and iron single element, were used to evaluate analytical methods applied. Three separate stages of ion-exchange chromatography were carried out using organic cation-exchange resin （AG 50W-X8）. Lithium was enriched for the three stages using different eluants, which are 2.8 M HCl, 0.15 M HCl and 0.5 M HCl in 30% ethanol, respectively. The columns for the first and second stages are made of polypropylene, and those for the third stage are made of quartz. Total reagent volume for the entire chemical process was 35 mL for three reference materials. The recovery yielded for the three stages is 98.9-101.2% with an average of 100.0%, 97.6-101.9% with an average of 99.9%, and 99.8-103.3% with an average of 100.6%, respectively. The precision of this technique is conservatively estimated to be ±0.72-1.04‰ （2σ population）, which is similar to the precision obtained by different authors in different laboratories with MC-ICP-MS. The δ7 Li values （ 7 Li/ 6 Li relative to the IRMM-016 standard） determined for andesite （AGV-2） and basalt （BHVO-2） are 5.68‰ （n=18）, 4.33‰ （n=18）, respectively. The δ7 Li value （ 7Li/6Li relative to the L-SVEC standard） determined for IRMM-016 is -0.01‰ （n=15）. All these analytical results are in good agreement with those previously reported. In addition, the results for the same kinds of samples analyzed at the MLR Key Laboratory of Metallogeny and Mineral Assessment, Institute of Mineral Resources, Chinese Academy of Geological Sciences, are consistent with those obtained at the Plasma Laboratory, University of Maryland, within analytical uncertainty. According to these experiment results, it is concluded that this proposed procedure is a suitable method for determining the lithium isotopic composition of natural samples.

An online method to determine chlorine stable isotope composition by continuous flow isotope ratio mass spectrometry (CF-IRMS) coupled with a Gasbench Ⅱ

An online method using continuous flow isotope ratio mass spectrometry （CF-IRMS） interfaced with a Gasbench Ⅱ was presented to determine chlorine stable isotope composition. Silver chloride （AgCl） was quantitatively derived from chloride by using silver nitrate （AgNO3）, and then was reacted with iodomethane （CH3Ⅰ） to produce methyl chloride （CH3Cl）. A GasBench Ⅱ equipped with a PoraPlot Q column was used to separate CH3Cl from any other gas species. Finally, chlorine stable isotope analysis was carried out on CH3Cl introduced to the IRMS in a helium stream via an active open split. The minimum amount of Cl used in this method is of the order of 1.4 μmol. Inter-laboratory and inter-technique comparisons show that the total uncertainty incorporating both the precision and accuracy of this method is better than 0.007%. Furthermore, ten seawaters sampled from different locations have a narrow δ37Cl value range from -0.008% to 0.010%, with a mean value of （0.000±0.006）%. This supports the assumption that any seawater can be representative of standard mean ocean chloride （SMOC） and used as an international reference material.

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.

A re-assessment of nickel-doping method in iron isotope analysis on rock samples using multi-collector inductively coupled plasma mass spectrometry

Element doping has been proved to be a useful method to correct for the mass bias fractionation when analyzing iron isotope compositions.We present a systematic re-assessment on how the doped nickel may affect the iron isotope analysis in this study by carrying out several experiments.We find three important factors that can affect the analytical results,including the Ni:Fe ratio in the analyte solutions,the match of the Ni:Fe ratio between the unknown sample and standard solutions,and the match of the Fe concentration between the sample and standard solutions.Thus,caution is required when adding Ni to the analyte Fe solutions before analysis.Using our method,theδ56Fe and δ57Fe values of the USGS standards W-2 a,BHVO-2,BCR-2,AGV-2 and GSP-2 are consistent with the recommended literature values,and the long-term(one year) external reproducibility is better than 0.03 and 0.05‰(2 SD) for δ56Fe and δ57Fe,respectively.Therefore,the analytical method established in our laboratory is a method of choice for high quantity Fe isotope data in geological materials.

Stable Isotope Dilution Analysis of Gibberellin Residues in Tomato Paste by Liquid Chromatography-Tandem Mass Spectrometry

An accurate and sensitive method for the simultaneous determination of gibberellic acid（GA3）, gibberellin A4（GA4） and gibberellin A7（GA7） residues in tomato paste was developed by coupling solid phase extraction to high performance liquid chromatography-tandem mass spectrometry（LC-MS/MS） with electrospray ionization based stable isotope dilution analysis（SIDA）. The isotope labeled internal standard can compensate for the losses during the extraction and cleanup steps and for discrimination due to ion suppression. After extraction from methanol, hydrophile lipophilic balance（HLB） solid phase extraction（SPE） column was tested for the capacity of the cleanup of the tomato paste in compared with C18 SPE column which is the common way to the detection of GAs, and the former gained better result. Spiked experiments were performed in the non-contaminated tomato pastes and the recoveries of GA3, GA4 and GA7 were 42.6%―75.0% in external standard method（ESM） and 91.1%―103.8% in internal standard method（ISM） respectively. The validities of this method were investigated and good analytical performance for the three GAs was obtained, including low limits of method detection（2 ng/g for GA3 and GA4, 0.3 ng/g for GA7）, excellent linear dynamic ranges（5―500 ng/g for GA3 and GA4, 1―100 ng/g for GA7） and good relative standard deviation ranges（4.8%―9.4% for the intra-day test and 3.5%―11.9% for the inter-day test）.

Fluid inclusion and H-O-S-Pb isotope systematics of the Chayong Cu-polymetallic deposit,Sanjiang Metallogenic Belt,Qinghai Province,China

The Chayong Cu-polymetallic deposit is a recently discovered Cu-polymetallic deposit hosted in the Sanjiang Metallogenic Belt within the Tibetan Plateau of China to the northeast of the North Qiangtang terrane.The ore body occurs in siltstone and is controlled by a northwest-trending fault structure.According to the associations,assemblages,and cutting relationships between ore veins,the hydrothermal mineralization period can be divided into three mineralization stages:(1)a molybdenite mineralization stage,(2)a Cu-polymetallic sulfide stage,and(3)a quartzcarbonate stage.Two types of fluid inclusions(FIs),namely,liquid and vapor-rich inclusions,are present in quartz as so ciated with sulfide minerals.Early-stage FIs are both iquid and vapor-rich,homogenized at temperatures ranging from 364.1 to 384.2℃,and have salinities ranging from0.70%to 9.60%NaCl equivalent(eqv).The middle-stage FIs are also both liquid-and vapor-rich,homogenized at temperatures ranging from 272.4 to 355.6℃,and have salinities ranging from 0.53%-17.10%NaCl eqv.The late-stage FIs are liquid,homogenized at temperatures ranging from 209.4to 255.3℃,and have salinities ranging from 0.35%-6.87%NaCl eqv.The samples from the deposit haveδ^(34)S values of-21.8‰to-19.2‰and-5.5‰to-6.0‰,suggesting that sulfur was derived from the host sediments and magmatic fluids,respectively.The metallic minerals within the deposit have^(206)Pb/^(204)Pb,^(207)Pb/^(204)Pb,and^(208)Pb/^(204)Pb values of 18.439-18.458,15.656-15.679,and 38.772-38.863,respectively,suggesting that the metals were derived from the upper crust and orogenic belts.The samples from the deposit haveδ^(18)O_(W)values of 2.99‰-7.99‰andδD_(W) values ranging from-84.4‰to-73.9‰,indicating that the pre-forming fluids were magmatic and mixed with minor amounts of meteoric water.The ore-forming fluid of the Chayong copper polymetallic deposit was a high-temperature,medium-to low-salinity H_(2)O-NaCl-CH_(4)-N_(2)±CO_(2)fluid system.The early high-temperature magmatic fluid,due to boiling,decreased in temperature,and via the mixing of meteoric water,gradually evolved towards the later-stage medium-to low-temperature and low-salinity fluid,causing nolybdenite mineralization and forming copper polymetallic sulfide veins and quartz carbonate veins.

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

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

Processes involving soil CO_(2)dynamic in a sector of Chaco-Pampean plain,Argentina:An isotope geochemical approach

The magnitude and spatial variability of CO_(2)surface emissions and processes involving CO_(2)released to the atmosphere from the soils are relevant issues in the context of climate change.This work evaluated CO_(2)fluxes and^(13)C/^(12)C ratio of vegetation,organic matter,and soil gases from no disturbed soils of Chaco Pampean Plain(Argentina)with different soil properties and environmental conditions(PL and PA units).Soil organic decomposition from individual layers was accompanied byδ^(13)C of total organic carbon(δ^(13)C-TOC)values more enriched to depth.δ^(13)C-TOC values in the upper soil profile~ca.0–15 cm were like the plant community of this area(~−33 to−29‰)whileδ^(13)CTOC varied stronger bellow horizon A,till~−24‰.Bothδ^(13)C-TOC and soilδ^(13)C-CO_(2)were similar(~−24 to 26‰)at deeper horizons(~50–60 cm).Toward the superficial layers,δ^(13)C-TOC andδ^(13)C-CO_(2)showed more differences(till~4‰),due influence of the diffusion process.Horizon A layer(~0–20 cm)from both PL and PA units contained the most enrichedδ^(13)C-CO_(2)values(~−15–17‰)because atmospheric CO_(2)permeated the soil air.A simple two-component mixing model between sources(atmosphericδ^(13)C-CO_(2)and soil CO_(2))confirmed that process.Isotopically,CO_(2)fluxes reflected the biodegradation of C3 plants(source),diffusive transport,and CO_(2)exchange(atmosphere/soil).Soil moisture content appeared as a determining factor in the diffusion process and the magnitude of CO_(2)surface emissions(12–60 g·m^(−2)·d^(−1)).That condition was confirmed by CO_(2)diffusion coefficients estimated by air-filled porosity parameters and soil radon gradient model.

Geology and S-Pb isotope geochemistry of the Hatu gold deposit in West Junggar,NW China:Insights into ore genesis and metal source

The Hatu gold deposit is the largest historical gold producer of the West Junggar,western China,with an Au reserve of about 62 t.The orebodies were controlled by NE-,EW-,and NW-trending subsidiary faults associated with the Anqi fault.This deposit exhibits characteristics typical of a fault-controlled lode system,and the orebodies consist of auriferous quartz veins and altered wall rocks within Early Carboniferous volcano-sedimentary rocks.Three stages of mineralization have been identified in the Hatu gold deposit:the early pyrite-albite-quartz stage,the middle polymetallic sulfides-ankerite-quartz stage,and late quartz-calcite stage.The sulfur isotopic values of pyrite and arsenopyrite vary in a narrow range from-0.8‰to1.3‰and an average of 0.4‰,the near-zeroδ~(34)S values implicate the thorough homogenization of the sulfur isotopes during the metamorphic dehydration of the Early Carboniferous volcano-sedimentary rocks.Lead isotopic results of pyrite and arsenopyrite(^(206)Pb/^(204)Pb=17.889-18.447,^(207)Pb/^(204)Pb=15.492-15.571,^(208)Pb/^(204)Pb=37.802-38.113)are clustered between orogenic and mantle/upper crust lines,indicating that the lead was mainly sourced from the hostrocks within the Early Carboniferous Tailegula Formation.The characteristics of S and Pb isotopes suggest that the ore-forming metals of the Hatu orogenic gold deposit are of metamorphogenic origin,associated with the continental collision between the Yili-Kazakhstan and Siberian plates during the Late Carboniferous.

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

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

The source of lithium in Lakkor Co Salt Lake on Qinghai-Tibet Plateau,China:evidence from hydrochemical characteristics and boron isotope

The availability of lithium resources is of great significance for the development of modern technologies,as well as for civil and military industries.The Qinghai-Tibet Plateau is a region known for its abundance of lithium-rich salt lakes.However,the specific origin of lithium in these lakes is still unknown,which hinders the advancement of the lithium resource business in this region.To research this issue,this study involved the collection of 20 samples from Lakkor Co Salt Lake on Qinghai-Tibet Plateau,encompassing samples of surface brine,cold springs,fresh lakes,and recharge rivers.The composition of anions and cations in these samples was determined.Furthermore,the analysis extensivelyutilizedthePiperthree-linediagram,Gibbs model,and ion proportion coefficient.The findings of this study indicate that as the moves from the recharge water system to salt lake,there is a transition in water type from strong carbonate to moderate carbonate and weak carbonate,as well as Na sulfate.This research based on a similar source of both lithium and boron,utilized ion correlation analysis and boron isotope study in the Lakkor Co area,and analyzed the source and transporting process of lithium.The main origin of lithium in Lakkor Co is the dissolution of lithiumrich rocks,recharge water systems,and deep hydrothermal fluids.These findings are highly significant in enhancing the foundational data of lithium-rich brine resources in the Qinghai-Tibet Plateau and are beneficial for assessing the future development of such deposits.

Catagenetic type of manganese ores:REE and isotope(δ^(13)C,δ^(18)O)geochemical features(on the example of the Usa deposit,Russia)

Chemical(REE and major elements)and isotope(δ^(13)C,δ^(18)O)composition of carbonate manganese ores and manganese-bearing carbonates of the Usa deposit(Siberia,Russia)were studied.Received data on the composition of REE exhibit both the distinct negative(Ce/Ce*_(PAAS)<1)and positive(Ce/Ce*_(PAAS)>1)cerium anomalies and the positive Eu-anomaly(Eu/Eu*_(PAAS)>1).Negative Eu-anomalies are not observed.The contents of Mn,Fe,REE,and Ce-anomalies show a positive correlation with each other.Ce-anomalies and the amount of manganese and REE in relation to the carbon isotope composition(δ^(13)C)show a negative relationship and indicate that oxidized carbon of organic matter played an important role in the concentration of manganese and REE in manganese ores.The chemical and isotope composition of examined rocks indicates on secondary formation of Mnores.Two major phases and sources are distinguished in the ore-forming process characterized by diff erent chemical(REE and ore elements)and isotope composition:(i)highgrade manganese ores(with high contents of REE and light carbon isotope composition)and(ii)low-grade manganese ores(with low contents of REE and heavy carbon isotope composition).

Nitrogen isotope stratigraphy of the Early Cambrian successions in the Tarim Basin:Spatial variability of nitrogen cycling and its implication for paleo-oceanic redox conditions

The Early Cambrian represents a critical time period characterized by extraordinary biological innovations and dynamic redox conditions in seawaters.Nitrogen isotopic signatures of ancient sediments have the potential to elucidate the evolutionary path of marine redox states and the biogeochemical nitrogen cycle within the water column of the Early Cambrian ocean.While existing research on this topic has predominantly focused on South China,the exploration of other continental margins has been limited,leaving contradictory hypotheses untested.In this study,pairedδ^(15)N andδ^(13)C org analyses were performed on the Lower Cambrian successions from the Shiairike section(inner ramp)and Well Tadong 2(deep shelf/basin)in the northwestern and eastern Tarim Basin,respectively.Our data from the Shiairike section reveal a discernible shift in the operation of different nitrogen cycles for the black chert-shale unit,also referred to as the black rock series in Chinese literature,of the Yurtus Formation(Fortunian stage to lower Stage 3).Oscillatingδ^(15)N values for its lower part are suggestive of alternating anaerobic assimilation of NH 4+and denitrification/anammox.This is likely attributed to a shallow,unstable chemocline consistent with the upwelling and incursion of deep,anoxic waters during a major transgression.In contrast,aerobic nitrogen cycling,indicated by positiveδ^(15)N values of>2‰,dominated the upper part alongside a reduction in upwelling intensity.On the other hand,theδ^(15)N signatures of Xishanbulake and Xidashan Formations of Well Tadong 2,which encompass a time interval from the Cambrian Fortunian Age to Age 4,are indicative of N_(2)fixation by diazotrophs as the major nitrogen source.The two studied intervals,although not time-equivalent,exhibit separated states of nitrogen cycling at least during the deposition of the Yurtus black rock series.The spatially different nitrogen cycling of the studied sections is compatible with a redox-stratified ocean during the deposition of the Yurtus black rock series.The build-up of a NO_(3)−reservoir and aerobic nitrogen cycling in seawater was largely restricted to near-shore settings whereas anaerobic nitrogen cycling dominated by N_(2)fixation served as the main nitrogen uptake pathway in off-shore settings.

Rebuilding the theory of isotope fractionation for evaporation of silicate melts under vacuum condition

Isotope eff ects are pivotal in understanding silicate melt evaporation and planetary accretion processes.Based on the Hertz-Knudsen equation,the current theory often fails to predict observed isotope fractionations of laboratory experiments due to its oversimplified assumptions.Here,we point out that the Hertz-Knudsen-equation-based theory is incomplete for silicate melt evaporation cases and can only be used for situations where the vaporized species is identical to the one in the melt.We propose a new model designed for silicate melt evaporation under vacuum.Our model considers multiple steps including mass transfer,chemical reaction,and nucleation.Our derivations reveal a kinetic isotopic fractionation factor(KIFF orα)αour model=[m(^(1)species)/m(^(2)species)]^(0.5),where m(species)is the mass of the reactant of reaction/nucleation-limiting step or species of diffusion-limiting step and superscript 1 and 2 represent light and heavy isotopes,respectively.This model can eff ectively reproduce most reported KIFFs of laboratory experiments for various elements,i.e.,Mg,Si,K,Rb,Fe,Ca,and Ti.And,the KIFF-mixing model referring that an overall rate of evaporation can be determined by two steps jointly can account for the eff ects of low P_(H2)pressure,composition,and temperature.In addition,we find that chemical reactions,diffusion,and nucleation can control the overall rate of evaporation of silicate melts by using the fitting slope in ln(−ln f)versus ln(t).Notably,our model allows for the theoretical calculations of parameters like activation energy(E_(a)),providing a novel approach to studying compositional and environmental eff ects on evaporation processes,and shedding light on the formation and evolution of the proto-solar and Earth-Moon systems.

Theoretical study of kinetic isotope effects for vacancy diffusion of impurity in solids

Theoretical studies of the diffusionalisotope effect in solids are still stuck in the 1960s and 1970s.With the development of high spatial resolution mass spectrometers,isotopic data of mineral grains are rapidly accumulated.To dig up information from these data,molecularlevel theoretical models are urgently needed.Based on the microscopic definition of the diffusion coe fficient(D),a new theoretical framework for calculating the diffusional isotope effect(DIE(v))(intermsofD*/D)forvacancy-mediated impurity diffusion in solids is provided based on statistical mechanics formalism.The newly derived equation shows that theDIE(v)can be easily calculated as long as the vibration frequencies of isotope-substituted solids are obtained.The calculatedDIE(v)values of^(199)Au/^(195)Au and^(60)Co/^(57)Co during diffusion in Cu and Au metals are all within 1%of errors compared to the experimental data,which shows that this theoretical model is reasonable and precise.

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.