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.

Geochemistry, U-Pb Geochronology and Sr-Nd-Hf Isotopes of the Early Cretaceous Volcanic Rocks in the Northern Da Hinggan Mountains

Whole-rock geochemical, zircon U-Pb geochronological and Sr-Nd-Hf isotopic data are presented for the Early Cretaceous volcanic rocks from the northern Da Hinggan Mountains. The volcanic rocks generally display high SiO2 （73.19-77.68 wt%） and Na20＋K20 （6.53-8.98 wt%） contents, with enrichment in Rb, Th, U, Pb and LREE, and depletion in Nb, Ta, P and Ti. Three rhyolite samples, one rhyolite porphyry sample, and one volcanic breccia sample yield weighted mean 206pb/23SU ages of 135.1±1.2 Ma, 116.5±1.1 Ma, 121.9±1.0 Ma, 118.1±0.9 Ma and 116.9±1.4 Ma, respectively. All these rocks have moderate （STSr/S6Sr）i values of 0.704912 to 0.705896, slightly negative eNd（t） values of -1.4 to -0.1, and positive Cur（t） values of 3.7 to 8. Their zircon Hf and whole-rock Nd isotopic model ages range from 594 to 1024 Ma. These results suggest that the Early Cretaceous volcanic rocks were originated from melting of subducted oceanic crust and associated sediments during the closure of the Mongol-Okhotsk Ocean.

Devonian alkaline magmatism in the northern North China Craton:Geochemistry,SHRIMP zircon U-Pb geochronology and Sr-Nd-Hf isotopes

The Wulanhada pluton is among the rare suite of Devonian alkaline plutons occurring along the northern margin of the North China Craton（NCC）.The intrusion is mainly composed of quartz-monzonite.Here we report zircon SHRIMP U-Pb data from this intrusion which shows emplacement age of ca.381.5 Ma.The rock is metaluminous with high（Na2O ＋ K2O） values ranging from 8.46 to 9.66 wt.%.The REE patterns of the rocks do not show any Eu anomaly whereas the primitive-mantle-normalized spider diagram shows strong positive Sr and Ba anomalies.The Wulanhada rocks exhibit high initial values of（87Sr/86Sr）t = 0.70762-0.70809,low εNd（t） =-12.76 to-12.15 values and negative values of εHf（t） =-23.49 to-17.02 with small variations in（176Hf/177Hf）,（0.281873-0.282049）.These geochemical features and quantitative isotopic modeling results suggest that the rocks might have been formed through the partial melting of Neoarchean basic rocks in the lower crust of the NCC.The Wulanhada rocks,together with the Devonian alkaline rocks and mafic-ultramafic complex from neighboring regions,constitute a post-collisional magmatic belt along the northern NCC.

Geochronology,Geochemistry,and Sr-Nd-Hf Isotopes of the Diorite Porphyrites from the Weining Beishan Area,Ningxia Hui Autonomous Region:Constraints on Their Source and Tectonic Implications

The Weining Beishan area of Ningxia Hui Autonomous Region is located at on the western edge of the Helanshan tectonic belt,which is a tectonic joint among Alxa Block,Ordos Block,and North Qilian orogenic belt.However,the tectonic evolution of this area remains unclear due to the lack of magmatic information.This paper conducted researches on geochronology,geochemistry,and Sr-Nd-Hf isotopes of the diorite porphyrites exposed in the Weining Beishan area.The zircon U-Pb dating yields two ages of 145.0±1.1 and 146.2±1.5 Ma,and the whole-rock geochemical data indicate that the diorite porphyrites are metaluminous to weakly peraluminous and high-K calc-alkaline series.The characteristics of highly initial^(87)Sr/^(86)Sr ratios(0.70816 to 0.71047),negativeε_(Nd)(t)(−8.9 to−8.4),and negativeε_(Hf)(t)(−13.8 to−21.2)indicate that the diorite porphyrites originated from partial melting of the middle-lower ancient crust related to the North China Craton.Combined with the regional geology,we suggested that partial melting was triggered by a tectonic activity of deep faults cutting through the crust under the regional stress transformation from compressing to extension during the Late Jurassic–Early Cretaceous,which is probably related to the westward subduction of the Paleo-Pacific Plate.

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.

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.

A review of classical hydrogen isotopes storage materials

Hydrogen storage alloys(HSAs)are attracting widespread interest in the nuclear industry because of the generation of stable metal hydrides after tritium absorption,thus effectively preventing the leakage of radioactive tritium.Commonly used HSAs in the hydrogen isotopes field are Zr2M(M=Co,Ni,Fe)alloys,metallic Pd,depleted U,and ZrCo alloy.Specifically,Zr2M(M=Co,Ni,Fe)alloys are considered promising tritium-getter materials,and metallic Pd is utilized to separate and purify hydrogen isotopes.Furthermore,depleted U and ZrCo alloy are well suited for storing and delivering hydrogen isotopes.Notably,all the aforementioned HSAs need to modulate their hydrogen storage properties for complex operating conditions.In this review,we present a comprehensive overview of the reported modification methods applied to the above alloys.Alloying is an effective amelioration method that mainly modulates the properties of HSAs by altering their local geometrical/electronic structures.Besides,microstructural modifications such as nano-sizing and nanopores have been used to increase the specific surface area and active sites of metallic Pd and ZrCo alloys for enhancing de-/hydrogenation kinetics.The combination of metallic Pd with support materials can significantly reduce the cost and enhance the pulverization resistance.Moreover,the poisoning resistance of ZrCo alloy is improved by constructing active surfaces with selective permeability.Overall,the review is constructive for better understanding the properties and mechanisms of hydrogen isotope storage alloys and provides effective guidance for future modification research.

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.

Petrogenesis of highly fractionated I-type granites in the Zayu area of eastern Gangdese, Tibet: Constraints from zircon U-Pb geochronology, geochemistry and Sr-Nd-Hf isotopes

The Cretaceous granitoids in the middle and northern Gangdese, Tibet are generally interpreted as the products of anatexis of thickened deep crust genetically associated with the Lhasa-Qiangtang collision. This paper reports bulk-rock major element, trace element and Sr-Nd isotopic data, zircon U-Pb age data, and zircon Hf isotopic data on the Zayu pluton in eastern Gangdese, Tibet. These data shed new light on the petrogenesis of the pluton. Our SHRIMP zircon U-Pb age dates, along with LA-ICPMS zircon U-Pb age dates recently reported in the literature, indicate that the Zayu pluton was emplaced at about 130 Ma, coeval with Early Cretaceous magmatic rocks in other areas of eastern Gangdese (e.g., Rawu, Baxoi areas) and the Middle Gangdese. The Zayu pluton samples lack amphibole and muscovite, and are compositionally characterized by high SiO2 (69.9%―76.8%), K2O (4.4%―5.7%), and low P2O5 (0.05%―0.12%). These samples also have A/CNK values of 1.00-1.05, and are enriched in Rb, Th, U, and Pb, and depleted in Ba, Nb, Ta, Sr, P, Ti, and Eu. These geochemical features suggest that the Zayu pluton samples are metaluminous to slightly peraluminous and are of highly fractionated I-type granite. The Zayu pluton samples have high εNd(t) values (-10.9--7.6) and low initial 87Sr/86Sr ratios (0.7120- 0.7179) relative to melts derived from mature continental crust in the Gangdese (e.g., Ningzhong Early Jurassic strongly peraluminous granite). The Zayu pluton samples are heterogeneous in zircon εHf(t) values (-12.8--2.9), yielding ancient zircon Hf crustal model ages of 1.4―2.0 Ga. The data obtained in this study together with the data in the recent literature suggest that the Early Cretaceous granitoids in eastern Gangdese represent the eastward extension of the Early Cretaceous magmatism in the middle Gangdese, and that the Lhasa micro-continent block with ancient basement may extend for ~2000 km from east to west. Zircon Hf isotopic data and bulk-rock zircon saturation temperature (789-821℃) indicate that mantle-derived materials likely played a role in the generation of the Zayu pluton. We propose that the Zayu pluton was most likely generated in a setting associated with southward sub- duction of the Bangong-Nujiang ocean floor, where mantle wedge-derived magmas may have providedthe heat and material for the anatexis of ancient crust of the Lhasa micro-continent, resulted in hybrid melts (i.e., mantle-derived basaltic magmas + crust-derived felsic magmas). Such hybrid melts with subsequent fractional crystallization are responsible for the highly evolved Zayu pluton (crust thick- ening is not a prerequisite).

Response to the Lomagundi-Jatuli Event in the southwestern margin of the Yangtze Plate:Evidence from the carbon and oxygen isotopes of the Paleoproterozoic Yongjingshao Formation

The Lomagundi-Jatuli Event(LJE)refers to the significant positive carbon isotope excursion in seawater constituents that occurred immediately after the increase in atmospheric oxygen content during the Paleoproterozoic(2.22-2.06 Ga).Theδ^(13)C values of 46 dolostone samples collected from the Paleoproterozoic Yongjingshao Formation varied in the range of 0.05‰-4.95‰(V-PDB;maximum:4.95‰)in this study,which may be related to the multicellular eukaryotes in the Liangshan Formation in the Yimen Group.They are much higher than theδ^(13)C values of marine carbonates(-1.16‰on average).Theδ^(13)C values of other formations in the Paleoproterozoic Yimen Group are negative.The notable positive carbon isotope anomalies of the Yongjingshao Formation indicate the response to the LJE at the southwestern margin of the Yangtze Block,which is reported for the first time.Furthermore,they are comparable to theδ^(13)C values of carbonates in the Dashiling Formation of the Hutuo Group in the Wutaishan area in the North China Craton,the Wuzhiling Formation of the Songshan Group in the Xiong'er area,Henan Province,and the Dashiqiao Formation of the Liaohe Group in the Guanmenshan area,Liaoning Province.Therefore,it can be further concluded that the LJE is a global event.This study reveals that LJE occurred in Central Yunnan at 2.15-2.10 Ga,lasting for about 50 Ma.The macro-columnar,bean-shaped,and microfilament fossils and reticular ultramicrofossils of multicellular eukaryotes in this period were discovered in the Liangshan Formation of the Yimen Group.They are the direct cause for the LJE and are also the oldest paleontological fossils ever found.The major events successively occurring in the early stage of the Earth include the Great Oxygenation Event(first occurrence),the global Superiortype banded iron formations(BIFs),the Huronian glaciation,the Great Oxygenation Event(second occurrence),the explosion of multicellular eukaryotes,the positive carbon isotope excursion,and the global anoxic and selenium-rich sedimentary event.The authors think that the North China Craton and the Yangtze Craton were possibly in different tectonic locations of the same continental block during the Proterozoic.

Zircon U-Pb geochronology,Hf isotopes,and geochemistry constraints on the age and tectonic affinity of the basement granitoids from the Qiongdongnan Basin,northern South China Sea

Studies in the northern South China Sea(SCS)basement remain important for understanding the evolution of the Southeast Asian continental margin.Due to a thick cover of sediments and scarce borehole penetration,little is known about the age and tectonic affinity of this basement.In this study,an integrated study of zircon U-Pb geochronology,Hf isotopes,and whole-rock major and trace elements on seven basement granitoids from seven boreholes of Qiongdongnan Basin has been carried out.New zircon U-Pb results for these granitoids present middle-late Permian((270.0±1.2)Ma;(253±3.4)Ma),middle to late Triassic((246.2±3.4)Ma;(239.3±0.96)Ma;(237.9±0.99)Ma;(228.9±1.0)Ma)and Late Cretaceous ages((120.6±0.6)Ma).New data from this study,in combination with the previous dataset,indicates that granitoid ages in northern SCS basement vary from 270 Ma to 70.5 Ma,with three age groups of 270–196 Ma,162–142 Ma,and 137–71 Ma,respectively.Except for the late Paleozoic-Mesozoic rocks in the basement of the northern SCS,a few old zircon grains with the age of(2708.1±17)Ma to(2166.6±19)Ma provide clues to the existence of the pre-Proterozoic components.The geochemical signatures indicate that the middle Permian-early Cretaceous granitoids from the Qiongdongnan Basin are I-type granites formed in a volcanic arc environment,which were probably related to the subduction of the Paleo-Pacific Plate.

Geodynamic Background of Intracontinental Cenozoic Alkaline Volcanic Rocks in Laojiezi, Western Yangtze Craton: Constraints from Sr-Nd-Hf-O Isotopes

The Laojiezi alkaline volcanic rocks, which are located in the intraplate region of the Yangtze craton, coincide with the formation of the Jinshajiang-Ailaoshan-Red River alkaline rock belt. Although this belt has been widely studied by geologists because of its porphyry-related Pb-Ag-Au polymetallic deposit and geotectonic location, the material sources of this belt are still debate. Whole-rock analyses show that these rocks have high total alkali contents(3.73–11.08 wt%), and their aluminum saturation index(ASI) values widely vary from 0.82 to 3.07, which comprise a metaluminous-peraluminous magma series. These rocks are characterized by high K(K2 O/Na2 O>1) and low Ti and Mg contents; enrichment in large-ion lithophile elements, such as Rb, Ba, K and light rare earth elements; and depletion in high field strength elements, such as Ta, Nb, P, and Ti. These rocks exhibit moderate Eu(Eu/Eu*=0.86–1.04) and Ce(Ce/Ce*=0.63–0.96) anomalies. Their(87 Sr/86 Sr)i, εNd(t), zircon εHf(t) and δ18 O values range from 0.70839 to 0.71013, from-10.16 to-12.45, from-19.6 to-5.8, and from 5.69‰ to 8.54‰, respectively, and their Nd and Hf two-stage model ages(TDM2) are 1.67–1.86 Ga and 1.27–2.02 Ga, respectively. These data reflect the primary partial melting of Paleoproterozoic to Mesoproterozoic lower crust with minor residual continental lithospheric mantle and supracrustal metasediments. The lithosphere was likely thickened along the southeastern margin of the Tibetan Plateau following the Indian-Asian continentcontinent collision(65–41 Ma). During the post-collision phase(36–16 Ma), the transition from a compressional to extensional setting triggered the convective removal of the over-thickened CLM beneath the Yangtze craton, which led to the upwelling of asthenospheric materials. This process created alkali-rich and high-K magma through the partial melting of the thickened lower crust. Magma that carried Cu-Au-Pb-Ag minerals was emplaced by strike-slip motion along the E-to W-or ENE-to WSWtrending tectonically weak zone, finally forming an alkaline porphyry Cu-Au-Pb-Ag polymetallic deposit.

Trace-element geochemistry and S–O isotopes in the fluorite-barite mineralization of Merguechoum,Moroccan eastern Meseta:insights into ore genesis to the Pangea rifting

The Merguechoum fluorite-barite mineralization,located in the Eastern Meseta of Morocco,is hosted in the Late Hercynian granite.The ore consists of fine crystals of fluorite 1,massive barite 1,euhedral crystals of fluorite 2,and barite 2 with calcite and minor quartz and sulfides.The Merguechoum ore deposits have never been investigated.This study was the first contribution that studied the genesis of fluorite and barite.The ore occurs as dissemination within granite intrusion and also fills the NE-SWtrending meter-sized fractures and faults.The values of the total Rare Earth Elements and Yttrium(REY)and the ratios of LREY/HREY,Y/Ho,Tb/Ca,and Tb/La indicate that the Merguechoum fluorite precipitated from hydrothermal fluids,likely basinal brines,which interacted with the Hercynian granite.The REY data indicate that the ore-forming fluids of the early stage have intensely interacted with the Hercynian granite compared to those of the late ore stage.The gradual decrease in the europium(Eu/Eu^(*)),yttrium(Y/Y^(*)),and cerium(Ce/Ce^(*))anomalies and a low concentration ofΣREY observed in the second ore stage compared to the first ore stage suggest an increase in p H and fO_(2)and by inference a decrease in temperature during the evolution of the hydrothermal system.This evolution could be explained by fluid mixing between the ascending basinal hydrothermal fluids and the diluted sulfate-rich meteoric water barite separates from selected samples reveal that the dissolved sulfates(SO_(4)^(2-))were derived from Permian–Triassic sulfates and/or coeval poreseawater sulfates.The proposed fluid mixing triggered the precipitation of an early-stage F-Ba assemblage followed by the second-stage F-Ba mineralization.Geologic fieldwork,REY inventories,and isotope data point to the ore genesis during the Permian–Triassic extensional tectonic activity concerning the Pangea rifting.This extensional tectonic environment is likely the driving force that mobilized a large amount of the ore-forming basinal brines along the available faults and fractures to the loci of ore deposition.

Sources and transformations of nitrite in the Amundsen Sea in summer 2019 and 2020 as revealed by nitrogen and oxygen isotopes

In this study,the nitrogen and oxygen isotope compositions of nitrite in the upper 150 m water column of the Amundsen Sea in the summer of 2019 and 2020 were measured to reveal the distribution and transformation of nitrite in the euphotic zone of the Southern Ocean.We found that primary nitrite maxima(PNMs)are widely present in the Amundsen Sea,where the depth of occurrence deepens from east to west and nitrite concentrations increases.Evidence from dual isotopes suggests that the formation of PNMs in all regions of the Amundsen Sea is dominated by ammonia oxidation.More importantly,the nitrogen and oxygen isotope compositions of nitrite in the Amundsen Sea mixed layer are abnormal,and their depth profiles are mirror symmetrical.Isotopic anomalies exhibit spatial variations,with central surface water having the lowest nitrogen isotope composition(−89.9‰±0.2‰)and western surface water having the highest oxygen isotope composition(63.3‰±0.3‰).Isotopic exchange reaction between nitrate and nitrite is responsible for these isotope anomalies,as both nitrogen and oxygen isotopes have large isotopic fractionation and opposite enrichment effects.This proves that isotopic exchange reaction operates extensively in different regions of the Amundsen Sea.Our study highlights the unique role of dual isotopes of nitrite in deepening the understanding of nitrogen cycle.Further studies on ammonia oxidation and isotopic exchange between nitrate and nitrite are warranted in the future to understand their roles in the nitrogen cycle in the Southern Ocean.

Procedure for determining the number of thermal diffusion columns in square cascade for separation of Ne stable isotopes

The thermal diffusion column represents one method of separating stable isotopes.This method is advantageous for smallscale operations because of the simplicity of the apparatus and small inventory,especially in gas-phase operations.Consequently,it has attracted attention for its applicability in tritium and noble gas separation systems.In this study,the R cascade was used to design and determine the number of columns.A square cascade was adopted for the final design because of its flexibility,and calculations were performed to separate 20Ne and 22Ne isotopes.All the R cascades that enriched the Ne isotopes by more than 99%were investigated,the number of columns was determined,and the square cascade parameters were optimized using the specified columns.Additionally,a calculation code“RSQ_CASCADE”was developed.A unit separation factor of three was considered,and the number of studied stages ranged from 10 to 20.The results showed that the column separation power,relative total flow rate,and required number of columns were linearly related to the number of stages.The separation power and relative total flow decreased and the number of columns increased as the stage number increased.Therefore,a cascade of 85 columns is recommended to separate the stable Ne isotopes.These calculations yielded a 17-stage square cascade with five columns in each stage.By changing the stage cut,feed point,and cascade feed flow rate,the best parameters for the square cascade were determined according to the cascade and column separation powers.As the column separation power had a maximum value in cascade feed 50,it was selected for separating Ne isotopes.

Features and factors of radium isotopes in Tianjin’s typical estuaries

In order to characterize the features of radium isotopes in estuaries of Tianjin,a continuous survey and sampling of typical estuaries were conducted from 2013 to 2017 in this study.The activities of natural radioactive radium isotopes(^(223)Ra,^(224)Ra,and ^(228)Ra)in groundwater and surface water were measured by the radium-delayed coincidence counting(RaDeCC)system.The non-conservative behavior of the radium isotopes was investigated under hydrogeochemical conditions and urbanization.The results indicated that in terms of horizontal distribution,the activities of radium in groundwater(Hangu,Tanggu,and Dagang)showed an upward trend from north to south and demonstrated a higher figure than surface water(Haihe River and Duliujian River).Concerning the vertical distribution,the activitives of radium at a 15 m burial depth was higher than that at a 30 m burial depth in all measurements.The activities of radium isotopes in the study area increased with the increase of total dissolved solids,and their desorption behavior on Fe-Mn oxides was constrained by the redox intensity.Different hydrogeological conditions resulted in variations in the vertical profile of radium activities.The activity of radium was regulated by seasonal variation and precipitation in groundwater and surface water.In addition,the rapid urbanization has caused a significant impact on the features of radium isotopes in typical estuaries of Tianjin.Meanwhile,radium isotopes can be applied to reflect the impact of urbanization on surface watergroundwater systems.Clarifying and cleverly utilizing the relationship between behavior of radium isotopes and urbanization will promote the development of the Tianjin Binhai New Area in a healthy way.

Geochemistry,Fluid Inclusions and Sulfur Isotopes of the Goshgarchay Cu-Au Deposit(Western Azerbaijan)in Lesser Caucasus:Implications for the Origins of Ore-forming Fluids

The Goshgarchay Cu-Au deposit is located in the central part of the northwest flank of the Murovdagh region in the Lesser Caucasus.The Goshgarchay Cu-Au deposit is associated with Middle Jurassic volcanic and Late Jurassic-Early Cretaceous high-K calc-alkaline intrusive rocks.The Cu-Au mineralization is commonly related to quartz-sericite-chlorite alteration dominantly composed of chalcopyrite,gold,sphalerite,pyrite,bornite,hematite,covellite,chalcocite,malachite,and azurite.The Goshgarchay copper-gold deposit,which is 600 m wide and approximately 1.2 km long,is seen as a faultcontrolled and vein-,stockwork-and disseminated type deposit.The Goshgarchay Cu-Au deposit predominantly comprises Cu(max.64500 ppm)and Au(max.11.3 ppm),while it comprises relatively less amounts Zn(max.437 ppm),Mo(max.47.5 ppm),Pb(max.134 ppm),and Ag(max.21 ppm).The homogenization temperatures and salinities of fluid inclusions in quartz for stage Ⅰ range from 380℃ to 327℃,and 6.9 wt% to 2.6 wt% NaCl eq.,respectively.Thand salinities in quartz for stage Ⅱ range from 304℃ to 253℃,and 7.6 wt% to 3.2 wt% NaCl eq.,respectively.The calculated δ^(34)S_(h2s)values(-1.5‰ to 5.5‰)of sulfides and especially the narrow range of δ^(34)S_(h2s) values of chalcopyrite and bornite(between -0.07‰ and +0.7‰)indicate that the source of the Goshgarchay Cu-Au mineralization is magmatic.Based on the mineralogical,geochemical,fluid inclusion,and sulfur isotopic data,the Goshgarchay Cu-Au deposit represents a late stage peripheral magmatic-hydrothermal mineralization probably underlain by a concealed porphyry deposit.

Using radium isotopes to quantify submarine groundwater discharge at different scales in the Huanghe River Estuary,China

As an important land-ocean interaction process,submarine groundwater discharge(SGD)is composed of multiple dynamical processes at different scales and plays an important role in the study of coastal ocean geochemical budgets.However,most of the existing studies focus on the quantification of the total groundwater discharge,few studies are about the differentiation and quantification of groundwater discharge processes at different scales(i.e.,short-scale SGD and long-scale SGD).As a world-class river,the Huanghe River is highly turbid and heavily regulated by humans.These natural and anthropogenic factors have a significant impact on groundwater discharge processes in the Huanghe River Estuary(HRE).In this study,the distribution patterns of the natural geochemical tracer radium isotopes(^(224)Ra and^(223)Ra)and other hydrological parameters in the HRE were investigated during four cruises.By solving the mass balance of^(224)Ra and^(223)Ra in the HRE,the long-scale SGD flux was quantified as 0.01−0.19 m/d,and the short-scale SGD flux was 0.03−0.04 m/d.The rate of short-scale SGD remained essentially constant among seasons,while the rate of long-scale SGD varied considerably at different periods and showed a synchronous trend with the variation of river discharge.The results of this study are significant for understanding the SGD dynamics in the HRE and the contribution of SGD to the ocean geochemical budgets.

Metallogenic Age and Ore-forming Material Sources of the Dahongshan Fe-Cu Deposit,Yunnan Province:Insights from Molybdenite Re-Os Dating and H-O-S-Pb Isotopes

The Dahongshan Fe-Cu(-Au)deposit is a superlarge deposit in the Kangdian metallogenic belt,southwestern China,comprising approximately 458 Mt of Fe ores(40%Fe)and 1.35 Mt Cu.Two main types of Fe-Cu(-Au)mineralization are present in the Dahongshan deposit:(1)early submarine volcanic exhalation and sedimentary mineralization characterized by strata-bound fine-grained magnetite and banded Fe-Cu sulfide(pyrite and chalcopyrite)hosted in the Na-rich metavolcanic rocks;(2)late hydrothermal(-vein)type mineralization characterized by Fe-Cu sulfide veins in the hosted strata or massive coarse-grained magnetite orebodies controlled by faults.While previous studies have focused primarily on the early submarine volcanic and sedimentary mineralization of the deposit,data related to late hydrothermal mineralization is lacking.In order to establish the metallogenic age and ore-forming material source of the late hydrothermal(-vein)type mineralization,this paper reports the Re-Os dating of molybdenite from the late hydrothermal vein Fe-Cu orebody and H,O,S,and Pb isotopic compositions of the hydrothermal quartz-sulfide veins.The primary aim of this study was to establish the metallogenic age and ore-forming material source of the hydrothermal type orebody.Results show that the molybdenite separated from quartz-sulfide veins has a Re-Os isochron age of 831±11 Ma,indicating that the Dahongshan Fe-Cu deposit experienced hydrothermal superimposed mineralization in Neoproterozoic.The molybdenite has a Re concentration of 99.7-382.4 ppm,indicating that the Re of the hydrothermal vein ores were primarily derived from the mantle.The δ^(34)S values of sulfides from the hydrothermal ores are 2‰-8‰ showing multi-peak tower distribution,suggesting that S in the ore-forming period was primarily derived from magma and partially from calcareous sedimentary rock.Furthermore,the abundance of radioactive Pb increased significantly from ore-bearing strata to layered and hydrothermal vein ores,which may be related to the later hydrothermal transformation.The composition of H and O isotopes within the hydrothermal quartz indicates that the ore-forming fluid is a mixture of magmatic water and a small quantity of water.These results further indicate that the late hydrothermal orebodies were formed by the Neoproterozoic magmatic hydrothermal event,which might be related to the breakup of the Rodinia supercontinent.Mantle derived magmatic hydrothermal fluid extracted ore-forming materials from the metavolcanic rocks of Dahongshan Group and formed the hydrothermal(-vein)type Fe-Cu orebodies by filling and metasomatism.