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.

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.

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.

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.

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.

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.

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

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

Comparison of isotope-based linear and Bayesian mixing models in determining moisture recycling ratio

Stable water isotopes are natural tracers quantifying the contribution of moisture recycling to local precipitation,i.e.,the moisture recycling ratio,but various isotope-based models usually lead to different results,which affects the accuracy of local moisture recycling.In this study,a total of 18 stations from four typical areas in China were selected to compare the performance of isotope-based linear and Bayesian mixing models and to determine local moisture recycling ratio.Among the three vapor sources including advection,transpiration,and surface evaporation,the advection vapor usually played a dominant role,and the contribution of surface evaporation was less than that of transpiration.When the abnormal values were ignored,the arithmetic averages of differences between isotope-based linear and the Bayesian mixing models were 0.9%for transpiration,0.2%for surface evaporation,and–1.1%for advection,respectively,and the medians were 0.5%,0.2%,and–0.8%,respectively.The importance of transpiration was slightly less for most cases when the Bayesian mixing model was applied,and the contribution of advection was relatively larger.The Bayesian mixing model was found to perform better in determining an efficient solution since linear model sometimes resulted in negative contribution ratios.Sensitivity test with two isotope scenarios indicated that the Bayesian model had a relatively low sensitivity to the changes in isotope input,and it was important to accurately estimate the isotopes in precipitation vapor.Generally,the Bayesian mixing model should be recommended instead of a linear model.The findings are useful for understanding the performance of isotope-based linear and Bayesian mixing models under various climate backgrounds.

Feasibility of medical radioisotope production based on the proton beams at China Spallation Neutron Source

The utilization of a proton beam from the China Spallation Neutron Source(CSNS)for producing medical radioisotopes is appealing owing to its high current intensity and high energy.The medical isotope production based on the proton beam at the CSNS is significant for the development of future radiopharmaceuticals,particularly for theα-emitting radiopharmaceu-ticals.The production yield and activity of typical medical isotopes were estimated using the FLUKA simulation.The results indicate that the 300-MeV proton beam with a power of 100 kW at CSNS-II is highly suitable for proof-of-principle studies of most medical radioisotopes.In particular,this proton beam offers tremendous advantages for the large-scale production of alpha radioisotopes,such as 225Ac,whose theoretical production yield can reach approximately 57 Ci/week.Based on these results,we provide perspectives on the use of CSNS proton beams to produce radioisotopes for medical applications.

Molybdenum isotope composition of the upper mantle and its origin:insight from mid-ocean ridge basalt

The molybdenum(Mo)isotope system is pivotal in reconstructing marine redox changes throughout Earth’s history and has emerged as a promising tracer for igneous and metamorphic processes.Understanding its composition and variation across major geochemical reservoirs is essential for its application in investigating high-temperature processes.However,there is debate regarding theδ^(98/95)Mo value of the Earth’s mantle,with estimates ranging from sub-chondritic to super-chondritic values.Recent analyses of global mid-ocean ridge basalt(MORB)glasses revealed significantδ^(98/95)Mo variations attributed to mantle heterogeneity,proposing a two-component mixing model to explain the observed variation.Complementary studies confirmed the sub-chondriticδ^(98/95)Mo of the depleted upper mantle,suggesting remixing of subduction-modified oceanic crust as a plausible mechanism.These findings underscore the role of Mo isotopes as effective tracers for understanding dynamic processes associated with mantle-crustal recycling.

Fracturing timing of Jurassic reservoirs in the Dibei-Tuziluoke gas field,Kuqa foreland basin:Evidence from petrography,fluid inclusions,and clumped isotopes

Determining the timing of fracturing is crucial for understanding reservoir evolution and hydrocarbon accumulation in foreland basins.Using fracturing data from cores,borehole images,and outcrops,combined with the clumped isotope(D47)and fluid inclusion analyses of carbonate minerals filled in pores and fractures,this study ascertained the fracturing timing of the Jurassic reservoirs in the Dibei-Tuziluoke Gas Field,Kuqa Foreland Basin.Data from outcrops and borehole images show two dominant fracture sets in the study area:W-E and NE-SW striking fractures.Some W-E striking fractures are carbonate-filled,while NE-SW striking fractures lack mineral fillings.Bitumen veins,not easy to be identified in borehole images,are prevalent in cores.The petrographic analysis reveals that these bitumen veins formed before the calcite cementation in pores and display high viscosity and low maturity.Homogenization temperatures(T_(h))from primary fluid inclusion assemblages in two representative calcite vein samples were notably lower than T_(△47) values from corresponding samples.This suggests the △_(47) signature underwent alteration due to partial reordering during burial.Thus,△_(47)-derived temperatures(apparent temperatures)may not faithfully represent the mineral precipitation temperatures.When plotting these apparent temperatures vs.the burial history,only the possible latest ages of fracturing emerged.These ages were further refined by considering petroleum charging,tectonic evolution,and stress orientation.Bitumen-filled fractures likely resulted from the Late Cretaceous uplift,marking the migration of low-maturity hydrocarbons in the study area.Carbonate-filled E-W striking fractures emerged during the late Miocene(~13-6.5 Ma)alongside fold development.NE-striking fractures that crosscut W-E ones possibly formed recently due to stress reorientation.

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.

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.

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.

Genesis of the Jianbeigou Gold Deposit on the Southern Margin of the North China Craton: Insights from Fluid Inclusions, H-O-S Isotopes, and Pyrite in situ Trace Element Analyses

The Jianbeigou gold deposit is a typical lode gold deposit in the Qinling metallogenic belt, located on the southern margin of the North China Craton. Three stages of the hydrothermal process can be distinguished, including the quartz ± pyrite, quartz-polymetallic sulfide, and quartz-carbonate ± pyrite stages. From the early to late stages, the homogenization temperatures of primary fluid inclusions are 281–362°C, 227–331°C, and 149–261°C, respectively. The corresponding salinities estimated for these fluids are 3.9–9.9 wt%, 0.4–9.4 wt%, and 0.7–7.2 wt% Na Cl equiv. Combined with laser Raman spectroscopy data, the ore-forming fluid belongs to a H_(2)O-CO_(2)-Na Cl ± CH_4 system with medium–low temperature and salinity. The δ~(18)Ofluid and δD values for the quartz veins are-1.0‰ to 6.0‰ and-105‰ to-84‰, respectively, which indicates that the ore-forming fluid is of mixed source, mainly derived from magma, with a contribution from meteoric water. Pyrite has been identified into three generations based on mineral paragenetic sequencing, including Py1, Py2, and Py3. The pyrites have δ~(34)S sulfur isotopic compositions from three stages between 3.7‰ and 8.4‰, indicating that sulfur mainly originated from magma. Te, Bi, Sb, and Cu contents in pyrite were all high and showed a strong correlation with Au concentrations. Native gold and the Au-Ag-Bi telluride minerals were formed concurrently, and the As concentration was low and decoupled from the Au content. Therefore, Te, Bi, Sb and other low-melting point chalcophile elements play an important role for gold mineralization in arsenic-deficient ore-forming fluid. Combined with the geological setting, evolution of pyrite, and ore-fluids geochemistry, we propose that the Jianbeigou deposit can be classified as a magmatic–hydrothermal lode gold deposit. Gold mineralization on the southern margin of the North China Craton is related to Early Cretaceous magmatism and formed in an extensional setting.

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

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

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

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

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

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

Origin of the Yueguang gold deposit in Xinhua, Hunan Province, South China: insights from fl uid inclusion and hydrogen–oxygen stable isotope analysis

The Yueguang gold deposit is located in Fengjia,Xinhua County,Hunan Province,South China.It represents a recently discovered small-scale gold deposit situated in the southwestern region of the Jiangnan Orogenic Belt,west of the Baimashan granitic batholith.In order to discern the characteristics of the ore-formingfluids,the underlying mineralization processes,and establish a foundation for the origin of the Yueguang gold depositfluid inclusion micro-thermometry,as well as quartz hydrogen and oxygen isotope analysis,have been carried out on samples obtained from various stages of mineralization.The hydrothermal miner-alization stages within the Yueguang gold deposit can be categorized into three stages:(i)the barren,pre-ore quartz-pyrite stage(Stage Ⅰ),the quartz-pyrite-gold stage(Stage Ⅱ),and the post-ore quartz-carbonate stage(Stage Ⅲ),with the second stage being the main mineralization stage.Thefluid inclusions identified in samples from the main min-eralization stage can predominantly be described with the NaCl–H_(2)O and CO_(2)–NaCl–H_(2)O systems.These inclusions display homogenization temperatures ranging from 158.8 to 334.9℃,and thefluid salinity ranges from 0.3%to 4.0%(wt.%NaCl equiv.).Laser Raman spectroscopy analysis of individual inclusions further reveals the presence of gas-phases such as CO_(2),CH_(4),and N_(2).Isotopic analysis indicatesδ^(18)Ofluid values ranging from 3.95 to 6.7‰ and δDH_(2)O values ranging from-71.9 to-55.7‰.These results indi-cate that the ore-formingfluid of the Yueguang gold deposit belongs to metamorphic hydrothermalfluids of middle-low temperature and low salinity.In the process of ore formation,gold is transported in the form of Au(HS)2-complexes,with gold deposition being driven byfluid immiscibility.Therefore,the Yueguang gold deposit is categorized as an orogenic gold deposit dominated by metamorphic hydrother-malfluid.It may become a new target for gold exploration in the Baimashan region,central Hunan Province.