氧化还原敏感微量元素对古海洋沉积环境的指示意义

海洋的氧化还原条件控制着U、V和Mo等氧化还原敏感微量元素在沉积物或沉积岩中的富集程度,所以可以利用沉积物或沉积岩中这些微量元素的含量来重建古海洋的氧化还原状态和沉积环境。海洋沉积物或沉积岩中U、V和Mo的来源少,除了海水提供外,还有陆源碎屑,不过陆源碎屑提供的那部分含量能够被估计。沉积物埋藏之后这些元素（几乎）不发生迁移,保存了沉积时的组成和含量,能较好地反映沉积环境的特征,是古海洋环境的理想指示。在氧化—次氧化的海水环境中U、V和Mo不会富集,缺氧的条件下U和V富集,而在硫化（含溶解的硫化氢）的沉积环境中U、V和Mo在沉积物中都会强烈地富集。利用这种差异,可以根据沉积物或沉积岩中各种微量元素的含量变化来判别沉积时海水的氧化还原状态。但是,必须注意沉积环境的开放与否、成岩作用及重新氧化作用等对微量元素含量的影响。在利用氧化还原敏感元素进行古环境重建时,应首先评估沉积物或沉积岩中特定元素的来源和贡献,剔除非自生部分的影响,然后利用多元素指标综合判别古环境的氧化还原条件,才能获得可靠的结论。     

海洋沉积物中氧化还原敏感元素对水体环境缺氧状况的指示作用

近年来由于人为污染水体富营养化加剧,缺氧区面积不断增大,利用沉积物中氧化还原敏感元素反演水体缺氧情况已经发展成为海洋化学领域的热点研究方向。本文详细阐述了氧化还原敏感元素的富集机制,并总结了利用沉积物中氧化还原敏感元素在不同氧化还原条件下的富集程度反映海水缺氧程度和底质氧化还原状况的一系列指标,如Re/Mo、Cd/U、Th/U、V/Sc、V/(V+Ni)值,U—Mo共变模型,δ~(98/95)Mo,多指标微/痕量元素模型以及氧化还原敏感元素-有机质共变模型等。沉积物中Re、Mo含量、Re/Mo值、自生Mo/U值、Th/U值对上层水体缺氧和氧化条件区分良好,可定量指征上层水体的缺氧情况。沉积物中Re含量近似于1 ng/g(地壳值),Mo含量1μg/g(地壳值),Re/Mo值接近0.3×10~(-3),Mo—U富集系数比为(0.1～0.3)×现代海水,Th/U值2,可指示氧化环境;Re含量在10～30 ng/g,Mo含量近似于1μg/g,Re/Mo值10×10~(-3)～30×10~(-3),Mo—U富集系数比1×现代海水,Th/U值在0～2范围内,可指示缺氧环境;Re含量30 ng/g,Mo富集达到20～40μg/g,Re/Mo值接近0.7×10~(-3)(海水中Re/Mo值),Mo—U富集系数比为(3～10)×现代海水,可指示极度缺氧的硫化环境。Mo_(EF)—U_(EF)交会对数坐标图、氧化还原敏感元素-有机质共变模型指标可定性分析上层水体的缺氧情况;V/(V+Ni)值对于次氧化沉积物指示效果不佳;Cd/U值在次缺氧条件下的变化机制复杂,还需进一步研究。生物扰动、成岩作用、人为污染、水体局限、高有机碳通量、Fe、Mn氧化物循环等因素通过影响氧化还原敏感元素在沉积物中的富集与迁移,从而影响氧化还原敏感元素指标的应用,应剔除有机质吸附与陆源输入等非自生部分的影响,结合各种指标互相印证,综合判别水体氧化还原状态。     

海洋Re、Mo和U对氧化还原环境的指示作用

氧化还原敏感微量元素 Re、Mo 和 U 主要依靠扩散作用通过沉积物—水界面,在不同氧化还原条件下的沉积物中自生富集,Re在轻度还原的次氧化沉积环境中富集,Mo在还原性更强的硫化环境中富集,而 U 具有较宽的富集沉积深度区间。Re、Mo和 U 独特的地球化学行为使其可用于指示海洋环境的氧化还原状态,其在沉积物中的自生富集程度与沉积时所处的氧化还原条件具有良好的相关性：Re、Mo 和 U 在氧化沉积环境(Re/Al<1.3×10^-7,Mo/Al<0.4×10^-4)和季节性缺氧区覆盖的沉积环境中富集程度较小,在常年性缺氧区覆盖的沉积环境(U/Al>5×10^-4,Mo/Al>5×10^-4)和硫化沉积环境(Mo/Al>5×10^-4)中富集程度较大。除依据其地球化学行为特征和相对富集程度进行定性分析之外,还可以结合元素富集系数(TM_EF<1 表示亏损,TM_EF>1 表示富集,TM_EF     

云南昆阳磷矿黑色页岩微量元素特征及其地质意义

昆阳磷矿是我国下寒武统黑色页岩中赋存的最大的磷块岩矿床。为了探讨磷块岩及上覆黑色页岩的源区性质及古海洋的氧化还原环境,本文对梅树村组中谊村段的磷块岩、石岩头段的黑色页岩以及筇竹寺组玉案山段的砂质黑色页岩的地层剖面进行了岩石地球化学研究。发现昆阳剖面磷矿区的下寒武统黑色页岩Th-Zr和Th-Y/Ho比值以及Y-Y/Ho比值与陆源碎屑物质更为接近,石岩头段黑色页岩样品的稀土元素总量平均为174×10^-6,与大陆壳稀土总量的平均丰度基本一致。稀土配分模式也十分类似,说明陆源碎屑物质来源比海水自生来源占的比重更大。受陆源碎屑物质的影响,Ni/Co,V/Cr和V/（V+Ni）等氧化还原敏感元素比值并不能很好的指示古海洋的沉积环境。但石岩头段黑色页岩的氧化还原敏感元素相对大陆壳具有一定程度的富集,并且富集程度不强烈,Ce具有轻微的负异常,反映了黑色页岩可能形成于次氧化环境。     

沉积物成岩蚀变过程中的Mn、Cd和Mo元素活动特征:以ODP 1148站钻孔沉积物记录为例

通过对南海北部的ODP 1148站岩芯600 mcd以上(约30 Ma以来)的沉积物中自生富集Mn、Cd和Mo等过渡金属元素的含量变化的研究,并结合相关的化学组成结果,探讨了岩芯内部氧化-还原条件的变化以及相关元素的活动特征,反演了相应沉积时期的环境演变.结果显示,岩芯387 mcd以上,自生Mn富集明显,代表氧化的环境;387～485 mcd之间,自生Cd含量明显富集,Mn含量显著降低,代表少氧的环境;485 mcd以下,Mn和Cd含量极低,自生Mo明显富集,代表缺氧的环境.随氧化-还原条件的变化,Mo存在明显的向下迁移并在缺氧界面的缺氧一方达到最大值的趋势,而Cd在少氧环境形成的固相态则可能在缺氧环境下不稳定,溶解态的Cd有向上迁移的趋势,并且在少氧/缺氧界面的少氧一方富集.这些过渡金属元素记录的氧化-还原条件的变化,反映出ODP 1148站所在海区的沉积环境变化:早期有较丰富的陆源输入,表层海水生产力较高,随着南海不断扩张以及全球海平面上升,该海区表层海水生产力逐渐降低.     

沉积物微量金属元素在重建水体环境变化中的意义

沉积物所记录的微量金属含量与形态的变化是指示人类活动影响下水体环境变化的有效指标,主要用于指示沉积物重金属污染、水体初级生产力变化和氧化还原条件等方面的水体环境状况。总体而言,沉积物中微量金属含量在近一个世纪以来显著上升,反映了采矿、冶金、污水排放、化肥使用、煤炭和石油燃烧等各种人类活动造成水体和沉积物重金属污染的记录作为浮游植物微量营养元素,Cu、Zn、Ni、Ba、Cd等在沉积物中的记录可以指示水体初级生产力水平。U、Mo、V、Cu、Cd、Mn等氧化还原敏感元素在沉积物中的富集或贫化,及其比值(如Re/Mo、Cd/U、Th/U和V/Sc)的变化,是指示水体和沉积物氧化还原环境的有效指标。但需要指出的是,在受人类活动影响的水体中,这些生产力和氧化还原指标很少能指示水体生产力或氧化还原状况,可能主要与人类活动同时造成这些金属元素大量污染输入而掩盖了其自生来源和内在变化的沉积记录有关。所以,对沉积物中微量金属元素来源的判别(陆源碎屑输入、人为输入和水体自生来源)是重建水体环境变化的重要前提。本文总结了多种化学和统计学方法(包括同位素示踪法、化学提取法、富集因子法和主成分分析法等)在沉积物金属来源判别中的应用另外,成岩作用等多种因素会干扰沉积物金属记录对环境变化的指示作用,所以构建多元素指标来综合判断沉积物记录所反映的环境信息是今后的研究所必须关注的     

藏南白垩系泥、页岩微量、稀土元素特征及氧化-还原环境分析

为了解藏南定日-岗巴盆地和江孜盆地白垩纪沉积时底层水体的氧化一还原环境,采用ICP-MS方法进行微量元素及稀土元素测试分析.结果表明:研究区微量元素在时空上均发生了变化,这与各元素对沉积水体的氧化一还原敏感程度有关.元素Al标准化后变化趋势也不尽相同,其垂向上的变化反映了沉积物底层水体氧化-还原状况、生物产率等沉积环境,与海平面升降、陆源碎屑输入、成岩作用再活化及沉积后氧化作用等多因素有关.V/(V+Ni)、U/Th、V/Cr、Ni/Co、Re/Mo、Uau及δU比值表明早白垩世及晚白垩世中、晚期藏南地区盆地内底层水体环境总体上为中等分层的含氧环境,但定日一岗巴盆地内晚白垩世早期Cenomanian-Turonian界线附近微量元素发生突变,显示为强烈的还原环境.稀土元素球粒陨石标准化后均表现为轻稀土富集的右倾型,LREE/HREE介于7.42～14.80之间,LaN/YbN变化范围为7.93～18.54,δEu负异常,δCe异常不明显,表明为含氧环境.因此微量、稀土元素微观分析与野外宏观露头观察相结合,不但可以作为地层划分对比的直接依据,且能更准确、有效地判断地层沉积时底层水体的环境状况.     

海相沉积氧化还原环境的地球化学识别指标

全球海洋在10-5.4亿年间演变成氧化环境,此后历经多次全球性的缺氧事件后演变到现在的氧化环境.海水和沉积物中多种无素的循环、分异和富集明显受氧化还原条件的影响.Mn、Mo、Cr、V和U等变价元素的溶解度随氧化还原条件的改变产生极大变化,导致沉积物中的元素含量分异:Ni、Co、Cu和Zn等在还原条件下形成硫化物沉淀,导致沉积物中对应元素的富集.这些元素的地球化学行为是古海洋氧化还原条件的灵敏指示剂,作为恢复古海洋氧化还原条件环境变化的地球化学指标.黄铁矿化程度(DOP)、生物樗化合物和Ce异常等也是沉积物氧化还原条件的常用判别指标.泥岩石研究中通常采用DOP、U/Th、自生U、V/Cr、Ni/Co和生物标志化合物等指标,碳酸盐岩则主要采用Ce异常指标.当前各种指标的定性分析都取得比较一致的结果,但是用一种或几种定量的地球化学指标来恢复整个古海洋的氧化还原环境目前还有很大的问题.     

长江口外海域表层沉积物微量元素地球化学特征

对采自长江口外海域187个表层沉积物的25个微量元素含量进行了标准差系数、相关分析及R型因子分析,探讨了微量元素的来源和分布特征。长江口外海域沉积物微量元素Li、V、Cr、Co、Ni、Ga、Cu、Zn、Th和Rb分布基本相似;Sr分布与Li、Cu、Pb、Zn、Th和Rb相反;研究区东南部Sr分布与生物作用有明显关系;Cd和Mo分布与粒度之间的相关性较差,主要受氧化还原环境的控制;Zr分布反映了长江物源的影响。相关分析和R型因子分析结果表明,沉积作用、粒度控制效应、海洋生物作用、氧化还原环境和源区地质背景等对长江口外海域表层沉积物中微量元素分布起着主要控制作用。     

南大巴山上奥陶统五峰组—下志留统龙马溪组泥岩元素地球化学特征

元素地球化学在沉积环境判别中发挥重要的作用,尤其是沉积物形成时的氧化-还原环境和底层水体状况。本文对南大巴山上奥陶统五峰组-下志留统龙马溪组泥岩开展了元素地球化学分析,结果表明：临湘组Al₂O₃含量高于五峰组,五峰组-龙马溪组向上逐渐增加,TiO₂和Al₂O₃具有相似的特征,二者与TOC呈负相关;氧化-还原敏感元素U、V和Mo较为富集,表明沉积时处于缺氧环境,不同剖面不同层位存在两次强烈富集异常,指示其为硫化环境;稀土元素均表现为轻稀土富集、重稀土亏损,略微右倾的稀土元素配分模式,具有明显Eu负异常,其中五峰组-龙马溪组Ce负异常,缺氧环境,栗子坪少数Eu正异常,可能存在热液活动;氧化-还原敏感元素比值、Mo/TOC及Mo_EF-U_EF的协变模式揭示了南大巴山奥陶纪-志留纪之交主体上处于弱滞留贫氧-中等滞留缺氧的开阔海环境,主要受控于海平面升降变化和沉积时古海底地形,局部受北侧秦岭洋盆内洋流影响。     

Redox environment effect on redox sensitive elements in surface sediments of the Changjiang Estuary hypoxia zone

The grain size and element (including redox sensitive elements and terrigenous elements) concentration of surface sediments from the Changjiang Estuary hypoxia zone and its adjacent sea area were measured in this research. Based on the obtained data, the hypoxic environment’s influence on the distribution of elements in surface sediments was further studied. We believe that the “redox environment effect” greatly influences the distribution of the RSE, which reveals the “patchy enrichment pattern” offshore in the hypoxia zone, while the distribution of the terrigenous elements which shows the “stripped enrichment pattern” near shore is mainly affected by “granularity effects”. Due to the existence of the hypoxia zone of the Changjiang Estuary, the distribution of the RSE such as Mo, Cd and V in the study area exhibits the characteristics of “redox environment effects”. __________ Translated from Marine Geology & Quaternary Geology, 2007, 27(3):1–8 [译自: 海洋地质与第四纪地质]     

Relationships Between Long-Term Trend of Satellite-Derived Chlorophyll-<Emphasis Type="Italic">a</Emphasis> and Hypoxia Off the Changjiang Estuary

The Changjiang Estuary is one of the largest estuaries in the world, where hypoxia frequently occurs during the summer season. Recent routine surveys in the observed area found that the low dissolved oxygen (DO) in the summer bottom water was not rapidly expanding with increasing nutrient loads in Changjiang diluted waters. Based on the remote sensing data and in situ data, we examined the historic seasonal hypoxia observations for the bottom waters of the Changjiang Estuary and investigated the short- and long-term effects that runoff had on variations in DO and chlorophyll-a (Chl-a). Our analysis indicated that the recent areal variation in hypoxia was due to the changing Chl-a distribution and stratification conditions. The correspondence between hypoxia and surface Chl-a concentration showed that remotely sensed Chl-a larger than 3.0 mg L^?1 was an essential condition for the formation of hypoxia off the Changjiang Estuary. The trend of Chl-a concentration was significantly impacted by the Three Gorges Dam (TGD), and the inter-annual variation of Chl-a was weakly affected by global-scale climate variability. After the TGD impoundment, the sediment loading in the Changjiang runoff and suspended sediments in Changjiang Estuary in August decreased, and the high Chl-a concentration moved landward. These shifted the hypoxia from its optimal forming conditions.     

长江口氧化还原敏感元素的早期成岩过程

通过测试长江口沉积物及间隙水中Fe、Mn、U及Mo的含量,结合早期成岩模型及地球化学热力学分析,探讨了在河口环境中影响间隙水氧化还原敏感元素(Fe、Mn、U及Mo)分布的主要因素.根据Fick第一定律,估算了Fe、Mn、U及Mo在沉积物-水界面的扩散通量.结果表明,间隙水Fe、Mn、U及Mo的含量分别介于0.8~106μmol/L、14.8~258μmol/L、1.9~14.4nmol/L及60~546nmol/L之间.在垂直剖面上,间隙水Fe、Mn峰值分别出现在约5cm或10cm的深度.早期成岩过程是影响长江口沉积物间隙水Fe、Mn分布的主要因素.吸附系数对间隙水Fe、Mn的分布也有重要的影响.吸附系数越高,间隙水Fe、Mn浓度越低.影响间隙水U分布的主要因素为Fe,而Mo与Fe、Mn之间不存在相关性.通量计算结果显示Fe、Mn、U及Mo的扩散通量分别介于3.0~10.5μmol·(m2·d)-1、35.7~439.5μmol·(m2·d)-1、-2.3~0.2nmol·(m2·d)-1及-36.0~94.6nmol·(m2·d)-1之间.沉积物中自生铀组分约占总铀的6%~67%.      

Research Advances in Sedimentary Records of Coastal Bottom-water Hypoxia

Sedimentary records are potential to provide long-term evidence for better understanding the development mechanism of coastal hypoxia, shedding some light on the forecast, prediction and controlling-measure development to mitigate hypoxia. Therefore, recent research advances in the formation mechanism and evolution history of coastal hypoxia were briefly reviewed, specially with focus on sedimentary records and proxy methods. First, marine environments with hypoxia were classified into semi-enclosed marginal sea/gulf and open shelf sea based on the degree of bottom-water circulation and ventilation, and main characteristics for the hypoxic development were discussed respectively. Secondly, the methodology was reviewed in the efficiency by using different proxies to reconstruct hypoxia development history from sediment cores, including redox indicators of sedimentology, biology, mineralogy and geochemistry. Ultimately, recent research advance in hypoxic development mechanism and evolution history off the Changjiang Estuary were summarized. It is worth noting that long-term evolution history has been less studied from long cores. It is therefore suggested that a synthetic methodology involving multi-core comparison with different-proxy interpretation should be employed to study the development history of seasonal hypoxia off the Changjiang Estuary.     

Heavy metal distribution in the surface layer of bottom sediments of the Kara Sea

This paper addresses the distribution of heavy metals (Co, Ni, Cu, Zn, Cd, Sn, Sb, Pb, and Bi) as well as Si, Al, Fe, and Mn in the surface (0–2 cm) layer of bottom sediments of the Kara Sea. The contents of these elements are determined in each of the previously distinguished facies-genetic types of terrigenous sediments: fluvial, glacial, estuarine, shallow water–marine, “background” marine, and relict sediments. It is shown that these types reflect the modern conditions of accumulation of river discharge material, which forms fans of two greatest Siberian rivers, Ob and Yenisei. The main stages are distinguished in heavy metal accumulation. The first stage is related to the avalanche sedimentation of terrigenous sediments in the estuary and characterized by the elevated contents of Co, Ni, Cu, Zn, Cd, Sb, and Bi. The second stage reflects the mechanical differentiation of sedimentary material by waves and bottom currents in a shallow-water sea part adjacent to the estuarine zone, with accumulation of Pb- and Sn-bearing “heavy” ore minerals. The deepwater background terrigenous–marine sediments accumulate mainly Ni, Zn, and Cd, as well as Mn. The relict sediments differ in the high contents of Si, Mn, and Sn.     

塔里木盆地北部下寒武统底部黑色页岩形成的次氧化条件

富有机质黑色页岩的形成长期以来被认为是缺氧沉积环境的证据,并被作为全球缺氧事件的标志。塔里木盆地下寒武统底部黑色页岩的岩石学特征说明其沉积在受陆源有一定影响的陆棚环境中。矿物学研究表明,硫均以硫酸盐状态存在,没有见到黄铁矿,说明其形成在硫酸盐还原带以上。黑色页岩中结核状氟磷灰石的存在以及剖面底部结核状磷块岩的出现,表明了一种与现代热带太平洋东海岸和阿拉伯海相类似的广泛发育上升洋流的大陆边缘沉积环境。黑色页岩的地球化学特征中,Re和Mo的高度富集、高的Re/Mo比以及含有一定量的Mn,Cd和U的相对富集以及低的Cd/U比等,这些特点均支持了黑色页岩沉积于次氧化条件的认识。     

Suboxic trace metal geochemistry in the Eastern Tropical North Pacific

We analyzed Al, Ti, Fe, Mn, Cu, Ba, Cd, U, Mo, V, and Re in water column, settling particulate, and sediment (0 to 22 cm) samples from the intense oxygen minimum zone (OMZ) of the eastern tropical North Pacific near Mazatlán, Mexico. The goal was to determine how the geochemistry of these elements was influenced by suboxic water column conditions and whether the sediments have a unique “suboxic” geochemical signature.The water column was characterized by a Mn maximum, reaching ∼8 nmol kg⁻¹ at 400 m. Concentrations of Cu, Ba, Cd, Mo, Re, U, and V were unaffected by the low O₂ conditions and were comparable to those of the open ocean. Sinking particles were composed of lithogenic particles of detrital origin and nonlithogenic particles of biogenic origin. Al, Ti, and Fe were mostly (at least 79%) lithogenic. About 75% of the Mn was nonlithogenic. Significant amounts (at least 58%) of Cu, Ba, Cd, and Mo were nonlithogenic.Sediment geochemistry varied across the continental shelf and slope. Cadmium, U, and Re have prominent maxima centered at 310 m, with 12.3 ppm, 10.9 ppm, and 68.3 ppb, respectively, at the core top. High values of Mo (averaging 6.8 ppm) and V (averaging 90 ppm) are seen in OMZ surface sediment. Additional down-core enrichment occurs for all redox-sensitive elements in the top 10 cm. For U, Mo, V, and Re, surface sediments are a poor indicator of metal enrichment. Comparison of the nonlithogenic composition of sediments with sinking particles suggests that direct input of plankton material enriched in metals makes a significant contribution to the total composition, especially for Cd, U, and Mo.We evaluated Re/Mo and Cd/U ratios as tracers for redox environments. Rhenium and Mo concentrations and Re/Mo ratios do not lead to consistent conclusions. Concurrent enrichments of Re and Mo are an indicator of an anoxic depositional environment. In contrast, high Re/Mo ratios are an indicator of suboxic conditions. Cadmium is enriched in surface sediments, while U has considerable down-core enrichment. The concentrations of Cd and U and the Cd/U ratio do not follow patterns predicted from thermodynamics. Though the water column is suboxic, these four redox-sensitive elements indicate that the sediments are anoxic. The implication for paleostudies is that a trace metal sediment signature that indicates anoxic conditions is not necessarily attributable to an anoxic water column.     

Reconstruction of nearshore chemical conditions in the Mesoproterozoic: evidence from red and grey beds of the Yangzhuang formation,North China Craton

ABSTRACT

Mesoproterozoic red beds near ancient coasts have not aroused extensive interest. A new geochemical study of the alternating red and grey dolostones from the Yangzhuang Formation provides a better understanding of the redox conditions of nearshore sedimentary environments. In this contribution, whole-rock samples are characterized by positive correlations of rare earth elements (REE) vs. Th and Fe_T vs. Th and flat-type REE distribution patterns, indicating massive terrigenous input, which is considered to be inherited from felsic rocks. Relatively high (Fe_mag+Fe_ox)/Fe_T and Fe³⁺/Fe²⁺ ratios in red beds indicate more oxidized conditions in supratidal environments compared with the lower oxygen contents in intertidal environments. Under these two distinct chemical sedimentary conditions, acetic acid-leached red and grey samples both have HREE-depleted distributions, suggesting significant freshwater invasion. Moreover, limited terrigenous redox-sensitive elements (RSEs) can reach the coast where the red beds are deposited, whereas relatively high RSE enrichment factors originating from shallow oceans are recorded in grey beds. In the Mesoproterozoic, limited oxidative weathering, shallow seawater desalination, and low organic production occurred near the coast. Meanwhile, a prolonged period of low Mo and U availability preserved in carbonate minerals confirmed that marine oxygen levels failed to satisfy the deposition of offshore red beds. During the regression, potentially exposed sediments connected to atmospheric oxygen guaranteed the oxidation of iron and the formation of red beds, and these events were coupled with negative δ¹³C_carb shifts in the Yanliao rift zone.     

The geochemistry of redox sensitive trace metals in sediments

We analyzed the redox sensitive elements V, Mo, U, Re and Cd in surface sediments from the Northwest African margin, the U.S. Northwest margin and the Arabian Sea to determine their response under a range of redox conditions. Where oxygen penetrates 1 cm or less into the sediments, Mo and V diffuse to the overlying water as Mn is reduced and remobilized. Authigenic enrichments of U, Re and Cd are evident under these redox conditions. With the onset of sulfate reduction, all of the metals accumulate authigenically with Re being by far the most enriched. General trends in authigenic metal accumulation are described by calculating authigenic fluxes for the 3 main redox regimes: oxic, reducing where oxygen penetrates ≤1 cm, and anoxic conditions. Using a simple diagenesis model and global estimates of organic carbon rain rate and bottom water oxygen concentrations, we calculate the area of sediments below 1000 m water depth in which oxygen penetration is ≤1 cm to be 4% of the ocean floor. We conclude that sediments where oxygen penetrates ≤1 cm release Mn, V and Mo to seawater at rates of 140%–260%, 60%–150% and 5%–10% of their respective riverine fluxes, using the authigenic metal concentrations and accumulation rates from this work and other literature. These sediments are sinks for Re, Cd and U, with burial fluxes of 70%–140%, 30%–80% and 20%–40%, respectively, of their dissolved riverine inputs. We modeled the sensitivity of the response of seawater Re, Cd and V concentrations to changes in the area of reducing sediments where oxygen penetrates ≤1 cm. Our analysis suggests a negligible change in seawater Re concentration, whereas seawater concentrations of Cd and V could have decreased and increased, respectively, by 5%–10% over 20 kyr if the area of reducing sediments increased by a factor of 2 and by 10%–20% if the area increased by a factor of 3. The concentration variations for a factor of 2 increase in the area of reducing sediments are at about the level of uncertainty of Cd/Ca and V/Ca ratios observed in foraminifera shells over the last 40 kyr. This implies that the area of reducing sediments in the ocean deeper than 1000 m (4%) has not been greater than twice the present value in the recent past.