海水硝酸盐氮、氧同位素组成研究进展

海洋中氮的生物地球化学循环影响着海洋生态系统的结构和功能,并和全球气候变化有着密切的联系,一直是海洋科学研究的重点和热点。海水硝酸盐的15N/14N和18O/16O比值可以反映海洋中氮循环的主要过程,因而成为研究海洋氮循环的一个重要手段。综述海水硝酸盐氮、氧同位素组成的测定方法,同化吸收作用、硝化作用、反硝化作用、生物固氮作用等氮循环过程所导致的氮、氧同位素分馏及其在海洋学研究中的应用。海洋生态系中硝酸盐氮、氧同位素的分布可以提供支持生物生产力的氮来源信息,以及氮在不同储库迁移转化的路径与机制。未来的研究需要发展适用于低含量硝酸盐的同位素测量方法,构筑海洋氮的收支平衡,掌握影响上层海洋硝酸盐氮、氧同位素变化的过程,获取全球海域有关硝酸盐氮、氧同位素组成的更多数据。     

Characterization of Aquatic Dissolved Organic Matter by Spectral Analysis： From Watershed to Deep Ocean

Since 1990s， spectral analysis has become an important technique to characterize the properties of chromophoric and fluorescent dissolved organic matter （CDOM and FDOM） from various aquatic systems and a series of spectral indices have been suggested to trace the sources of DOM and their biogeochemical regulation processes. DOM samples were collected from an aquatic continuum from watershed to deep ocean， i.e. Zhangjiang River and Estuary， Dongshan Bay， Taiwan Strait， Northeast basin of the South China Sea， Luzon Strait and the vertical profile of the Kuroshio region of the West Pacific Ocean. This continuum covered many critical interfaces （land-ocean， shelf-basin， marginal sea basin-open ocean and euphotic and aphotic layer）. The spatial distribution and variation of various qualitative and quantitative parameters along the continuum were clearly revealed. Combined with literature review， the sources and sinks of CDOM/FDOM and their inherent regulation processes under significant hydrological and biogeochemical gradient variation were systematically summarized. The geochemical differentiation of the quantitative DOM spectral index in various aquatic systems was discussed. The tracing ability of the qualitative DOM spectral index was commented. The coupling study of soil-river organic matter systems， mechanism of mineralization-related microbial production of CDOM/FDOM， quantified geochemical framework concept and perturbation of global change on CDOM/FDOM dynamics were suggested as future key topics.     

海洋沉积物的锌同位素地球化学及其应用

锌同位素体系是海洋地球化学研究的新示踪剂,应用于示踪海水中锌元素的来源及其运移过程.海洋沉积物作为锌元素重要的"源"与/或"汇",其锌同位素组成的研究有助于理解海洋锌元素的地球化学循环.海洋沉积物记录了海水组成的信息,可以反演古海水锌同位素组成的变化,前提是理解沉积物与海水之间的分馏.对海水及海洋不同储库锌同位素研究进行系统总结,包括河流输入、热液体系、不同类型海洋沉积物(如富碳酸盐的沉积物、陆源硅酸盐碎屑、硅质沉积物、铁锰结核、贫氧-缺氧沉积物)的锌同位素组成,阐述了海洋沉积物锌同位素组成变化在古气候、古环境重建以及古海洋学等领域的应用以及重要性.      

国际地球化学研究现状与发展前沿——国际地球化学大会Goldschmidt 2011印象

对国际地球化学大会Goldschmidt 2011的基本情况、5个大会主题报告和23个分会报告作了较详细介绍与评述。这5个大会主题报告是:地幔中的挥发组分对板内岩浆作用的影响,地球深部挥发组分的循环:从远古到现代,利用地球化学信息研究末次冰川消退及其对河流的影响,外星大气:一个由热到可居住的世界,深海中的微生物群落与甲烷氧化作用。23个分会报告包括:宇宙化学,行星形成;早期地球:从地核到大气;地球深部动力学及其演化;从地幔至地壳:洋脊与板内岩浆活动;大陆壳的形成及演化;循环:俯冲,地幔楔与弧火山作用;地球环境演化;从纳米到大陆尺度界面与界面过程;火山与自然灾害地球化学;地球资源:能源;地球资源:矿;气候变化;大气气溶胶的源、汇及影响;风化、气候、构造与地表过程;海洋大气:过去与现在;人类活动产生的地球化学影响;生物地球化学:从微生物到宏观与循环;分析技术前沿;计算地球化学前沿;矿物学与矿物物理学前沿;水文地球化学与全球水资源可持续发展;一般主题;特别议题。文章重点阐述了国际地球化学目前的研究现状、热点领域、未来发展方向三个方面。对生物地球化学的研究现状与发展趋势作了专题评述。     

生态系统营养离子循环及水化学演经的锶同位素示踪

综述了Ｓｒ同位素示踪生态系统离子循环水化学演化的基本原理、主要内容和最新进展。着重介绍了Ｓｒ同位素在矿物风化速率研究、流域营养离子来源识别及其循环通量计算、地下水体化学尬发演化机制的示踪应用;最后展望了Ｓｒ同位素在生物地球化学过程示踪上的潜在价值。     

生态系统营养离子循环及水化学演化的锶同位素示踪

综述了Ｓｒ同位素示踪生态系统离子循环和水化学演化的基本原理、主要内容和最新进展。着重介绍了Ｓｒ同位素在矿物风化速率研究、流域营养离子来源识别及其循环通量计算、地下水体化学成分演化机制的研究中的示踪应用;最后展望了Ｓｒ同位素在生物地球化学过程示踪上的潜在价值。     

无机地球化学参数与有效烃源岩发育环境的相关研究

探索海相有效烃源岩判识指标仍是我国油气勘探中尚待解决的重要科研任务之一。古生产力及氧化还原条件是研究全球变化和海洋环境的重要内容,也是重塑有效烃源岩发育环境的主要参数。Si、Ba是古生产力的替代指标,Cd对古营养盐的反演具良好前景。过渡金属及其相关比值是缺氧环境的有效判识指标,可用其推断有机质保存条件。δ13Ccarb正偏移指示有机质埋藏量增加,是底部水体缺氧的响应。过渡金属同位素（δ65Cu、δ66Zn、δ97Mo）受生物活动及氧化还原条件的影响发生较大分馏,示踪环境变化具灵敏、高效性。将这些无机参数对古环境的示踪意义引入油气地质研究,从环境角度分析某一套地层能否发育有效烃源岩,进而探讨高演化海相有效烃源岩的判识,就更具特殊意义。     

Marine biogeochemistries of Be and Al: A study based on cosmogenic10Be, Be and Al in marine calcite, aragonite, and opal

The geochemical behaviors of Be and Al in ocean waters have been successfully studied in recent years using natural, cosmogenic, radioactive¹⁰Be and²⁶Al as tracers. The present day dissolved concentrations and distribution of the stable and radioactive isotopes of Be and Al in ocean waters have revealed their short residence times and appreciable effects of exchange fluxes at the coastal and ocean-sediment interfaces. It follows that concentrations of these particle-active elements must have varied in the past with temporal changes in climate, biological productivity and aeolian flux of continental detritus to the oceans. We therefore investigated the feasibility of extending the measurements of Be and Al isotope concentrations in marine systems to the 10³–10⁶ y BP time scale. We report here the discovery of significant amounts of intrinsic Be and Al in marine foraminiferal calcite and coral aragonite, and of Al in opal (radiolarians) and aragonite (coral), which makes it possible to determine¹⁰Be/Be and²⁶Al/Al in oceans in the past. We also report measured¹⁰Be/⁹Be in foraminiferal calcite in Pacific Ocean cores, which reveal that the concentrations and ratios of the stable and cosmogenic isotopes of Be and Al have varied significantly in the past 30 ky. The implications of these results are discussed.     

Geochemical interaction between the freshwater and marine hydrospheres

The results of more than 40 years long authors’ investigations in the field of the freshwater (river input) and marine (ocean waters) hydrospheres are summarized. The latest estimations of the global average concentrations of many chemical elements in river water and suspended matter and in ocean water and suspended matter are presented. It is shown that particulate suspended forms of many elements are predominant in river waters (“rivers are the kingdom of suspended forms of elements”), while their dissolved forms prevail in ocean waters (“ocean is the kingdom of dissolved forms of elements”). Sedimentary and biogeochemical processes of the river material transformation in the river-sea mixing zone (the so-called “marginal filter of the ocean”) were studied thoroughly. It was shown that radical quantitative and qualitative changes of dissolved and particulate suspended substances take place in this zone, resulting in the governed transformation of dissolved forms into suspended particulate forms and their following deposition on the bottom. The first data on the losses of 35 chemical elements in the river-sea mixing zone are presented. These data prove that the concentrations of dissolved elements in river and ocean waters are in regular and close relationship with their losses in the river-sea mixing zone and with the types of element distribution in ocean water column (conservative, biogenic, and lithogenic). This indicates the existence of a geochemical system in the entire (freshwater and marine) hydrosphere, which calls for deep and detailed investigations.     

Isotopic Geochemistry of Cadmium: A Review

Cadmium (Cd) is a scarce, but not an extremely rare element in the Earth’s crust (crustal average: 0.2 ppm Cd). Geochemically, Cd exhibits thiophile, lithophile, and volatile behavior in different geologic processes. Biologically, it is a nutrient-like element that is closely related to P and Zn and is toxic element to organisms. Presently, Cd isotopes have been successfully utilized to trace Cd sources and nutrient cycling in marine systems in addition to unearthing other geochemical processes. Using published studies and our recent work, this survey summarizes the chemical preparation and mass spectrometry of Cd isotopes. It also reviews Cd isotopic compositions and fractionation mechanisms in nature as well as experiments.     

水—岩相互作用研究的机遇与挑战

简要回顾水—岩相互作用研究的历史, 它基本经历了一个从水—岩相互作用, 到水—岩—有机物相互作用, 最后到水—岩—气—有机物—微生物相互作用研究的发展历程.近年来, 除基础地质及与矿产资源有关的课题继续深入外, 地下水环境演化与全球变化、含水系统中微量变价元素的迁移、转化与富集、地下水环境污染治理与修复、废物地质处置与CO₂封存等, 已经成为水—岩相互作用领域的研究热点.随着物理、化学、生物等领域中各种新理论和新方法的不断应用, 水—岩相互作用研究面临着新的机遇和挑战, 主要包括: 地下水系统中生物地球化学过程研究、水—岩相互作用中微观机理与宏观地球化学过程的耦合, 以及水—岩相互作用中的同位素分馏及应用等.      

Severe selenium depletion in the Phanerozoic oceans as a factor in three global mass extinction events

Selenium (Se) is one of the key trace elements required by all animal and most plant life, and Se deficiencies in the food chain cause pathologies or death. Here we show from new geochemical analyses of trace elements in Phanerozoic marine pyrite that sustained periods of severe Se depletion in the past oceans correlate closely with three major mass extinction events, at the end of the Ordovician, Devonian and Triassic periods. These represent periods of Se depletion > 1.5–2 orders of magnitude lower than current ocean abundances, being within the range to cause severe pathological damage in extant Se-reliant organisms. Se depletion may have been one of several factors in these complex extinction scenarios. Recovery from the depletion/extinction events is likely part of a natural marine cycle, although rapid rises in global oxygen from sudden major increases in marine productivity and plant biomass after each extinction event may also have played a crucial role.     

海洋环境中铁的来源、微生物作用过程及生态效应

铁在地壳中的含量位列第四,在海洋中常以微量元素的身份出现。铁拥有多变的价态和多样的功能,是调节海洋初级生产力和驱动海洋生物地球化学循环的重要力量。以往的研究表明,铁在维持初级生产力、耦合物质循环以及调节生源要素转化中具有重要作用。近年来微生物生态学的发展将铁的研究推向了新的高度,包括微生物驱动的铁氧化-还原行为、代谢过程以及与主要元素(C/N/P)的交互关系等。以近15年发表的文献为重点,尝试综述铁的最新进展。首先梳理了海洋中铁的来源和赋存状态(溶解态、胶体态、颗粒态和有机态);其次阐释了微生物介导的铁氧化还原类型和过程机制(如硝酸盐氧化、生物还原等);最后总结了铁与C/N/P循环的耦合关系以及在特定生态事件中的生态效应。此外,对海洋铁研究的“化学-生物-物理”理论框架也进行了展望,旨在为更好地认识铁循环及其在海洋微生态过程的作用提供资料借鉴。     

The State of Arts: Sources,Microbial Processes and Ecological Effects of Iron in the Marine Environment

Iron is the fourth most abundant element in the earth's crust, and it often appears as a trace element in the ocean. Iron has a variable valence and diverse functions, and is an important force to regulate marine primary productivity and drive the geochemical cycle in the ocean. Previous studies have shown that iron plays an important role in maintaining primary productivity, coupling matter cycles, and regulating the transformation of biogenic factors. In recent years, with the development of microbial ecology, iron research has enter more in-depth levels, including microbial-driven iron oxidation-reduction behavior, metabolic processes, and interactions with other major elements(C/N/P). This paper attempts to review the latest progress of iron, focusing on the published literatures of the past fifteen years. Firstly, we explained the sources and occurrence states of iron in the ocean (such as dissolved, colloidal, granular and organic state); Secondly, we reviewed the types and process mechanisms of microbial-mediated iron redoxbehavior (for example nitrate oxidation, and biological reduction, etc.); Finally, we summarized the coupling relationship between iron and C/N/P cycle. Additionally, the ecological roles of iron in specific ecological event (for instance algal bloom) has also been described. Furthermore, the "chemical-biological-physical" theoretical framework for marine iron research is also discussed. The purpose of this paper is to provide more information for marine microecological research and their effects on iron cycle under changing environment, such as global change.     

Thirty Years of the Seafloor CORK Borehole Observatories: Development,Applications and Future Perspective

In the past 50 years, we have witnessed remarkable progress in our understanding of the Earth and ocean system, as a result of the internationally integrated deep ocean drilling programs, the Deep Sea Drilling Program (DSDP), the Ocean Drilling Program (ODP), and the Integrated Ocean Drilling Program (IODP). One of the legacies of the deep ocean drilling programs is the development and applications of the CORK, Circulation Obviation Retrofit Kit. Earth and ocean sciences have been shifting from a traditional discontinuous, expeditionary mode toward a mode of sustained in situ observations today. The seafloor CORK observatories offer Earth, ocean and life scientists new opportunities to study multiple, interrelated deep marine subsurface processes, over time scales ranging from seconds to decades. Here, we first provided a concise examination of the development history of the CORKs, then described the first installations of ODP CORKs, the evolution of different models of CORK, and finally, summarized the scientific lessons learned in the installation and operation effort of the CORKs. In the end, we offered our perspectives on using CORKs to study geological, hydrogeological, microbiological, and biogeochemical processes in the deep marine subsurface biosphere, particularly pertaining to China’s efforts in establishing and enhancing its deep-sea and deep-biosphere research and monitoring programs.     

分散元素(Ge,Cd, Tl)稳定同位素研究

近年来,非传统稳定同位素地球化学得到了飞跃性的发展,其主要研究对象为海洋体系的演化。特别是氧化还原敏感元素(Se,Mo,Fe等)稳定同位素已经在古海洋环境的示踪研究中发挥重要的作用。相比分散元素(Ge,Cd,Tl)稳定同位素研究比较薄弱,但这些元素在海洋体系中有特殊的循环模式,这使得它们的同位素研究将可能存在很大地质潜力。海洋体系中它们的源汇简单,而且有机无机吸附过程都可能导致同位素分馏。Ge,Cd,Tl均属于挥发性元素,原始星云的形成过程可能存在较大的同位素分馏。我国南方大面积的低温成矿域,将为Ge,Cd,Tl稳定同位素的发展提供天然的平台。另外,Cd,Tl是环境污染的主要潜在元素,因此采用稳定同位素示踪还可能示踪表生环境中的污染来源。     

A non-steady-state compartmental model of global-scale mercury biogeochemistry with interhemispheric atmospheric gradients

A box model of mercury (Hg) cycling between the atmosphere and ocean is described and used to estimate Hg fluxes on a global scale (The Global/Regional Interhemispheric Mercury Model, GRIMM). Unlike previous simulations of this system, few assumptions are made concerning the rate of prominent marine biogeochemical processes affecting Hg (e.g., evasion, particle scavenging, and deep ocean burial). Instead, consistency with two observed atmospheric distributions was required: the interhemispheric gradient in total atmospheric Hg and the value for changes in the deposition of Hg from the atmosphere since industrialization observed in both hemispheres. Sensitivity analyses underscore the importance to modeling of the atmospheric lifetime of Hg, the magnitude of the interhemispheric gradient, the historical changes in Hg concentrations of various reservoirs, and vertical exchange between the surface ocean and the permanent thermocline. Results of the model indicate: lower evasional fluxes of Hg from the global ocean than previous estimates; a prominent role for particle scavenging as a removal mechanism from the surface ocean; a modest influence of dry processes (dust and gas) on Hg removal from the atmosphere; and an estimate of natural land-based sources of Hg to the atmosphere that is no more than about half that of anthropogenic sources.     

海水痕量元素——有机配体的配分特征与影响因素研究进展

在痕量元素的海洋生物地球化学循环过程中,有机配体直接控制痕量元素在不同形态及粒径范围内的分配,进而影响痕量元素的迁移转化过程和生物可利用性。深入研究海水中痕量元素-有机配体的配分特征及影响因素,明确有机配体分子量组分及其对痕量元素的配合作用差异,对于了解痕量元素的生物地球化学行为,评估痕量元素的生物可利用性和毒性效应均具有十分重要的意义。对海水中痕量元素-有机配体的分布规律、配分特征及盐度、pH、氧化还原条件和生物活动对配体的影响进行了系统总结。海水中的有机配体一般以低分子量部分为主体,配合能力因元素性质差异存在随分子量增加而提高或降低的不同趋势。除此之外,有机配体的结构、配合能力及分子量分布随水体各物理化学参数的变化而改变。盐度的增加会降低有机配体相邻官能团的静电排斥力从而降低配体的配合能力,还会导致高分子量金属有机配合物发生絮凝和降解而去除。pH的增加不仅可以促使有机配体离子化,还能促进部分痕量元素水解为与有机配体亲和力更高的形式,提高有机配体配合率。氧化还原环境同时影响了痕量元素的价态和有机配体的浓度,间接影响痕量元素-有机配体的配合率。浮游植物利用及微生物分解可以增加低分子量有机配体的比例,从而提高其配合能力,但当生物遭受过量金属离子的毒性胁迫时,其细胞内会释放胞内配体,将致毒元素转化为配合物并排出体外,从而增加水体中痕量元素高分子量有机配体的浓度。未来应结合有机物结构分析技术及痕量元素分离检测技术,系统研究海洋环境中不同分子量有机配体的结构及与痕量元素配合强度的相互关系,进一步揭示痕量元素的迁移转化过程与生态学意义。     

The Distribution of Trace Elements-Organic Ligands in Seawater and Factors Influencing Their Complexation

Organic metal-binding ligands represent an essential role in the bioavailability of trace elements since they govern the species and sizes of those elements in seawater. The distribution and properties of organic ligands in seawater as well as the factors influencing their complexation abilities were summarized in this paper. Most organic ligands exist in the low molecular weight fraction, and their concentration nearshore is often higher than that of open ocean while the vertical distribution varies in different areas. The complexation of trace elements and organic ligands is influenced by several factors such as molecular weight of organic ligands, salinity, pH, biological activities and redox conditions. Ligand with a lower molecular weight usually represents stronger complexation ability, whereas the opposite seems to be true sometimes due to the specific affinity between some elements and ligands. Increasing salinity lowers the electrostatic repulsion among adjacent functional groups of ligands and thus decreases their complexing rate, yet increasing pH promotes the ionization of organic ligands and results in the formation of more complexes. The utilization of phytoplankton and degradation of microorganism release more low molecular weight organic ligands while more high molecular weight ligands are released from marine organisms under heavy metal stress. Therefore, sufficient significance should be attached to characterizing the structure and molecular weight of organic ligands and exploring the interaction between trace elements and organic ligands and the influence of related marine factors on their behaviors, which will certainly help us to understand the global biogeochemical cycles and ecological significance of trace elements.     

Li同位素在矿床学中的应用:现状与展望

矿床的形成受制于多种复杂的地质作用,包括全球尺度的板块构造运动、岩浆活动、变质沉积改造等过程,并普遍伴随热液活动、流体迁移、水-岩相互作用、元素分异及同位素分馏等一系列局部区域地质和地球化学过程.在过去的矿床学研究中,地球化学方法主要围绕在主、微量元素和传统的稳定同位素等手段,解决了很多矿床成因问题.但仍存在不少的多解和难解问题,比如许多矿床在矿化类型、蚀变分带与金属矿物组合方面具有诸多相似之处,常规地球化学指标难以区分.随着测试精度的提高和自然储库组成的完善,Li同位素近些年来已成为新兴的稳定同位素体系.Li同位素在自然界过程中高达80‰的同位素分馏使其具有更好的辨识能力,同时兼有直接和间接指示作用,有潜力成为研究各种复杂成矿过程的良好示踪剂.本文总结了近年来有关矿床学中Li同位素的研究和应用进展,以俯冲带成矿为主,阐述了斑岩型-热液矿床、伟晶岩型矿床和沉积矿床等类型矿床的Li同位素地球化学特征,并探究新的Li同位素方法在矿床中的应用前景.基于Li同位素体系在各类矿床的应用实例,我们认为Li同位素体系将为矿床学研究提供更多的指示信息和依据.