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.

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_2O-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.

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.

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).

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.

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.

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.

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.

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.

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.

Principle of Hydrogen Isotope Geochemistry Paleo-altimeter and its Potential in Reconstructing Paleo-elevation of the Southeastern Tibetan Plateau

The reconstruction of paleo-elevation serves a dual purpose to enhance our comprehension of geodynamic processes affecting terrestrial landforms and to contribute significantly to the interpretation of atmospheric circulation and biodiversity.The oxygen(δ~(18)O_w)and deuterium(δD_w)isotopes in atmospheric precipitation are systematically depleted with the increase of altitude,which are typical and widely applicated paleo-altimeters.The utilization of hydrogen isotope of hydrous silicate minerals within the shear zone system,volcanic glass,and plant leaf wax alkanes offers valuable insights for addressing evaporation and diagenesis.In this paper,we review the principle,application conditions,and influencing factors of the hydrogen isotope paleo-altimeter.In addition,we discuss the feasibility of utilizing this technique for quantitatively estimating the paleo-elevation of the southeastern Tibetan Plateau,where multiple shear zones extend over hundred kilometers parallel to the topographic gradient.

Distribution and sources of sedimentary organic matter in different aquaculture areas of northeastern Zhanjiang Bay using stable carbon and nitrogen isotopes

Zhanjiang Bay is a major aquaculture area in China with many types of mariculture products(such as oysters,fish,and shrimp).The culture area and shrimp output in Zhanjiang Bay are ranked first in China.We investigated the total organic carbon(TOC),total nitrogen(TN),TOC/TN ratio,and stable isotopes(δ^(13)C and δ^(15)N) of the fish and shrimp feed,fish and shrimp feces,and sedimentary organic matter(SOM) in and around different aquaculture areas of northeastern Zhanjiang B ay to study the impact of aquaculture activities on SOM.The average TOC contents of fish and shrimp feed were 39.20%±0.91% and 39.29%±0.21%,respectively.The average TOC content in the surface sediments of the oyster culture area,the mixed(fish and shrimp) culture area,and the cage fish farm area were 0.66%,0.88%±0.10%,and 0.58%±0.19%,respectively,which may indicate that mixed culture had a greater impact on SOM.The relatively high TOC and TN contents and relatively low TOC/TN ratios,and δ^(15)N values in the upper layer of the core sediment in the mixed culture area could also support the significant influence of mixed culture.The average δ^(13)C and δ^(15)N values of fish and shrimp feed were -20.6‰±2.2‰ and 1.8‰±1.2‰,respectively,which were different from the isotopic values of SOM in the study area.δ^(13)C and δ^(15)N values for SOM in different aquaculture areas were different from those of nearby reference stations,probably reflecting the influence of aquaculture.The δ^(13)C and δ^(15)N values in the oyster culture area(-25.9‰ and6.0‰,respectively) seemed to have reduced δ^(13)C and enriched δ^(15)N relative to those of the reference station(-24.6‰ and 5.8‰,respectively).This may reflect the influence of organic matter on oyster culture.The δ^(15)N value of the station in the mixed culture area(7.1‰±0.4‰) seemed to be relatively enriched in δ^(15)N relative to that of the reference station(6.6‰).Sedimentation and the subsequent degradation of organic matter from mixed cultures may have contributed to this phenomenon.The surface sediment at the cage fish farm area seemed to be affected by fish feces and primary production based on the indication of δ^(13)C and δ^(15)N values.The sediment core at the mixed culture region(NS6) had lower TOC/TN ratios and more positive δ^(13)C and δ^(15)N values than the sediment core at the oyster culture area,suggesting a higher proportionate contribution of marine organic matter in the mixed culture area.In summary,oyster culture,mixed culture,and cage fish culture in northeastern Zhanjiang Bay had a certain degree of impact on SOM,and mixed culture had more significant influences on SOM based on the high TOC contents and the significant vertical variations of TOC/TN ratio and δ^(15)N value in the sediment of this area.This study provides new insights into the impact of aquaculture activities on SOM content.

Isotope constraints on seasonal dynamics of nitrogen in Zhanjiang Bay, a typical mariculture bay in South China

Eutrophication in coastal waters has been increasing remarkably,severely impacting the water quality in mariculture bays.In this study,we conducted multiple isotopic measurements on suspended particulate nitrogen(δ^(15)N-PN) and dissolved nitrate(δ^(15)N-NO_(3)^(-)and δ^(18)O-NO_(3)^(-)) in Zhanjiang Bay,a typical mariculture bay with a high level of eutrophication in South China,to investigate the changes in nitrogen sources and their cycling between the rainy and dry seasons.During the rainy season,the study found no significant relation between δ^(15)NPN and δ^(15)N-NO_(3)^(-)due to the impact of heavy rainfall and terrestrial erosion.In the upper bay,a slight nitrate loss and slightly higher δ_(15)N-NO_(3)^(-)and δ^(18)O-NO_(3)^(-)values were observed,attributed to intense physical sedimentwater interactions.Despite some fluctuations,nitrate concentrations in the lower bay mainly aligned with the theoretical mixing line during the rainy season,suggesting that nitrate was primarily influenced by terrestrial erosion and that nitrate isotopes resembled the source.Consequently,the isotopic values of nitrate can be used for source apportionment in the rainy season.The results indicated that soil nitrogen(36%) and manure and sewage(33%) were the predominant nitrogen sources contributing to nitrogen loads during this period.In contrast,the dry season saw a deficient ammonium concentration(<0.2 μmol/L) in the bay,due to nearly complete consumption by phytoplankton during the red tide period.Additionally,the significant loss of nitrate and simultaneous increase in the stable isotopes of dissolved and particulate nitrogen suggest a strong coupling of assimilation and mineralization during the dry season.More active biogeochemical processes during the dry season may be related to decreased runoff and increased water retention time.Overall,our study illustrated the major seasonal nitrogen sources and their dynamics in Zhanjiang B ay,providing valuable insights for formulating effective policies to mitigate eutrophication in mariculture bays.

Cu-Zn isotope compositions of hydrothermal sediments from the southern Mid-Atlantic Ridge:implications to the sediment formation and mineral exploration

Six hydrothermal sediment samples were collected from the Xunmei and Tongguan hydrothermal fields along the southern Mid-Atlantic Ridge during the China Ocean Cruise DY46 in 2017.Sulfides and oxides in the samples were separated,and Cu and Zn isotope compositions were analyzed.Results show that the ranges ofδ^(65)Cu values of the bulk sediments,sulfides,and oxides were 0.36‰-2.46‰,-0.21‰-1.10‰,and 0.68‰-1.52‰,respectively.Theδ^(65)Cu values of sulfides in four samples(46II-14,46II-30,46III-06,and 46II-09)were relatively low(-0.21‰-0.50‰),corresponding to theδ^(65)Cu values of sulfides from inactive old hydrothermal chimneys in northern Mid-Atlantic Ridge(n MAR),suggesting that the sulfides in the sediments were originated from collapsed dead chimney mainly.While theδ^(65)Cu values of the other two samples(46III-02 and 46III-08)were relatively high(1.10‰-0.96‰),corresponding to theδ^(65)Cu values for active hydrothermal chimneys sulfides in n MAR,which indicated that the sulfides in these two samples might mainly come from sulfide particles settled from active hydrothermal plume.Because of the high density of sulfide particles,they tended to settle near the hydrothermal vents first.Therefore,highδ^(65)Cu values of sulfides in 46III-02 and 46III-08 implied that undiscovered active hydrothermal vents near the sampling positions of 46III-02 in the Xunmei hydrothermal field and 46III-08 in the Tongguan hydrothermal field.Theδ^(66)Zn values of hydrothermal sediments and sulfides ranged 0.11‰-0.43‰and 0.29‰-0.67‰,respectively.In the four samples from the Xunmei hydrothermal field,a positive correlation was found between the distance of the sampling position from sulfide mineralized spot and the Zn isotopic ratio,showing that the greater the distance from the mineralized spot,the heavier the Zn isotope composition as seen in two samples(46II-30 and 46II-14)of the Xunmei-3 spot.This result aligned with the findings of Wilkinson et al.(2005)and Baumgartner et al.(2023),suggesting that the lower the Zn isotope composition,the closer it is to the hydrothermal vent.However,in the Xunmei hydrothermal field,the Zn isotope composition in the other two samples(46III-02and 46III-06)showed the opposite trend.This indicated that there might be an active hydrothermal vent near the sampling location of sample 46III-02.This observation aligned with the Cu isotope analysis results.This study showed that Cu-Zn isotopes are good indicators for understanding the formation mechanisms of hydrothermal sediments and for locating active hydrothermal vents.

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.