冲绳海槽中南部柱状沉积物氧化还原敏感元素赋存机理与环境指示意义

沉积物中氧化还原敏感元素（Redox Sensitive Element,RSE）含量变化是上覆水体氧化还原环境良好的替代指标。本文通过冲绳海槽中南部两个柱状沉积物（深度:30 cm）粒度、总有机碳、总氮及其同位素含量和氧化还原敏感元素含量等指标,探究复杂环境背景下冲绳海槽柱状沉积物中RSE的赋存机理与环境指示意义。研究发现,柱状沉积物中除了Cr亏损,其他RSE均显示有不同程度的富集。“粒控效应”对冲绳海槽柱状沉积物的RSE含量影响较小;分析可知,海水表层生产力是影响沉积物氧化还原环境的主要因素,通过Mn（氢）氧化物的吸附或解吸附作用实现RSE的富集与亏损。δCe、V/Cr、Ni/Co和V/（V+Ni）等指标指示沉积物整体处于氧化?弱氧化环境。沉积物中Mn元素通过还原作用以Mn2+形式向上扩散,在25～30 cm处被含氧间隙水氧化富集形成锰峰,指示柱状沉积物0～25 cm处为氧化环境,25～30 cm处为弱氧化环境。     

氧化还原敏感性元素在沉积环境判别中的应用研究进展

部分元素对氧化还原环境非常敏感,氧化还原条件往往决定着这些元素的迁移或富集,这些元素被称为氧化还原敏感性元素(redox sensitive elements,RSE).除Fe、Mn外大部分RSE在氧化环境条件下以溶解态离子形式存在于海洋水体而发生迁移,在还原环境条件下则容易从海洋水体中析出向沉积物中迁移并发生富集.RSE的这种特性常被用来判断现代或地质历史中的沉积环境.本文在总结RSE与沉积氧化还原环境判别的基础上,分析了影响RSE地球化学行为的因素,进而探讨了RSE应用中存在的主要问题及今后研究方向.RSE及相关指标在沉积环境判别中的应用主要包括:氧化还原状态的识别、指示海洋水体生产力变化、指示海洋水体的局限程度、指示沉积物物源等.影响或控制RSE迁移、转化、沉积和富集的主要因素有:成岩作用、陆源物质加入、粒控效应、Fe-Mn氧化物/氢氧化物的吸附、有机质含量、水体局限、人类活动等.迄今对部分RSE的迁移富集机制还不十分清楚,元素指标的应用较粗略.近期在RSE的应用中应重视样品的选取与保存、测量分析技术的提升以及多指标的互相印证,通过综合分析判断,才能得出更接近实际的结果.     

海洋环境中氧化还原敏感性微量元素的地球化学行为及环境指示意义

依据国内外最新研究成果,初步讨论了氧化还原敏感性微量元素(RSE)Re、Cd、Mo、U、V等的地球化学行为,其中包括海洋沉积物中RSE的来源、RSE在缺氧和无氧海区的沉淀富集机理及其环境指示意义。在此基础上讨论了利用RSE研究氧化还原环境时应注意的一些问题。RSE的沉淀富集机制不尽相同,但具有以下共同特点:①对底层海水的溶解氧浓度敏感。在正常溶解氧条件下,氧化还原敏感性微量元素在海水中呈溶解态稳定存在,而当底层海水处于缺氧或无氧条件时容易发生还原。②当底层海水处于缺氧或无氧条件时,经过沉积物—海水界面过程,受缺氧程度不同的制约,海水中呈溶解态的RSE依次在沉积物中沉淀,出现不同程度的富集。③持续还原条件下,RSE在沉积物中稳定存在;受氧化作用后,容易在沉积物中发生二次迁移和重新富集。不同的RSE其氧化还原电位不同,在氧化还原序列中的位置不同,Re在U之后Mo之前发生还原。因此,RSE在海洋沉积物中的不同富集特征和富集程度可作为还原程度指标研究底层海水的缺氧程度和底质的氧化还原环境。研究RSE的氧化还原环境指示意义,必须对RSE陆源碎屑来源组分进行剔除,同时,还应充分注意到还原沉积区发生氧化后,RSE在沉积物中会发生重新迁移和二次富集。     

南海琼东南海域沉积物的微量元素地球化学特征及其对天然气水合物的指示意义

天然气水合物已成为重要的战略资源。为探讨天然气水合物富集区的微量元素特征及其指示意义,对琼东南海域沉积物进行系统采样,分析了样品主、微量元素和TOC地球化学特征,并采用氧化还原状态以及氧化还原敏感元素与TOC相关关系的分析方法进行探讨。结果显示:沉积物相较于上地壳更为富集Sr、Pb、Th、U、Zn、Cu和Mo元素,Th/U和V/Sc比值在纵向上呈系统的变化,表层沉积物处于还原的沉积状态,大量富集Mo和U。初步推断研究区部分沉积物可能处于硫化带,使其出现氧化还原敏感元素(Mo和U)的富集,这些特征或由下部天然气水合物分解释放大量的甲烷所导致。表层沉积物孔隙水中出现的硫化带以及Mo和U元素异常,可作为新的地球化学指标以识别下部可能存在的天然气水合物资源。     

南海典型断面表层沉积物中氧化还原敏感元素的分布特征及其控制因素

氧化还原敏感元素在环境研究中发挥着日益重要的作用,然而对于海底表层沉积物中氧化还原敏感元素的分布规律与特征的研究鲜有涉及。本文以采集自南海4条典型断面(18°N、10°N、6°N、113°E)的75个表层沉积物样品为研究对象,通过主量元素和微量元素(含氧化还原敏感元素Mo、V、U)分析,并结合沉积物粒度、元素富集系数等数据,探讨了表层沉积物中氧化还原敏感元素的分布特征及其控制因素。结果表明,研究区每个断面中的V、U含量变化趋势十分相似,Mo含量变化与V、U的总体变化趋势相近,但Mo在断面上的变化波动比V、U更强烈。4条断面中Mo平均含量表现出明显富集,除了V在断面Ⅰ中表现为轻度富集外,V和U平均含量都表现为亏损。影响沉积物中Mo、V、U含量分布的因素主要包括陆源碎屑含量、生物碳酸盐含量、细粒沉积物的吸附作用和氧化还原环境等。所有断面中V和U的含量分布主要受控于陆源碎屑组分,同时也受到生物碳酸盐含量和细粒沉积物的吸附作用的影响,氧化还原环境对其含量影响较小,受环境影响的自生组分含量较低。Mo的含量分布主要受控于海底氧化还原环境,陆源碎屑组分的贡献和细粒沉积物吸附作用的影响较小,受环境影响的自生组分含量较高。西南次海盆的Mo含量及其富集系数都较低,可能是由于西南次海盆的底流活动使其海底存在氧化环境所致。     

长江口外缺氧区柱样沉积物元素的分布及其百年沉积环境效应

在210Pb定年的基础上,对取自长江口外缺氧区内外的柱样沉积物开展了10种常量元素、13种微量元素和粒度的测定分析,研究了其物源及分布特征。结果表明,缺氧区外柱样沉积物主要来源于老黄河口海岸泥沙,大部分元素具有"粒度控制"规律。缺氧区内沉积物主要来源于夏季长江陆源的输入和海洋自生生物死亡后的沉降,部分氧化还原敏感元素(RSE)和亲生物元素不受控于"粒控效应",其中Mo、Cd、As等氧化还原敏感元素自20世纪70年代以来明显富集,分别增加了83%、73%和50%,而Mn出现贫化,指示了缺氧区水体富营养化加剧和底层水体季节性缺氧,引起底层水-沉积物界面氧化还原环境变化;亲生物元素Ca、Sr、P含量自20世纪70年代起分别增加了129%、65%和38%,反映了受化肥使用等人类活动影响,近40年来长江口外水体生产力提高和生物量增加。     

东海陆架晚第四纪沉积物化学成分及物源示踪

东海陆架EA1孔和EA5孔沉积物化学成分变化范围较大。与东海陆架表层沉积物相比，钻孔沉积物的Si,Al,Mg,Mn,Ti,P,Ba,Zr,Co,Ni,Cu,Zn,Cr明显偏高，而Fe,Na,Ca,Sr,Li,U明显偏低，与全球大陆地壳化学组成相比，钻孔沉积物的Si,Li,Rb,Ba,Th,Zr,Hf,Cu,Zn,Pb偏高，而Al,Na,Ca,Mg,Fe,Mn,Ti,P,Sr,U,Co,Ni,V,Cr偏低，钻孔沉积物的化学成分在垂向上具有明显变化，主要受岩性和沉积环境的控制，钻孔沉积物中元素的富集因子（EF）均小于10，接近于1，表明钻孔沉积物主要来自大陆地壳，一些元素因分异或外来物质加入而富集，一些元素则因分异带出而亏损，钻孔沉积物源区的DF值判别表明，钻孔沉积物与现代黄河，长江沉积物均有亲缘关系，可能是在末次冰期最盛期，由于气候带南移，干旱区域扩大，在古长江搬运沉积物中类似现今黄河沉积物的干旱组分明显增加，从而导致了地球化学示踪结果的长江与黄河双重性，或者说古气候的变化导致了古长江搬运物质成分的变化。     

南海北部神狐海域水合物钻探区沉积物地球化学特征

海底水合物形成分解/甲烷渗漏的甲烷以及相关的生物地球化学过程可能对海底的沉积环境产生影响,因此识别水合物的形成分解/甲烷渗漏对海洋沉积环境改造有助于了解水合物成藏特征及其形成分解过程。选取南海北部神狐海域2007年水合物钻探区的SH3钻孔沉积物为研究对象,对SH3钻孔岩心的碳硫数据、主微量元素,尤其是氧化还原敏感元素(U、Mo、U/Mo、V/Sr)进行分析测试,同时结合SH3钻孔孔隙水数据和前人对神狐水合物钻探区的研究成果等进行对比研究。结果表明南海北部神狐海域沉积物来源除河流沉积物以外,同时还有少量中国黄土以及大陆岛弧的长英质岩浆岩沉积物;通过对U、Mo、U/Mo以及碳硫数据分析,发现SH3钻孔在10~25mbsf(meter below the seafloor)层位为硫酸盐驱动的甲烷厌氧氧化作用(Anaerobic oxidation of methane,AOM)造成的还原沉积环境,AOM作用导致了在这一层位发生了LREE/HREE、MREE/HREE的分馏;SH3钻孔沉积物在约180~215mbsf的含水合物层位出现了浊流沉积的次氧化的沉积环境,同时其赋存的细粒沉积环境也导致了轻重稀土元素的分馏,与水合物饱和度存在一定的相关性。     

长江口外缺氧区沉积物中元素分布的氧化还原环境效应

对取自长江口外缺氧区及其邻近海域表层沉积物样品进行了粒度组成和元素(主要包括氧化还原敏感性元素和亲碎屑元素)丰度的分析与测试,对长江口外缺氧区缺氧环境对元素分布的影响进行了探讨,提出了长江口外缺氧区沉积物中氧化还原敏感性元素(Redox sensitive elements,简称RSE)分布的氧化还原环境效应。亲碎屑元素丰度的分布显示出明显的粒控效应,而氧化还原敏感元素的分布受粒度效应的制约很弱,主要受离岸缺氧区还原环境的制约,具有在缺氧区富集的特点。缺氧环境对RSE分布的影响超过了元素的粒控效应,从而使研究区RSE的分布呈现出典型的氧化还原环境效应。     

长江口外缺氧区沉积物中氧化还原敏感性元素的"粒控效应"

对长江口外缺氧区及其邻近海域表层沉积物和沉积物岩芯样品的粒度和元素（主要包括氧化还原敏感性元素简称RSE,和典型陆源碎屑元素）进行了分析,并对元素的“粒控效应”进行了深入研究.结果表明,在近岸底层水溶解氧浓度正常海区沉积物中,元素（包括典型陆源碎屑元素和RSE）的分布显示出明显的“粒控效应”,在缺氧区沉积物中,RSE与粒度之间的相关性较差,其分布不受“粒控效应”的制约,而主要受氧化还原环境的影响.另外缺氧区缺氧程度的不同会导致不同的RSE的富集.     

Intense reducing conditions during the last deglaciation and Heinrich events (H1, H2, H3) in sediments from the oxygen minimum zone off Goa,eastern Arabian Sea

Two sediment cores, ABP-32/GC-01R and ABP-32/GC-03 were collected at a water depth of 642 m and 1086 m off Goa from the present day Oxygen Minimum Zone (OMZ) of eastern Arabian Sea (EAS) cover time span of last 18 ka and 32 ka respectively were analysed for multi-proxy redox-sensitive elements to understand the variation in the redox conditions and factors responsible for its development.Redox-sensitive elements concentration and their normalized ratios (Mn/Al, U/Th, Mo/Al and Ce/Ce*) suggest that sediment core ABP-32/GC-01R is under more reducing conditions due to its location within the centre of OMZ compared to core ABP-32/GC-03 which is at the base of OMZ. Sediments from the EAS are of non-euxinic environments where dissolved sulfide is present but restricted to the sediment pore-waters. Lack of significant correlation (r=< 0.1) of organic carbon with U and Mo suggest that productivity may not have control on the development of reducing conditions. The lowest Mn/Al ratio, strong negative Ce/Ce* anomaly and remarkable enrichment of U/Th and Mo/Al ratios during the last deglaciation, and Heinrich events (H1, H2, H3) indicate intense reducing conditions probably due to poor ventilation by oxygen depleted bottom waters from Subantarctic Mode Waters (SAMW) - Antarctic Intermediate waters (AAIW). There is a distinct lathanide fractionation in the sediment cores where, La_(n)/Yb_(n) ratio is <1, ≈1 and >1 during the last 10 ka (Holocene), 14–10 ka (includes-Younger Dryas and Bǿlling-Allerǿd), 18–14 ka (last deglaciation) and Heinrich events suggesting less reducing, terrigenous dominated and intense reducing condition respectively.     

Organic matter accumulation,redox, and diagenetic history of the Marcellus Formation,southwestern Pennsylvania,Appalachian basin

Variations in the concentration of redox sensitive elements combined with pyrite framboid size data documented from a Marcellus Formation (Middle Devonian) core recovered from southwestern Pennsylvania elucidate the redox, organic matter accumulation, and diagenetic history of these deposits in this region of the basin. Uranium and Mo enrichment and Fe/Al display sharp increases coincident with diminishing Th/U upward through the initial 3rd order trangressive systems tract (lower Union Springs Member). These data as well as abundant small (<6 μm) pyrite framboids record establishment of strongly reducing benthic conditions, perhaps related to the expansion of an oxygen minimum zone induced by increased surface productivity. Strongly anoxic, even euxinic, conditions were interrupted by episodes of dysoxia, perhaps seasonal or longer term. Overlying regressive systems tract (RST) deposits record modestly improved redox conditions, likely a reflection of a receding oxygen minimum zone as base level dropped. A subsequent 3rd order base level rise and renewed expansion of the oxygen minimum zone triggered by increased surface productivity resulted in the accumulation of the organic-rich lower Oatka Creek Member. Still, the mix of abundant small and subordinate large (>10 μm) framboids preserves the record of oxygen deficient to sulfidic bottom conditions frequently interrupted by episodes of (dys)oxia. Improving redox conditions through the overlying RST were accompanied by a two-fold increase in Al and consequent dilution of the organic matter flux and authigenic trace metal uptake at the sediment–water interface. The upper half of the Oatka Creek comprises a depositional sequence not obvious from core inspection or gamma-ray signature but revealed by Mo enrichment and Al concentration profiles. Diagenetic modification of the Marcellus includes several horizons of authigenic calcium carbonate concretions and marked Ba enrichment. Both features reflect the effects of non-steady state microbial diagenesis within a methane-rich sedimentary column.     

The geochemical characteristics and factors controlling the organic matter accumulation of the Late Ordovician-Early Silurian black shale in the Upper Yangtze Basin,South China

Organic-rich black shale of the Upper Yangtze Basin from the Late Ordovician and Early Silurian is considered an excellent source rock in South China. The formation and preservation conditions of this resource are revealed by its geochemical characteristics in this study. Geochemical indices, including redox indices (V/(V + Ni), V/Cr, V/Sc, and Ni/Co) and primary productivity indices (P/Ti and Ba/Al), and paleoclimate, clastic flux and sedimentary rate analyses are presented to investigate the accumulation mechanism of organic matter. Redox indices suggest that a stagnant, anoxic environment predominated in the Upper Yangtze Basin during accumulation of Wufeng and Longmaxi formations. In contrast, ventilated and oxygenated marine conditions pervaded the Upper Yangtze Basin during deposition of Linxiang and Guanyinqiao formations. The concentrations of V and U demonstrate that accumulation of organic matter was mainly controlled by redox conditions. Besides, such factors as clastic fluxes, fresh water inflows or a mixed deposition with a rapid sedimentary rate cannot be ignored due to their influences on organic matter enrichment and preservation. However, weak co-variance relationship of TOC content and productivity proxies, including P/Ti and Ba/Al, demonstrates that the accumulation of organic matter was not controlled by primary productivity. Results of the present study suggest a depositional model that stresses the importance of tectonic movements and glacial events on the accumulation and preservation of organic matter. The model shows that the Upper Yangtze Basin was a semi-restricted basin system influenced by the isolation of Xuefeng, but also it implies that oxygen-depleted bottom water of the basin favored the accumulation and preservation of sedimentary organic matter, resulting in the formation of organic-rich black shale.     

Sedimentary record of redox-sensitive elements (U, Mn, Mo) in a transitory anoxic basin (the Thau lagoon, France)

In order to further document the relation between redox conditions and the sedimentary record of Mn, U and Mo in a transitory anoxic water basin, their distribution has been studied along two profiles in the Thau lagoon (France). Sediments and pore-water have been sampled at two contrasting sites located, respectively, in the shellfish-farming area and in the centre of the lagoon. In the shellfish-farming area, the particulate organic carbon (POC) data indicate a more rapid organic matter mineralisation compared to the centre of the lagoon. This results in a sharper redox gradient characterized by the appearance of H₂S in pore-water a few millimetres below the sediment–water interface. In the centre of the lagoon, H₂S appears at a depth of 35 cm.In both cores, sedimentary Mn is relatively depleted through out the whole sedimentary column and varies with the proportion of clay minerals. After an initial release into solution at the sediment–water interface in relation to Mn-oxide reductive dissolution, authigenic U is immobilized when sulphides appear. Despite the occurrence of anoxic conditions at the sediment–water interface at the site influenced by shellfish farming, the burial of U is reduced by bioturbation, which raises reducing sediments to the surface. In the centre of the lagoon, Mo profiles reflect continuous diffusion into pore water and immobilization at 15 cm probably in anoxic microenvironments. At shellfish farms, dissolved Mo undergoes removal with sulphides but contrary to U, sedimentary Mo does not appear to be strongly affected by bioturbation. The profile indicates an increase in the frequency of anoxia crises during the second half of the 20th century.     

南海北部琼东南盆地冷泉区表层沉积物微量元素的分析及其对甲烷渗漏的指示

Recent studies have shown that specific geochemical characteristics of sediments can be used to reconstruct past methane seepage events. In this work, the correlation between the Sr/Ca and Mg/Ca ratios of sediment samples is analyzed and the sulfate concentration profile in Site C14 from cold-seep sediments in the Qiongdongnan Basin in northern South China Sea is obtained. The results confirmed that, sulfate at 0–247 cm below sea floor(Unit I) is mainly consumed by organic matter sulfate reduction(OSR), while sulfate at 247–655 cm(Unit II) is consumed by both the OSR and the anaerobic oxidation of methane(AOM). In addition, the bottom sediment layer is affected by weak methane seepage. The Mo and U enrichment factors also exhibit similar trends in their respective depth profiles. The responses of trace elements, including Co/Al, Ni/Al, Cr/Al and Zn/Al ratios to methane seepage allowed the study of depositional conditions and methane seepage events. Based on the results, it is speculated that the depositional conditions of Unit II changed with depth from moderate conditions of sulfidic and oxic conditions to locally anoxic conditions, and finally to suboxic conditions due to methane fluid leakage. The stable isotope values of chromium-reducible sulfide produced by AOM and those of sulfide formed by OSR in the early diagenetic environment suffered serious depletion of 34 S. This was probably due to weak methane leakage, which caused the slower upward diffusion and the effect of early diagenesis on the samples. It is necessary to consider the effects of depositional environments and diagenesis on these geochemical parameters.     

Mineralogical and chemical distribution of the Es3L oil shale in the Jiyang Depression,Bohai Bay Basin (E China): Implications for paleoenvironmental reconstruction and organic matter accumulation

The Es₃^L (lower sub-member of the third member of the Eocene Shahejie Formation) shale in the Jiyang Depression is a set of relatively thick and widely deposited lacustrine sediments with elevated organic carbon, and is considered to be one of the most important source rocks in East China. We can determine the mineralogy, organic and inorganic geochemistry of the Es₃^L shale and calculate paleoclimate indexes by using multiple geochemical proxies based on organic chemistry (total organic carbon [TOC] and Rock-Eval pyrolysis), major and trace elements, X-Ray diffraction, and carbon and oxygen isotope data from key wells alongside ECS (Elemental Capture Spectroscopy) well log data. These indicators can be used to analyze the evolution of the paleoenvironment and provide a mechanism of organic matter (OM) accumulation. The Es₃^L oil shale has high TOC abundance (most samples >3.0%) and is dominated by Type I kerogens. Additionally, the organic-rich shale is rich in CaO and enrichment in some trace metals is present, such as Sr, Ba and U. The positive δ¹³C and negative δ¹⁸O values, high Sr/Ba, B/Ga and Ca/Ca + Fe ratios and low C/S ratios indicate that the Es₃^L shales were mainly deposited in a semi-closed freshwater-brackish water lacustrine environment. The consistently low Ti/Al and Si/Al ratios reflect a restricted but rather homogeneous nature for the detrital supply. Many redox indicators, including the Th/U, V/(V + Ni), and δU ratios, pyrite morphology and TOC-TS-Fe diagrams suggest deposition under dysoxic to suboxic conditions. Subsequently, the brackish saline bottom water evolved into an anoxic water body under a relatively arid environment, during which organic-lean marls were deposited in the early stage. Later, an enhanced warm-humid climate provided an abundant mineral nutrient supply and promoted the accumulation of algal material. OM input from algal blooms reached a maximum during the deposition of the organic-rich calcareous shale with seasonal laminations. High P/Ti ratios and a strongly positive relationship between the P and TOC contents indicate that OM accumulation in the oil shale was mainly controlled by the high primary productivity of surface waters with help from a less stratified water column. Factors such as the physical protection of clay minerals and the dilution of detrital influx show less influence on OM enrichment.