Geochemistry of trace elements and Sr-Nd isotopes of foraminifera shell from the Okinawa Trough

Trace elemental associations and Sr-Nd isotopic compositions are of important to recognition of biogenic material from mixed marine sediments. The foraminifera shell from the Okinawa Trough strongly enriches Sr,P,Mn and Ba, enriches Li,U,Th,Sc,Co,Cu,Pb,Zn,Cr,Rb,Y,Sb and light rare earth elements,slightly enriches V,Ga,Zr,Nb,Cd and middle rare earth elements,is short of Mo,In,Sn,Cs,Hf,Ta,W,Ti,Bi and heavy rare earth elements. The mechanism of elemental enrichment in forminifera is the concentrations of trace elements in sea water and selective absorption of trace elements during foraminifera living, as well as the geochemical affinity between major elements and trace elements.The REE (rare earth elements)partition pattern of foraminifera shell of the Okinawa Trough shows enrichment of middle rare earth elements with slightly negative Ce anomaly,which are different from those of foraminifera of the Pacific Ocean.The Sr,Nd isotopic ratios of the Okinawa Trough foraminifera are 0 709 769 and 0 512 162,respectively, which are different not only from those of oceanic water, but also from those of river water of China's Mainland, the former is slightly higher than those of oceanic water,but much lower than those of river water;the latter is slightly lower than those of oceanic water,but higher than those of river water,demonstrating that the Okinawa Trough sea water has been influenced by river water of China's Mainland.

REE and Sr-Nd isotope characteristics of hydrothermal chimney at Jade area in the Okinawa Trough

Hydrothermal chimney is a product of hydrothermal activity on the seabed. Chimney samples dredged from Jade hydrothermal area in Izena depression of the Okinawa Trough, are characterized by relatively enriched light rare earth elements (LREE) and strongly positive Eu anomalies. 87Sr/86Sr and 143Nd/144Nd of these samples are exactly between those of seawater and of acidic pumice, averaged at 0.708928 and 0.512292, respectively. These characteristics imply that the main source of hydrothermal sulfide at Jade area is possibly the undersurface acidic rocks. The mineralizing mechanism can be summarized as follows: Large amount of mineralized material would be leached out and LREE-enriched hydrothermal solution would be subsequently produced as a result of thermo-chemical exchange reaction between acidic volcanic rocks and heated seawater that penetrated in advance from upper water mass. The spurting out from the seabed and quickly crystallizing in the seawater of hydrothermal solution are responsible for the formation of Cu-Zn sulfide and barite-amorphous SiO2 minerals that are characterized by enriched LREE and positively strong Eu anomalies.

Geochemistry of Late Mesozoic mafic dykes in western Fujian Province of China: Sr-Nd isotope and trace element constraints

The Bancun diabase dyke and the Bali hornblende gabbro dyke in western Fujian Province were emplaced in the Early and Late Cretaceous periods, respectively; the former is designated to calc-alkaline series and the latter to K-high-calc-alkaline rock series. Both the dykes are characterized by such geochemical characteristics as high Al and Na2O>K2O. As for the Bancun dyke, Al2O3=16.32%–17.54% and K2O/Na2O=0.65–0.77; as for the Bali dyke, Al2O3=16.89%–17.81% and K2O/Na2O=0.93–0.99. Both the Bancun and Bali mafic dykes are relatively enriched in LILE and LREE, but depleted in HSFE, displaying the geochemical characteristics of continental marginal arc, with high initial Sr isotopic ratios and low εNd (t) values. The (87Sr/86Sr)i ratios of the Bancun diabase dyke are within the range of 0.708556–0.70903 and their εNd (t) values vary between -6.8 and -6.3; those of the Bali hornblende dyke are within the range of 0.710726–0.710746 and their εNd (t) values are -4.7– -4.9, showing the characteristics of enriched mantle EM II. The isotope and trace element data showed that the mafic dykes have not experienced obvious crustal contamination, and metasomatism caused by subduction fluids is the main factor leading to LILE and LREE enrichments. The enriched mantle is the source region for the mafic dykes, and mixing of subduction fluid metasomatized enriched mantle and EM II-type mantle constituted the mantle source region of both the Bancun and Bali mafic dykes. Upwelling of the asthenosphere mantle provided sufficient heat energy for the generation of magmas. In accordance with the discrimination diagram of their tectonic settings as well as their trace element geochemical characteristics, it is considered that the dykes both at Bancun and Bali possess the characteristics of continental marginal arc, revealing the tectonic environment of formation of the mafic dykes, the continental dynamic background as an intraplate tensional belt in which the mafic dykes were emplaced. Meanwhile, it is also indicated that the tensional tectonic stress mechanism is responsible for the formation of the mafic dykes in western Fujian Province.

Petrogenesis of the Langdu High-K Calc-Alkaline Intrusions in Yunnan Province: Constraints from Geochemistry and Sr-Nd Isotopes

The Langdu high-K calc-alkaline intrusions are located in the Zhongdian area, which is the southern part of the Yidun island arc. These intrusive rocks consist mainly of monzonite porphyry, granodiorite, and diorite porphyry. The K20 content of majority of these rocks is greater than 3%, and, in the K20-SiO2 diagram, all the samples fall into the high-K calc-alkaline to shoshonitic fields. They are enriched in light rare earth elements （LREEs） and depleted in heavy rare earth elements （HREEs; LaN/YbN = 14.3-21.2）, and show slightly negative Eu anomalies （6Eu = 0.77-1.00）. These rocks have high K, Rb, Sr, and Ba contents; moderate to high enrichment of compatible elements （Cr = 36.7-79.9 ppm, Co = 9.6-16.4 ppm, and MgO = 2.2%-3.4%）; low Nb, Ta, and Ti contents, and characteristic of low high field strength elements（HFSEs） versus incompatible elements ratios （Nb/Th = 0.75, Nb/La = 0.34） and incompatible elements ratios （Nb/U = 3.0 and Ce/Pb = 5.1, Ba/Rb = 12.0）. These rocks exhibit restricted Sr and Nd isotopic compositions, with （87Sr/S6Sr）i values ranging from 0.7044 to 0.7069 and ENd（t） values from -2.8 to -2.2. The Sr-Nd isotope systematic and specific trace element ratios suggest that Langdu high-K calc-alkaline intrusive rocks derived from a metasomatized mantle source. The unique geochemical feature of intrusive rocks can be modeled successfully using different members of a slightly enriched mantle, a slab-derived fluid, and terrigenous sediments. It can be inferred that the degree of partial melting and the presence of specific components are temporally related to the tectonic evolution of the Zhongdian island arc. Formation of these rocks can be explained by the various degrees of melting within an ascending region of the slightly enriched mantle, triggered by the subduction of the Garz^--Litang ocean, and an interaction between the slab-derived fluid and the terrigenous sediments.

Zircon U-Pb Chronology and Whole-rock Sr-Nd Isotope Compositions of Granite Porphyry in the Kaladaban Area of the Northern Altyn

Objective The Altyn Tagh marks the northern margin of the Qinghai-Tibet Plateau and lies between the Tarim block to the north and the Qaidam block,Qilian Orogen,and Kunlun orogenic belt to the south.The Altyn Tagh region contains ophiolite,high-to ultrahigh-pressure metamorphic rocks,and igneous rocks.Previous research has virified the occurrence of continental rifting,subduction,slab roll-back,and collision between the Tarim block and Proto-Tethys oceanic plate.Moreover,Kaladaban volcanic rocks are mainly distributed in the north Altyn region.Studies of the magmatic evolution of this region have proposed that Altyn oceanic plate was subducted during the Ordovician(Han et al.,2012;Wang et al.,2017).However,the specific timing and other aspects of the subduction are debated,and an investigation of granite porphyry in the Kaladaban area would improve our understanding of this subduction event.In this study,we present new U-Pb zircon dating result and Sr-Nd isotope composition data for granite porphyry from the North Altyn region.The objective is to constrain the timing of subduction of the North Altyn oceanic plate and establish the petrogenesis and magma source of the granite porphyry.

Petrology and Sr-Nd isotope systematics of the Ahobil kimberlite(Pipe-16)from the Wajrakarur field, Eastern Dharwar craton, southern India

Detailed mineralogical, bulk-rock geochemical and Sr-Nd isotopic data for the recently discovered Ahobil kimberlite(Pipe-16) from the Wajrakarur kimberlite field(WKF), Eastern Dharwar craton(EDC),southern India, are presented. Two generations of compositionally distinct olivine, Ti-poor phlogopite showing orangeitic evolutionary trends, spinel displaying magmatic trend-1, abundant perovskite, Tirich hydrogarnet, calcite and serpentine are the various mineral constituents. On the basis of(i) liquidus mineral composition,(ii) bulk-rock chemistry, and(iii) Sr-Nd isotopic composition, we show that Ahobil kimberlite shares several characteristic features of archetypal kimberlites than orangeites and lamproites. Geochemical modelling indicate Ahobil kimberlite magma derivation from small-degree melting of a carbonated peridotite source having higher Gd/Yb and lower La/Sm in contrast to those of orangeites from the Eastern Dharwar and Bastar cratons of Indian shield. The T_(Dm) Nd model age(～2.0 Ga) of the Ahobil kimberlite is(i) significantly older than those(1.5～1.3 Ga) reported for Wajrakarur and Narayanpet kimberlites of EDC,(ii) indistinguishable from those of the Mesoproterozoic EDC lamproites,and(iii) strikingly coincides with the timing of the amalgamation of the Columbia supercontinent. High bulk-rock Fe-Ti contents and wide variation in oxygen fugacity fO_2, as inferred from perovskite oxybarometry, suggest non-prospective nature of the Ahobil kimberlite for diamond.

Zircon LA-ICP-MS U-Pb dating and Sr-Nd isotope study of the Guposhan granite complex, Guangxi, China

Zircon U-Pb dating by the LA-ICP-MS method was applied to determining the ages of different units of the Guposhan granite complex, among which the East Guposhan unit is 160.8±1.6 Ma, the West Guposhan unit is 165.0±1.9 Ma, and the Lisong unit is 163.0±1.3 Ma in age. Much similarity in ages of the three units has thus proved that the whole Guposhan granite complex was formed in the same period of time. They were the products of large-scale granitic magmatism through crust-remelting in the first stage of the Middle Yanshanian in South China. However, the three units have differences both in petrology and in geochemistry. Besides the differences in major, trace and rare-earth elements, they are distinct in their Rb-Sr and Sm-Nd isotopic compositions. The East Guposhan unit and Lisong unit and its enclaves have a similar (87Sr/86Sr)i value of 0.7064 with an average of εNd(t)=-3.03, indicating that more mantle material was evolved in the magma derivation; whereas the West Guposhan unit has a higher (87Sr/86Sr)i value of 0.7173 but a lower εNd(t) value of -5.00, and is characterized by strong negative Eu anomalies and higher Rb/Sr ratios, suggesting that its source materials were composed of relatively old crust components and new mantle-derived components. In addition, an inherited zircon grain in the East Guposhan unit (GP-1) yielded a 206Pb/238U age of 806.4 Ma, which is similar to the ages of the Jiulin cordierite granite in northern Jiangxi and of the Yinqiao migmatic granite in Guangxi in the HZH granite zone. All this may provide new evidence for Late Proterozoic magmatism in the HZH granite zone.

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.

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.

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.

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.

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.

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.

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.

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.

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.

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(~13e6.5 Ma)alongside fold development.NE-striking fractures that crosscut W-E ones possibly formed recently due to stress reorientation.

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.