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.

Geochronology, Geochemistry and Sr-Nd-Pb-Hf Isotopes of No. I Complex from the Shitoukengde Ni–Cu Sulfide Deposit in the Eastern Kunlun Orogen, Western China: Implications for the Magmatic Source, Geodynamic Setting and Genesis

The Shitoukengde Ni-Cu deposit, located in the Eastern Kunlun Orogen, comprises three mafic-ultramafic complexes, with the No. I complex hosting six Ni-Cu orebodies found recently. The deposit is hosted in the small ultramafic bodies intruding Proterozoic metamorphic rocks. Complexes at Shitoukengde contain all kinds of mafic-ultramafic rocks, and olivine websterite and pyroxene peridotite are the most important Ni-Cu-hosted rocks. Zircon U-Pb dating suggests that the Shitoukengde Ni-Cu deposit formed in late Silurian （426-422 Ma）, and their zircons have ~Hf（t） values of-9.4 to 5.9 with the older TDMm ages （0.80-1.42 Ga）. Mafic-ultramafic rocks from the No. I complex show the similar rare earth and trace element patterns, which are enriched in light rare earth elements and large ion iithophile elements （e.g., K, Rb, Th） and depleted in heavy rare earth elements and high field strength elements （e.g., Ta, Nb, Zr, Ti）. Sulfides from the deposit have the slightly higher ~34S values of 1.9-4.3%o than the mantle （0 ~ 2%o）. The major and trace element characteristics, and Sr-Nd-Pb and Hf, S isotopes indicate that their parental magmas originated from a metasomatised, asthenospheric mantle source which had previously been modified by subduction-related fluids, and experienced significant crustal contamination both in the magma chamber and during ascent triggering S oversaturation by addition of S and Si, that resulted in the deposition and enrichment of sulfides. Combined with the tectonic evolution, we suggest that the Shitoukengde Ni-Cu deposit formed in the post-collisional, extensional regime related to the subducted oceanic slab break-off after the Wanbaogou oceanic basalt plateau collaged northward to the Qaidam Block in late Silurian.

Genesis of the Bianjiadayuan Pb-Zn polymetallic deposit, Inner Mongolia, China:Constraints from in-situ sulfur isotope and trace element geochemistry of pyrite

The Southern Great Xing’an Range (SGXR) which forms part of the eastern segment of the Central Asian Orogenic Belt (CAOB) is known as one of the most important Cu-Mo-Pb-Zn-Ag-Au metallogenic belts in China,hosting a number of porphyry Mo (Cu),skarn Fe (Sn),epithermal Au-Ag,and hydrothermal veintype Ag-Pb-Zn ore deposits.Here we investigate the Bianjiadayuan hydrothermal vein-type Ag-Pb-Zn ore deposit in the southern part of the SGXR.Porphyry Sn ±Cu ± Mo mineralization is also developed to the west of the Ag-Pb-Zn veins in the ore field.We identify a five-stage mineralization process based on field and petrologic studies including (i) the early porphyry mineralization stage,(ii) main porphyry mineralization stage,(iii) transition mineralization stage,(iv) vein-type mineralization stage and (v) late mineralization stage.Pyrite is the predominant sulfide mineral in all stages except in the late mineralization stage,and we identify corresponding four types of pyrites: Py1 is medium-grained subhedral to euhedral occurring in the early barren quartz vein;Py2 is medium- to fine-grained euhedral pyrite mainly coexisting with molybdenite,chalcopyrite,minor sphalerite and galena;Py3 is fine-grained,subhedral to irregular pyrite and displays cataclastic textures with micro-fractures;Py4 occurs as euhedral microcrystals and forms irregularly shaped aggregate with sphalerite and galena.LA-ICP-MS trace element analyses of pyrite show that Cu,Pb,Zn,Ag,Sn,Cd and Sb are partitioned into pyrite as structurally bound metals or mineral micro/nano-inclusions,whereas Co,Ni,As and Se enter the lattice via isomorphism in all types of pyrite.The Cu,Zn,Ag,Cd concentrations gradually increase from Py1 to Py4,which we correlate with cooling and mixing of ore-forming fluid with meteoric water.Py2 contains the highest contents of Co,Ni,Se,Te and Bi,suggesting high temperature conditions for the porphyry mineralization stage.Ratios of Co/Ni (0.03-10.79,average 2.13) and sulphur isotope composition of sulfide indicate typical hydrothermal origin for pyrites.The δ^34SCDT values of Py1 (0.42‰-1.61‰,average 1.16‰),Py2 (-1.23‰ to 0.82‰,average 0.35‰),Py3 (-0.36‰ to 2.47‰,average 0.97‰),Py4 (2.51‰-3.72‰,average 3.06‰),and other sulfides are consistent with those of typical porphyry deposit (-5‰ to 5‰),indicating that the Pb-Zn polymetallic mineralization in the Bianjiadayuan deposit is genetically linked to the Yanshanian (JurassiceCretaceous) magmatic-hydrothermal events.Variations of d34S values are ascribed to the changes in physical and chemical conditions during the evolution and migration of the ore-forming fluid.We propose that the high Sn content of pyrite in the Bianjiadayuan hydrothermal vein-type PbeZn polymetallic deposit can be used as a possible pathfinder to prospect for Sn mineralization in the surrounding area or deeper level of the ore field in this region.

Geology and Isotope Geochemistry of the Yinchanggou-Qiluogou Pb-Zn Deposit,Sichuan Province,Southwest China

The Yinchanggou-Qiluogou Pb-Zn deposit,located in the western Yangtze Block,southwest China,is hosted by the Upper Sinian Dengying Formation dolostone.Ore bodies occur in the Qiluogou anticline and the NS-and NNW-trending faults.Sulfide ores mainly consist of sphalerite,pyrite,galena and calcite,with subordinate dolomite and quartz.Seventeen ore bodies have been discovered to date and they have a combined 1.0 million tons of sulfide ores with average grades of 2.27wt%Zn and 6.89wt%Pb.The δD（H2O-SMOW） and δ18O（H2O-SMOW） values of fluid inclusions in quartz and calcite samples range from-68.9‰ to-48.7‰ and 7.3‰ to 15.9‰,respectively,suggesting that H2O in the hydrothermal fluids sourced from metamorphic water.Calcite samples have δ13C（PDB） values ranging from-6.2‰ to-4.1‰ and δ18O（SMOW） values ranging from 15.1‰ to 17.4‰,indicating C and O in the hydrothermal fluids likely derived from a mixed source of metamorphic fluids and the host carbonates.The δ34S（CDT） values of sulfide minerals range from 5.5‰ to 20.3‰,suggesting that thermal chemical reduction of sulfate minerals in evaporates were the most probable source of S in the hydrothermal fluids.The 206Pb/204Pb,207Pb/204Pb and 208Pb/204Pb ratios of sulfide minerals fall in the range of 18.11 to 18.40,15.66 to 15.76 and 38.25 to 38.88,respectively.The Pb isotopic data of the studied deposit plot near the upper crust Pb evolution curve and overlap with the age-corrected Proterozoic basement rocks and the Upper Sinian Dengying Formation hosting dolostone.This indicates that the Pb originated from a mixed source of the basement metamorphic rocks and the ore-hosting carbonate rocks.The ore geology and C-H-O-S-Pb isotopic data suggest that the YinchanggouQiluogou deposit is an unusual carbonate-hosted,strata-bound and epigenetic deposit that derived ore-forming materials from a mixed source of the underlying Porterozoic basements and the Sinian hosting carbonates.

Coupled trace element and SIMS sulfur isotope geochemistry of sedimentary pyrite:Implications on pyrite growth of Caixiashan Pb-Zn deposit

Colloform pyrite with core-rim texture is commonly deposited in carbonate platforms associated with the sulfide ores such as the Caixiashan Pb-Zn deposit.However,the genesis of colloform pyrite in Pb-Zn deposits,its growth controls and their geological implication are insufficiently understood.Integration of in-situ trace element and SIMS sulfur isotopes has revealed geochemical variations among these pyrite layers.These colloform pyrite occur as residual phases of core-rim aggregates,the cores are made up of very fine-grained anhedral pyrite particles,with some rims being made up of fine-grained and poorlycrystallized pyrite,while the other rims were featured with euhedral cubic pyrite.which are cemented by fine-grained calcite and/or dolomite with minor quartz.Sulfur isotope analysis shows that some wellpreserved rims have negative δ^34 S values(-28.12‰to-0.49‰),whereas most of the cores and rims have positive δ^34 S values(>0 to+44.28‰;peak at+14.91‰).Integrating with the methane and sulfate were observed in previous fluid inclusion study,we suggest that the 34 S depleted rims were initially formed by bacteria sulfate reduction(BSR),whereas the positive δ^34 S values were resulted from the sulfate reduction driven by anaerobic methane oxidation(AOM).The well-developed authigenic pyrite and calcite may also support the reaction of AOM.Combined with petrographic observations,trace element composition of the colloform pyrite reveals the incorporation and precipitation behavior of those high abundance elements in the pyrite:Pb and Zn were present as mineral inclusion and likely precipitated before Fe,as supported by the time-resolved Pb-Zn signal spikes in most of the analyzed pyrite grains.Other metals,such as Hg,Co and Ni,may have migrated as chloride complexes and entered the pyrite lattice.Arsenic and Sb,generally influenced by complex-forming reactions rather than substitution ones,could also enter the pyrite lattice,or slightly predate the precipitation of colloform pyrite as mineral inclusions,which are controlled by their hydrolysis constant in the ore fluids.The colloform pyrite may have grown inward from the rims.The successive BSR reaction process would enrich H^32/2S in the overlying water column but reduce the metal content,the nucleation of these pyrite rims was featured by strongly negative sulfur isotopes.The following AOM process should be activated by deformation like the turbidity sediment of the mudstone as the sulfide deposition are associated with fault activities that caused the emission of methane migration upward and simultaneously replenishing the metal in the column.The higher AOM reaction rate and the higher metal supply(not only Fe.but with minor other metals such as Pb and Zn) caused by sediment movement enhanced the metal concentration within the pyrite lattice.

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.

Isotopes and Geochronology of the Meixian-type Pb-Zn-(Ag)Deposits,Central Fujian Rift,South China:Implications for Geological Events

Central Fujian Rift is another new and important volcanogenic massive sulfide Pb-Zn polymetallic metallogenetic belt. In order to find out the material genesis and mineralization period of Meixian-type Pb-Zn-Ag deposits, S and Pb isotope analysis and isotope geochronology of ores and wall rocks for five major deposits are discussed. It is concluded that the composition of sulfur isotope from sulfide ore vary slightly in different deposits and the mean value is close to zero with the 834S ranging from -3.5‰ to ＋5.6‰ averaging at ＋2.0‰, which indicates that the sulfur might originate from magma or possibly erupted directly from volcano or was leached from ore-hosted volcanic rock. The lead from ores in most deposits displays radioactive genesis character （206pb/204pb〉18.140, 207Pb/204pb〉15.584, 208pb/204pb〉38.569） and lead isotope values of ores are higher than those of wall rocks, which indicates that the lead was likely leached from the ore-hosted volcanic rocks. Based on isotope data, two significant Pb-Zn metallogenesis are delineated, which are Mid- and Late-Proterozoic sedimentary exhalative metailogenesis （The single zircon U-Pb, Sm-Nd isochronal and Ar-Ar dating ages of ore- hosted wall rocks are calculated to be among 933-1788 Ma.） and Yanshanian magmatic hydrothermal superimposed and alternated metallogenesis （intrusive SHRIMP zircon U-Pb and Rb-Sr isochronal ages between 127-154 Ma）.

Genesis of the Changba–Lijiagou Giant Pb-Zn Deposit, West Qinling, Central China: Constraints from S-Pb-C-O isotopes

The extensive Changba-Lijiagou Pb-Zn deposit is located in the north of the Xihe–Chengxian ore cluster in West Qinling. The ore bodies are mainly hosted in the marble, dolomitic marble and biotite-calcite-quartz schist of the Middle Devonian Anjiacha Formation, and are structurally controlled by the fault and anticline. The ore-forming process can be divided into three main stages, based on field geological features and mineral assemblages. The mineral assemblages of hydrothermal stage I are pale-yellow coarse grain, low Fe sphalerite, pyrite with pits, barite and biotite. The mineral assemblages of hydrothermal stage II are black-brown cryptocrystalline, high Fe shalerite, pyrite without pits, marcasite or arsenopyrite replace the pyrite with pits, K-feldspar. The features of hydrothermal stage III are calcite-quartz-sulfide vein cutting the laminated, banded ore body. Forty-two sulfur isotope analyses, twenty-five lead isotope analyses and nineteen carbon and oxygen isotope analyses were determined on sphalerite, pyrite, galena and calcite. The δ34 S values of stage I(20.3 to 29.0‰) are consistent with the δ34 S of sulfate(barite) in the stratum. Combined with geological feature, inclusion characteristics and EPMA data, we propose that TSR has played a key role in the formation of the sulfides in stage I. The δ34 S values of stage II sphalerite and pyrite(15.1 to 23.0‰) are between sulfides in the host rock, magmatic sulfur and the sulfate(barite) in the stratum. This result suggests that multiple S reservoirs were the sources for S2-in stage II. The δ34 S values of stage III(13.1 to 22‰) combined with the structure of the geological and mineral features suggest a magmatic hydrothermal origin of the mineralization. The lead isotope compositions of the sulfides have 206 Pb/204 Pb ranging from 17.9480 to 17.9782, 207 Pb/204 Pb ranging from 15.611 to 15.622, and 208 Pb/204 Pb ranging from 38.1368 to 38.1691 in the three ore-forming stages. The narrow and symmetric distributions of the lead isotope values reflect homogenization of granite and mantle sources before the Pb-Zn mineralization. The δ13 CPDB and δ18 OSMOW values of stage I range from-0.1 to 2.4‰ and from 18.8 to 21.7‰. The values and inclusion data indicate that the source of fluids in stage I was the dissolution of marine carbonate. The δ13 CPDB and δ18 OSMOW values of stage II range from-4 to 1‰ and from 12.3 to 20.3‰, suggesting multiple C-O reservoirs in the Changba deposit and the addition of mantle-source fluid to the system. The values in stage III are-3.1‰ and 19.7‰, respectively. We infer that the process of mineralization involved evaporitic salt and sedimentary organic-bearing units interacting through thermochemical sulfate reduction through the isotopic, mineralogy and inclusion evidences. Subsequently, the geology feature, mineral assemblages, EPMA data and isotopic values support the conclusion that the ore-forming hydrothermal fluids were mixed with magmatic hydrothermal fluids and forming the massive dark sphalerite, then yielding the calcite-quartz-sulfide vein ore type at the last stage. The genesis of this ore deposit was epigenetic rather than the previously-proposed sedimentary-exhalative(SEDEX) type.

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.

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.

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.

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.

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).

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.

Hydrogen and Oxygen Isotope Study on the Water-Rock Interaction of the Yinshan (Cu-) Pb-Zn-Ag Ore Deposit, Jiangxi Province

The δ18O values of vein quartz of different stages from the Yinshan ore deposit are constant around 16‰ and the calculated δ18OH2O values attain 8‰± ; the δDH2O values of fluid inclu-sions in vein quartz are constant at about-60‰. From the surface down to 1200 m below the δ18O values of altered rocks gradually decrease from 15‰± to 11‰± . Various water-rock inversion calculations indicate that the ore fluids were formed by the interaction between meteoric water and phyllite at 350℃ and the effective W/ R value of around 0.1. When the water-rock exchange in the upper mineralization system took place, the effective W / R value increased to 5.0 or more. As a result, an evolution and mineralization model of a buffered open system with two-stage water-rock interactions is proposed in this study.

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.

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.

Analysis of level structure and monopole effects in Ca isotopes

Understanding the properties of nuclei near the double magic nucleus^(40)Ca is crucial for both nuclear theory and experiments.In this study,Ca isotopes were investigated using an extended pairing-plus-quadrupole model with monopole corrections.The negative-parity states of^(44)Ca were coupled with the intruder orbital g_(9/2)at 4 MeV.The values of E_(4+)/E_(2+)agree well with experimental trend from^(42)Ca to^(50)Ca,considering monopole effects between νf_(7/2)and νp_(3/2)(νf_(5/2)).This monopole effect,determined from data of^(48)Ca and^(50)Ca,supports the proposed new nuclear magic number N=34 by predicting a high-energy 2^(+)state in^(54)Ca.

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.