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Revisiting the Mg isotopic systematics of siliciclastic components of sediments and sedimentary rocks:A new geochemical proxy of continental weathering in Earth's history

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Science China Earth Sciences 2024年第2期67卷 620-633页

作者： Tianzheng huang Bing SHEN kangjun huang Meng NING Chao LI Jinzhuang XUE Yuanlin SUN Baoqi huang Key Laboratory of Orogenic Belt and Crustal Evolution MOESchool of Earth and Space SciencesPeking UniversityBeijing100871China State Key Laboratory of Continental Dynamics Shaanxi Key Laboratory of Early Life and EnvironmentsDepartment of GeologyNorthwest UniversityXi’an710069China Institute of Sedimentary Geology Chengdu University of TechnologyChengdu610059China Key Laboratory of Rhenium-Osmium Isotopic Geochemistry Chinese Academy of Geological SciencesBeijing100037China

The Mg isotopic compositions of siliciclastic components(δ^(26)Mg_(sili))of sediments and sedimentary rocks have been commonly used to constrain the intensity of continental weathering,based on observations of,(1)an upward enrichment of26Mg in modern weathering profiles,(2)preferential uptake of26Mg in soil clays,and(3)general positive correlations between weathering intensities andδ^(26)Mg_(sili)***,not all weathering profiles display an upward increase ofδ^(26)Mg_(sili),and not all soil clays enrich in26Mg,complicating the interpretations ofδ^(26)Mg_(sili)data of sediments and sedimentary *** further explore the controls ofδ^(26)Mg_(sili)of sediments and sedimentary rocks,here we measuredδ^(26)Mg_(sili),mineralogical compositions and major element compositions of deep sea sediments from South China Sea(SCS)and carbonate rock samples from two late Paleozoic sections in South *** samples show decreasing trends of both normalized Mg concentration(Mgnorm)andδ^(26)Mg_(sili)values with the increase of weathering intensity,while SCS sediments samples do not show any correlation between Mgnormorδ^(26)Mg_(sili)values and weathering intensity.A three-stages weathering model is developed to explain the observed Mgnorm andδ^(26)Mg_(sili)*** the new model,weathering can be divided into three stages,(1)the preliminary weathering stage characterized by dissolution of primary minerals and formation of secondary clay minerals in saprolite,(2)the transitional stage with massive vermiculite and chlorite formation on the bottom of soil,and(3)the advanced stage showing dissolution of vermiculite and chlorite in the top of *** new model explains anδ^(26)Mg_(sili)increase and Mgnormdecrease with an increase weathering intensity in preliminary weathering stage and decrease of Mgnormandδ^(26)Mg_(sili)with increase weathering intensity in advanced weathering *** revised weathering model warrants the application of Mg isotope in the study of contin

关键词： Clay mineral Chemical weathering CIA Soil Weathering model

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Marine Carbon-Sulfur Biogeochemical Cycles during the Steptoean Positive Carbon Isotope Excursion(SPICE) in the Jiangnan Basin, South China

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Journal of Earth Science 2016年第2期27卷 242-254页

作者： Yang Peng Yongbo Peng Xianguo Lang Haoran Ma kangjun huang Fangbing Li Bing Shen Key Laboratory of Orogenic Belts and Crustal Evolution School of Earth and Space Science Peking University Beijing 100871 China Department of Geology & Geophysics Louisiana State University Baton Rouge LA 70803 USA

Global occurrences of Steptoean Positive Carbon Isotope Excursion（SPICE） during Late Cambrian recorded a significant perturbation in marine carbon cycle, and might have had profound impacts on the biological evolution. In previous studies, SPICE has been reported from the Jiangnan slope belt in South China. To evaluate the bathymetric extent of SPICE, we investigate the limestone samples from the upper Qingxi Formation in the Shaijiang Section in the Jiangnan Basin. Our results show the positive excursions for both carbonate carbon（δ^（13）C） and organic carbon（δ^（13）C_（org）） isotopes, as well as the concurrent positive shifts in sulfur isotopes of carbonate associated sulfate（CAS, δ^（34）S_（CAS）） and pyrite（δ^（34）S_（pyrite））, unequivocally indicating the presence of SPICE in the Jiangnan Basin. A 4‰ increase in δ^（13）C_（carb） of the Qingxi limestone implies the increase of the relative flux of organic carbon burial by a factor of two. Concurrent positive excursions in δ^（34）S_（CAS） and δ^（34）S_（pyrite） have been attributed to the enhanced pyrite burial in oceans with extremely low concentration and spatially heterogeneous isotopic composition of seawater sulfate. Here, we propose that the seawater sulfur isotopic heterogeneity can be generated by volatile organic sulfur compound（VOSC, such as methanethiol and dimethyl sulfide） formation in sulfidic continental margins that were widespread during SPICE. Emission of 32S-enriched VOSC in atmosphere, followed by lateral transportation and aerobic oxidation in atmosphere, and precipitation in open oceans result in a net flux of ^（32）S from continental margins to open oceans, elevating δ^（34）S of seawater sulfate in continental margins. A simple box model indicates that about 35% to 75% of seawater sulfate in continental margins needs to be transported to open oceans via VOSC formation.

关键词： steptoean positive carbon isotope excursion sulfur isotope Qingxi Formation SouthChina volatile organic sulfur compound.

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Sulfur and Oxygen Isotopes of Sulfate Extracted from Early Cambrian Phosphorite Nodules： Implications for Marine Redox Evolution in the Yangtze Platform

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Journal of Earth Science 2016年第2期27卷 170-179页

作者： Wenlang Qiao Xianguo Lang Yongbo Peng Kaiyuan Jiang Wu Chen kangjun huang Bing Shen Guizhou Geological Survey Guiyang Guizhou Province 550018 China Key Laboratory of Orogenic Belts and Crustal Evolution MOE & School of Earth and Space Sciences Peking University Beijing 100871 China Department of Geology and Geophysics Louisiana State University Baton Rouge LA 70803 USA

Phosphorite nodule beds are discovered in the black shale of basal Niutitang Formation throughout the Yangtze Platform in South China, recording an important phosphorite-generation event. Platform-wide phosphorite precipitation requires special oceanographic and geochemical conditions, thus the origin of the Niutitang phosphorite nodules may provide valuable information about the ocean chemistry in the Early Cambrian. In this study, we measured sulfur and oxygen isotopic compositions of sulfate extracted from phosphorite nodules collected from the basal Niutitang Formation. Phosphorite associated sulfate（PAS） is a trace amount of sulfate that incorporates into crystal lattice during phosphorite precipitation, accordingly PAS records the geochemical signals during phosphorite nodule formation. Sulfur isotopic composition of PAS（δ^（34）S_（PAS）） ranges from-1.16‰ to ＋24.48‰（mean=＋8.19‰, n=11）, and oxygen isotopic value（δ^（18）O_（PAS）） varies between-5.3‰ and ＋26.3‰（mean=＋7.0‰, n=8）. Most phosphorite nodules have low δ^（34）SPAS and low δ^（18）O_（PAS） values, suggesting PAS mainly derived from anaerobic oxidation of H_2S within suboxic sediment porewater. We propose that phosphate was delivered to the Yangtze Platform by a series of upwelling events, and was scavenged from seawater with the precipitation of FeOOH. The absorbed phosphate was released into suboxic porewater by the reduction of FeOOH at the oxic-suboxic redox boundary in sediments, and phosphorite nodule precipitated by the reaction of phosphate with Ca^（2＋） diffused from the overlying seawater. The platform-wide deposition of phosphorite nodules in the basal Niutitang Formation implies the bottom water might be suboxic or even oxic, at least sporadically, in Early Cambrian. We speculate that the intensified ocean circulation as evident with frequent occurrences of upwelling events might be the primary reason for the episodic oxidation of the Yangtze Platform in Early Cambrian.

关键词： phosphorite nodules Niutitang Formation phosphorite associated sulfate sulfurisotope oxygen isotope.

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Quantifying the carbon source of pedogenic calcite veins in weathered limestone: implications for the terrestrial carbon cycle

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Acta Geochimica 2019年第4期38卷 481-496页

作者： Lin Zou Lin Dong Meng Ning kangjun huang Yongbo Peng Shujian Qin Honglin Yuan Bing Shen Key Laboratory of Orogenic Belts and Crustal Evolution MOE and School of Earth and Space SciencePeking UniversityBeijingPeople's Republic of China Shaanxi Key Laboratory of Early Life and Environments Department of GeologyNorthwest UniversityXi'anPeople's Republic of China Department of Geology and Geophysics Louisiana State UniversityBaton RougeLA 70803USA

The continent is the second largest carbon sink on Earth’s *** the diversification of vascular land plants in the late Paleozoic,terrestrial organic carbon burial is represented by massive coal formation,while the development of soil profiles would account for both organic and inorganic carbon *** compared with soil organic carbon,inorganic carbon burial,collectively known as the soil carbonate,would have a greater impact on the long-term carbon *** carbonate would have multiple carbon sources,including dissolution of host calcareous rocks,dissolved inorganic carbon from freshwater,and oxidation of organic matter,but the host calcareous rock dissolution would not cause atmospheric ***,to evaluate the potential effect of soil carbonate formation on the atmospheric p CO2level,different carbon sources of soil carbonate should be quantitatively *** this study,we analyzed the carbon and magnesium isotopes of pedogenic calcite veins developed in a heavily weathered outcrop,consisting of limestone of the early Paleogene Guanzhuang Group in North *** on the C and Mg isotope data,we developed a numerical model to quantify the carbon source of calcite *** modeling results indicate that4–37 wt%of carbon in these calcite veins was derived from atmospheric *** low contribution from atmospheric CO2might be attributed to the host limestone that might have diluted the atmospheric ***,taking this value into consideration,it is estimated that soil carbonate formation would lower 1 ppm atmospheric CO2within 2000 years,i.e.,soil carbonate alone would sequester all atmospheric CO2within 1 million ***,our study suggests the C–Mg isotope system might be a better tool in quantifying the carbon source of soil carbonate.

关键词： Mg isotope Calcite veins Pedogenic carbonate Silicate weathering Carbonate weathering

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Heterogeneous Mg isotopic composition of the early Carboniferous limestone: implications for carbonate as a seawater archive

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Acta Geochimica 2018年第1期37卷 1-18页

作者： Haoran Ma Yihe Xu kangjun huang Yuanlin Sun Shan Ke Yang Peng Xianguo Lang Zhen Yan Bing Shen Key Laboratory of Orogenic Belts and Crustal Evolution MOE School of Earth and Space Sciences Peking University State Key Laboratory of Geological Processes and Mineral Resources China University of Geosciences

Carbonate precipitation and hydrothermal reaction are the two major processes that remove Mg from *** isotopes are significantly(up to 5%)fractionated during carbonate precipitation by preferential incorporation of ^(24)Mg,while hydrothermal reactions are associated with negligible Mg isotope fractionation by preferential sequestration of^( 26)***,the marine Mg cycle could be reflected by seawater Mg isotopic composition(δ^(26)Mg_(sw)),which might be recorded in marine ***,carbonates are both texturally and compositionally heterogeneous,and it is unclear which carbonate component is the most reliable for reconstructing δ^(26)Mg_(sw).In this study,we measured Mg isotopic compositions of limestone samples collected from the early Carboniferous huangjin Formation in South *** on petrographic studies,four carbonate components were recognized:micrite,marine cement,brachiopod shell,and *** four components had distinct δ^(26)Mg:(1)micrite samples ranged from -2.86% to -2.97%;(2)pure marine cements varied from -3.40% to -3.54%,while impure cement samples containing small amount of Rugosa coral skeletons showed a wider range(-3.27% to-3.75%);(3)values for the mixture component were-3.17% and -3.49%;and (4)brachiopod shells ranged from -2.20% to -3.07%,with the thickened hinge area enriched in ^( 24)*** to having multiple carbonate sources,neither the micrite nor the mixture component could be used to reconstruct δ^(26)Mg_(sw).In addition,the marine cement was homogenous in Mg isotopes,but lacking the fractionation by inorganic carbonate precipitation that is prerequisite for the accurate determination of δ^(26)Mg_(sw).Furthermore,brachiopod shells had heterogeneous C and Mg isotopes,suggesting a significant vital effect during ***,the heterogeneous δ^(26)Mg of the huangjin limestone makes it difficult to reconstruct δ^(26)Mg_(sw)using bulk carbonate/calcareous ***,δ^(26)Mg_(sw)was only slightly affected by

关键词： Seawater Mg isotopic composition Limestone Fossil Micrite Cement

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Cracking the superheavy pyrite enigma: possible roles of volatile organosulfur compound emission

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National Science Review 2021年第10期8卷 101-114页

作者： Xianguo Lang Zhouqiao Zhao Haoran Ma kangjun huang Songzhuo Li Chuanming Zhou Shuhai Xiao Yongbo Peng Yonggang Liu Wenbo Tang Bing Shen State Key Laboratory of Oil and Gas Reservoir Geology and Exploitation and Institute of Sedimentary Geology Chengdu University of Technology Key Laboratory of Orogenic Belts and Crustal Evolution of the Ministry of Education and School of Earth and Space Science Peking University State Key Laboratory of Palaeobiology and Stratigraphy Nanjing Institute of Geology and Palaeontology and Center for Excellence in Life and Palaeoenvironment Chinese Academy of Sciences School of Physics Peking University State Key Laboratory of Continental Dynamics Northwest University Shaanxi Key Laboratory of Early Life and Environments Department of Geology Northwest University Department of Geosciences Virginia Polytechnic Institute and State University International Center for Isotope Effect Research Nanjing University School of Earth Sciences and Engineering Nanjing University School of Mathematical and Statistical Sciences Arizona State University

The global deposition of superheavy pyrite(pyrite isotopically heavier than coeval seawater sulfate in the Neoproterozoic Era and particularly in the Cryogenian Period) defies explanation using the canonical marine sulfur cycle system. Here we report petrographic and sulfur isotopic data(δS) of superheavy pyrite from the Cryogenian Datangpo Formation(660–650 Ma) in South China. Our data indicate a syndepositional/early diagenetic origin of the Datangpo superheavy pyrite, withS-enriched HS supplied from sulfidic(HS rich) seawater. Instructed by a novel sulfur-cycling model, we propose that the emission ofS-depleted volatile organosulfur compounds(VOSC) that were generated via sulfide methylation may have contributed to the formation ofS-enriched sulfidic seawater and superheavy pyrite. The global emission of VOSC may be attributed to enhanced organic matter production after the Sturtian glaciation in the context of widespread sulfidic conditions. These findings demonstrate that VOSC cycling is an important component of the sulfur cycle in Proterozoic oceans.

关键词： sulfur isotope organosulfur compound sulfur cycle Cryogenian Datangpo Formation

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Primary and Secondary Calcite in Chinese Loess Distinguished by Crystallinity and Implications for Illuviation Depth and East Asian Summer Monsoon Intensity

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Journal of Earth Science 2024年

作者： Yan Zhao kangjun huang Yuanqiang Guo Pan Zhang Yawen Lu Long Ma State Key Laboratory of Continental Dynamics， Shaanxi Key Laboratory of Early Life and Environment， Department of Geology， Northwest University

The crystallinity has the potential to distinguish the primary and secondary calcite in Chinese loess， which then provides insights into illuviation depth and variations of the East Asian summer monsoon. However， this aspect has been rarely investigated. In this study， we defined the crystallinity of calcite as the Height/Area (H/A) ratio of the diffracted peak at crystal face (1 0 4). The H/A ratio inversely correlates with the average width of the diffracted peak， where a higher H/A ratio indicates higher crystallinity of calcite. Through the mixing and synthetic experiments， we found that the H/A ratio is minimally affected by factors such as calcite content， deposition temperature or rate but significantly influenced by the ionic impurity and the mixing proportion of different calcites. Subsequently， we examined desert samples of loess sources and loess carbonate nodules. Desert samples predominantly consist of primary calcite which inherits characteristics from cryptocrystalline limestone with high levels of ionic impurities resulting in low H/A ratio of 4.30 ± 0.51. In contrast， loess carbonate nodules contain abundant secondary calcite precipitated within soil interstices with low levels of ionic impurities leading to a significantly higher H/A ratio of 7.76 ± 0.82. Consequently， higher H/A ratios during interglacial periods compared to glacial periods are attributed to variations in relative proportions between primary and secondary calcite in loess sequences. The thickness， between the glacial-interglacial boundary and the depth where the H/A ratio starts to increase from the bottom to the top in the loess layer， can be used to indicate the illuviation depth of upper-soil carbonates and the intensity of the East Asian summer monsoon. This proxy can be further applied in long-term loess sequences to uncover the summer monsoon evolution.

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不同类型鲕粒灰岩储集层溶解动力学特征

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石油勘探与开发 2011年第4期38卷 495-502页

作者：王炜黄康俊鲍征宇钱一雄中国石化勘探南方分公司中国地质大学(武汉)地球科学学院中国地质大学(武汉)地质过程与矿产资源国家重点实验室中国石化石油勘探开发研究院无锡石油地质研究所

采用溶解动力学实验方法研究四川盆地东北部鲕粒灰岩储集层中孔-洞-缝等油气储集空间的发育、演化规律。不同温度和CO2分压(pCO2)条件下鲕粒灰岩的溶解动力学实验和微观形貌观察发现:温度为50℃、pCO2由1 MPa升高至4 MPa时,鲕粒灰岩的... 详细信息

采用溶解动力学实验方法研究四川盆地东北部鲕粒灰岩储集层中孔-洞-缝等油气储集空间的发育、演化规律。不同温度和CO2分压(pCO2)条件下鲕粒灰岩的溶解动力学实验和微观形貌观察发现:温度为50℃、pCO2由1 MPa升高至4 MPa时,鲕粒灰岩的溶解速率增大,并且鲕粒灰岩的溶解速率大于白云石化鲕粒灰岩的溶解速率;pCO2为3 MPa、温度由25℃升高至150℃,鲕粒灰岩溶蚀呈弱—强—弱的变化趋势,最大溶蚀速率在100℃左右,但白云石化鲕粒灰岩溶解速率随着温度的升高而增大,并且高于非白云石化鲕粒灰岩的溶解速率。扫描电镜图像显示,除原生构造裂隙外,白云石化鲕粒灰岩比非白云石化鲕粒灰岩更容易形成粒间孔、粒内孔等微观孔隙,说明溶蚀作用不是深埋环境下鲕滩优质储集层形成的单一控制因素,白云石化和溶蚀的共同作用更利于形成优质储集层。

关键词：四川盆地东北部鲕粒灰岩溶解动力学白云石化溶蚀

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金属稳定同位素示踪地球增氧事件

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地球科学 2021年第12期46卷 4427-4451页

作者：王振飞黄康俊路雅雯罗瑾鞠鹏程蒙泽坤大陆动力学国家重点实验室陕西省早期生命与环境重点实验室西北大学地质学系陕西西安710069

早期贫氧地球如何演化至现今富氧地球是理解地球宜居性形成与演化的关键,但重建地质历史时期地球大气与海洋氧含量仍是地球科学领域的重大挑战.金属稳定同位素的高精度测试分析为示踪地球大气与海洋氧化历史提供了新的研究手段.以Mo、U... 详细信息

早期贫氧地球如何演化至现今富氧地球是理解地球宜居性形成与演化的关键,但重建地质历史时期地球大气与海洋氧含量仍是地球科学领域的重大挑战.金属稳定同位素的高精度测试分析为示踪地球大气与海洋氧化历史提供了新的研究手段.以Mo、U、Tl、Cr四种氧化还原敏感金属稳定同位素体系为例,详细介绍了氧化还原敏感金属稳定同位素地球化学行为及分馏机理.在此基础上,系统回顾了金属稳定同位素在研究产氧光合作用的起源、大氧化事件(Great Oxidation Event,GOE)、中元古代大气和海洋氧化还原状态、新元古代氧化事件(NOE)等重大科学问题中的研究进展.金属稳定同位素在重建地球表层圈层氧化过程具有广阔的应用前景,对认识地球宜居性的演化历史以及探索其未来发展趋势具有深远意义.

关键词：氧循环地球宜居性氧化还原敏感金属元素产氧光合作用大氧化事件中元古代新元古代氧化事件地球化学

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基于HPLC和MC-ICP-MS的植物叶绿素镁同位素测试方法

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岩矿测试 2024年第3期43卷 476-486页

作者：安子涵张宏宇殷佳欣张攀姚敏黄康俊西北大学地质学系大陆动力学国家重点实验室陕西西安710069 中国科学院广州地球化学研究所同位素地球化学国家重点实验室广东广州510640

叶绿素a和叶绿素b是植物光合作用时吸收光能的主要色素,其中叶绿素b能帮助叶绿素a扩展吸收光谱促使其吸收更多光能,叶绿素a和叶绿素b比例的改变有助于植物适应光照变化。准确测定叶绿素a和叶绿素b的镁同位素值对研究叶绿素形成过程中镁... 详细信息

叶绿素a和叶绿素b是植物光合作用时吸收光能的主要色素,其中叶绿素b能帮助叶绿素a扩展吸收光谱促使其吸收更多光能,叶绿素a和叶绿素b比例的改变有助于植物适应光照变化。准确测定叶绿素a和叶绿素b的镁同位素值对研究叶绿素形成过程中镁的生物合成路径等问题具有重要意义,其中将叶绿素a和叶绿素b分离并收集是使用多接收电感耦合等离子体质谱仪(MC-ICP-MS)准确测定两者镁同位素值的关键。高效液相色谱(HPLC)是分离叶绿素的常用仪器,但目前HPLC分离叶绿素的方法主要聚焦于细菌和藻类叶绿素分离。因此,需开发一套能将植物叶绿素a和叶绿素b分离的方法,且该方法分离的样品适用于MC-ICP-MS的镁同位素测定。本文基于665nm检测波长和C18色谱柱(7.6mm×250mm,5μm),以三因素三水平正交设计优化HPLC条件,分析影响样品运行因素间的关系,得出符合要求的参数条件。经过优化的HPLC方法柱温为25℃,流速为1mL/min,流动相为甲醇-丙酮(80∶20,V/V)。结果表明:通过外标法定量分析叶绿素a和叶绿素b所得标准曲线在5~50mg/L浓度范围内的相关系数均大于0.9996,检测限为0.40~1.09mg/L,定量限为1.22~3.31mg/L,相对标准偏差(RSD)小于8.10%,样品加标回收率介于91.92%~111.11%。采用该方法对样品进行分离后,再利用MC-ICP-MS对前处理后的样品进行镁同位素测定,标准-样品间插法测定的数据表明镁同位素测试结果可靠,证明本文建立的方法为植物叶绿素a和叶绿素b的分离提供了技术支撑,且分离样品可用于镁同位素测定。

关键词：镁同位素标准-样品间插法高效液相色谱法流动相叶绿素a 叶绿素b

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