火山活动与海侵影响下的典型湖相页岩有机质保存差异分析

黑色富有机质页岩是页岩油气生成和赋存的主要母体,是强还原环境水体的沉积产物,在其形成过程中,细菌硫酸盐还原作用(BSR)对水体环境影响明显,但BSR强度如何影响有机质的保存尚未得到关注。我国陆相湖盆富有机质泥页岩广泛发育,形成过程中常常伴随有火山活动或者海侵等事件,大量硫酸盐进入湖盆,改变水体的沉积环境,不同环境下BSR对黑色页岩有机质保存的影响明显不同。本次研究选取鄂尔多斯盆地延长组长7段页岩、松辽盆地青山口组和嫩江组页岩作为对象,同时与现代沉积物进行对比。研究表明,TOC与TS之间关系复杂,但细菌硫酸盐还原强度指数(SRI)与TOC呈现幂指数变化,且表现出两阶段变化的特征。当SRI大于1.375时,TOC整体偏低,指示了强硫酸盐还原作用消耗大量有机质;当SRI小于1.375时,TOC明显较高,指示了弱硫酸盐还原作用对有机质消耗相对较少,更有利于有机质保存。火山活动和海侵作用均向水体提供了大量硫酸盐,但对陆相湖盆页岩中有机质的保存影响不同。火山活动影响的长7段页岩SRI普遍小于1.375,BSR对有机质消耗相对弱,页岩TOC高。而受海侵影响的青山口组一段底部和嫩江组一段底部页岩SRI大于1.375,BSR过度消耗了大量有机质,使得页岩TOC偏低。嫩江组一段下部SRI指数更高,海侵强度更大,BSR反应更强,更不利于有机质保存。     

广东三水盆地古近系(土布)心组地球化学特征及其所指示的氧化还原条件

古近系心组红岗段是广东三水盆地的主要生油层,以一套黑—灰黑色页岩沉积为主,其富含有机质、纹层理发育良好的岩层与相对贫有机质、含微体生物化石的微扰动层交替出现。根据纹层状页岩与生物扰动页岩的C-S-Fe关系以及对氧化还原条件敏感的痕量元素(Mo、U、V、Co、Ni、Pb和Cu)地球化学记录,对这两种不同岩相的地球化学特征及其所反映的水体氧化还原条件进行了分析。纹层状页岩的TOC、S含量和DOPT值均较高,TOC-S、TOC-DOPT显示较弱的相关性;而生物扰动页岩的TOC、S含量和DOPT值相对较低,TOC-S、TOC-DOPT相关性显著。痕量元素在两种岩相中的分布也有差别,各元素在纹层状页岩中的丰度均高于生物扰动页岩,尤其是Mo和U具有较高的丰度水平、且在不同岩相中显示明显差别。黑色页岩中的C-S-Fe关系和痕量元素(特别是Mo和U)分布反映了心组红岗段沉积时期湖盆水体的氧化还原条件变化。生物扰动页岩沉积期间,底部水体主要为氧化环境,间歇性出现贫氧条件,硫酸盐还原作用发生于沉积物/水界面及其以下沉积物中。纹层状页岩形成于缺氧的底部水体条件下,水体和沉积物中均可含H2S,为有机质保存以及对氧化还原条件敏感的痕量元素的富集提供了有利条件。     

四川盆地东北部三叠系飞仙关组硫酸盐还原作用对碳酸盐成岩作用的影响

四川盆地东北部三叠系飞仙关组存在广泛的硫酸盐还原作用,同时地层中也存在锶含量异常高的成岩流体。研究表明:热化学硫酸盐还原作用（TSR）和（或）细菌硫酸盐还原作用（BSR）造成的SO42-离子的消耗对成岩孔隙流体中SrSO4溶解度的改变是三叠系中高Sr成岩流体的形成机制之一,该机制使得孔隙流体从白云石化作用和碳酸盐矿物的新生变形作用中获得的Sr在流体中以高浓度的Sr2+形式存在,并使之在流体中极度富集,这也是四川盆地东北部三叠系中大型和超大型天青石矿床的形成机制之一。H2S和CO2是硫酸盐还原作用的重要产物,不同温度条件下溶于水中的H2S和CO2,与不溶于水的气体分子之间的平衡反应H2S（aq）H2S(g)和CO2(aq)CO2(g)的平衡常数和吉布斯自由能增量计算表明,当温度从25℃升高至220℃时,两个反应的平衡常数分别大致从10增至240和从20增至500,两个反应的平衡常数都始终大于1,说明H2S和CO2更趋向于以气体形式存在,同时温度越高,系统中以气体形式存在的H2S和CO2会越多,溶解于水中的H2S和CO2会越少,因而在深埋藏的高温条件下,H2S和CO2对碳酸盐矿物的溶解能力可能相对很小。相对低温的成岩环境、高温流体的向上和侧向运移、构造抬升、富氧流体与含有H2S流体的混合以及金属硫化物的沉淀是提高含H2S和（或）CO2流体对碳酸盐矿物溶解能力的五个途径。因此,与较早成岩阶段相对浅埋藏环境的碳酸盐溶解作用有关的H2S和CO2流体可能与细菌硫酸盐还原作用（BSR）关系更为密切;断层或其它流体运移通道是高温含有H2S和CO2流体向上运移的基础条件,具有原生孔隙度和渗透率的礁、滩相高能沉积物也是流体发生侧向运移的先决条件;大幅度的构造抬升造成的地层温度降低是提高含H2S和（或）CO2地层流体对碳酸盐矿物溶解能力的重要因素,地壳抬升至近地表造成的古喀斯特作用也可以为H2S的氧化提供良好的地质环境。在有关的勘探中应注意:在断层等流体运移通道造成高温含H2S和CO2流体向上运移的条件下,与之有关的构造低点应该是主要的勘探目标;在燕山运动导致的地层抬升并导致深部热流体降温的条件下,与之有关的构造高点应该是主要的勘探目标,应分别对待。     

沉积盆地热化学硫酸盐还原作用评述

川东天然气藏H2S 气体泄露而导致重大伤亡事故后,热化学硫酸盐还原作用（TSR）成为了国内研究的热点。在油气储层条件下,尽管甲烷是最稳定的烃类,但TSR被诱发后,因为甲烷浓度远高于其它烃类,水溶甲烷能与硫酸根离子反应产生H2S 气体。同时,发现在参与TSR反应的有机质、起始温度、硫同位素分馏效应等方面,实验模拟结果均与地质实例观察结果有较大的差异,可能与TSR反应的催化剂等方面认识不足有关。并认为,TSR成因的H2S或元素硫可以在晚成岩期合并入有机质中,形成新的有机含硫化合物。但在自然界中,这类化合物很少被鉴别出来。     

黔北镇远牛蹄塘组黑色页岩沉积环境与有机质富集关系

通过矿物组分、主量元素、微量元素、碳氧同位素等特征,分析了黔北地区镇远县ZX井牛蹄塘组黑色页岩的岩相类型和不同岩相页岩的沉积环境及其与有机质富集间的关系。结果表明,牛蹄塘组下段以硅质页岩为主,TOC含量4. 96%~10. 10%;上段以富泥硅质页岩为主,TOC含量1. 43%~9. 04%。下段硅质页岩沉积于水流停滞的深水陆棚环境,沉积古水体为贫氧的还原状态;上段富泥硅质页岩沉积时期,仍为贫氧的还原环境,但水体滞留程度、还原性较下段硅质页岩沉积期弱。贫氧的还原环境是影响牛蹄塘组黑色页岩有机质富集的主要因素,热液作用和陆源碎屑对牛蹄塘组黑色页岩有机质富集的影响较小。     

晚三叠世龙门山前陆盆地须家河组泥页岩沉积环境及有机质富集模式

晚三叠世龙门山前陆盆地形成早期的沉积环境长期存在争议。本文通过对须家河组中泥页岩的元素地球化学分析,并结合古生物、矿物组成和沉积特征对须家河组的沉积环境进行分析,探讨有机质富集模式。研究表明,龙门山前陆盆地须家河组沉积时期属于温暖潮湿的热带—亚热带气候。其中,须一段为海相沉积,泥页岩主要形成于还原环境,可见少量黄铁矿,有机质富集受氧化还原条件控制。须二段—须五段的地球化学特征、古生物特征和泥页岩有机质特征上具有相似性,与须一段的海相沉积有明显差别,在与里海进行分析对比后认为,从须二段开始,须家河组逐渐转为陆相沉积。研究表明,须二段—须五段为半咸水—淡水沉积,泥页岩中黄铁矿消失,菱铁矿出现,结合V/Cr、U/Th和dU等地化指标反映,泥页岩应沉积于弱氧化的水体。须二段—须五段泥页岩TOC含量与古生产力和沉积速率相关性好,有机质富集受古生产力和沉积速率共同控制。前陆盆地持续沉降的构造背景下形成的泥页岩具有较快的沉积速率,使得有机质在弱氧化条件下也能得到较好的保存,在沉积速率大于10 cm/kyr,古生产力充足的条件下,有机质富集和保存不再受氧化还原条件控制。     

烃源岩中C19~C29甾烷系列和25 降藿烷系列的检出及其地质意义

沉积有机质中通常可检测到C21（孕甾烷）、C22（升孕甾烷）和C27~C29甾烷,但C19、C20和C23~C26甾烷并不常见。在三塘湖盆地芦草沟组黑色页岩中检出了完整的C19~C29甾烷系列和25 降藿烷系列。如此完整且丰度较高的此类化合物,尚无文献报道。这一新的资料可能蕴含着丰富的油气地球化学信息。初步认为这2个系列的化合物指示:其古环境为干旱和咸化水体环境;有机质以藻类和浮游生物等低等水生生物来源为主,在沉积初期遭受强烈的生物降解作用;原始有机质与细菌降解的产物共存,成为生烃先质。     

上扬子地区龙马溪组黑色富有机质页岩的浅水超覆沉积模式

细粒沉积作用决定着页岩储集层的物质基础，对优质页岩的形成具有重要作用。文中以上扬子地区龙马溪组黑色页岩为研究对象，通过岩心、露头、薄片、地震资料等分析，对该套黑色页岩的沉积发育模式进行研究。结果表明：(1)研究区龙马溪组黑色富有机质页岩段发育粉砂岩与页岩互层，见生物扰动、交错纹层、波状纹层、粒序纹层、泥砾定向排列、底部侵蚀面等沉积构造，具明显的浅水沉积特征；(2)黑色页岩内部发育多期受波浪作用影响而形成的页岩—粉砂质页岩—粉砂岩反粒序沉积旋回，显示出波浪作用对龙马溪组黑色页岩的形成具有重要影响；(3)风暴作用对于龙马溪组黑色页岩的形成具有一定的影响，表现为在不规则侵蚀面之上形成粉砂岩—黑色页岩正粒序沉积旋回；(4)从地震剖面以及连井剖面对比可以看出，随着海平面的不断上升，页岩总体上具有向古隆起边缘不断超覆迁移的特征。推测上扬子地区龙马溪组黑色页岩形成于水体较浅且受限的沉积环境，易受波浪以及风暴作用的影响，具有随着海平面上升而不断超覆迁移的特征。研究区龙马溪组富有机质黑色页岩的浅水超覆模式对于上扬子地区富有机质页岩的勘探具有重要的指导意义。     

浙江西部建德群锆石LA ICP MS之U Pb同位素年龄及其地层学意义

为进一步认识华南埃迪卡拉纪(震旦纪)海水硫化条件的演变过程,本文对斜坡相沉积的陡山沱组中的黄铁矿进行形态与粒度分布研究。结果表明陡山沱期沉积的多数黄铁矿是早期成岩作用形成,以自形、半自形晶体为主;个别层位中草莓状黄铁矿粒径大于10μm的比例较高（89%~96%）,反映是在海水、沉积物界面以下生长的,不能充分指示水体硫化状态。但在陡山沱组中部和上部发育有数层从水体中析出的同沉积草莓状黄铁矿（96%以上的莓球粒径小于10μm）,反映出海水硫化条件发育。黄铁矿铁与高活性铁的比值（FePY/FeHR）作为判别海洋硫化状态的重要指标,可能会因次生黄铁矿的叠加效应影响而产生偏差,应结合黄铁矿矿物形态—粒度分析和其他手段加以校正。通过这2种方法并结合碳、硫同位素等研究表明,陡山沱组沉积旋回Ⅰ顶部和旋回Ⅲ底部沉积期间华南古海洋曾经历了两幕规模较大的间歇性硫化时期,在此期间硫化水体的覆盖范围至少包括陆架至斜坡中部相区。硫化水体的形成和时空演变主要受大气含氧量、海水硫酸盐浓度、细菌硫酸盐活动（BSR）及海平面变化等因素控制。重要的生物类群主要出现在非硫化间隔期,表明海水硫化条件是限制生物发展的重要环境因素之一。     

鄂尔多斯盆地长7段细粒沉积岩特征与古环境——以铜川地区瑶页1井为例

三叠系延长组长7段是鄂尔多斯盆地中生界重要的烃源岩层系。为探究长7段细粒沉积岩发育特征、沉积环境及有机质富集控制因素,以盆地南缘瑶页1井为例,运用X射线衍射、偏光显微镜、扫描电镜、XRF成像等方法,对长7段细粒沉积岩沉积特征及其纵向演化规律开展系统分析。研究表明,长7段主要发育三种细粒沉积岩类型:块状泥岩、水平纹层状页岩和透镜纹层状页岩。其中块状泥岩主要位于长7段的上部和下部,发育块状构造,石英长石含量较高,黄铁矿多以八面体自形晶产出,判断块状泥岩是高能环境中的产物,水体富氧,不利于有机质的生成和保存,有机质丰度较低。透镜纹层状页岩主要发育于长7段的中部,黄铁矿异常丰富,含有大量火山灰组分;草莓状黄铁矿粒度分布指示水体缺氧但具有一定波动;在较好保存环境和火山营养物质注入的双重作用下,透镜纹层状页岩的平均有机质丰度最高。水平纹层状页岩则多位于长7段中上部,以"有机质+黏土"或"有机质+黏土+火山灰"的结构产出,黄铁矿粒度分析指示沉积环境安静,水体缺氧,有利于有机质保存,有机质丰度介于块状泥岩和透镜纹层状页岩之间。瑶页1井长7段有机质丰度与黄铁矿含量的高相关性指示铜川地区长7期水体可能具有较高的硫酸盐浓度,硫酸盐的来源可能与湖底热液、海侵、火山喷发等事件相关。     

Sulfur speciation in the upper Black Sea sediments

We report solid phase sulfur speciation of six cores from sediments underlying oxic, suboxic and anoxic-sulfidic waters of the Black Sea. Our dataset includes the five sulfur species [pyrite-sulfur, acid volatile sulfides (AVS), zerovalent sulfur (S(0)), organic polysulfides (RS_x), humic sulfur] together with reactive iron and manganese, as quantified by dithionite extraction, and total organic carbon. Pyrite – sulfur was the major phase in all cores [200-400 µmol (g dry wt)^- 1] except for the suboxic core. However, zerovalent sulfur and humic sulfur also reached very significant levels: up to about 109 and 80 µmol (g dry wt)^- 1, respectively. Humic sulfur enrichment was observed in the surface fluff layers of the eastern central basin sediments where Unit-1 type depositional conditions prevail. Elemental sulfur accumulated as a result of porewater sulfide oxidation by reactive iron oxides in turbidities from the anoxic basin margin and western central basin sediments. The accumulation of elemental sulfur to a level close to that of pyrite-S in any part of central Black Sea sediments has never been reported before and our finding indicates deep basin turbidites prevent the build-up of dissolved sulfide in the sediment. This process also contributes to diagenetic pyrite formation whereas in the non-turbiditic parts of the deep basin water column formed (syngenetic) pyrite dominates the sulfur inventory. In slope sediments under suboxic waters, organic sulfur (humic sulfur + organic polysulfides) account for 33-42% of total solid phase S, indicating that the suboxic conditions favor organosulfur formation. Our study shows that the interactions between depositional patterns (Unit 1 vs. turbidite), redox state of overlying waters (oxic-suboxic-sulfidic) and organic matter content determine sulfur speciation and enable the accumulation of elemental sulfur and organic sulfur species close to a level of pyrite-S.     

Zur Systematik der Kohlenstoff-Schwefel-Eisen-Verhältnisse in Auftriebssedimenten

Abundances of organic carbon, sulfur, and reactive iron in sediments of three upwelling environments (Peru, Oman and Benguela) suggest that organic carbon/reduced sulfur ratios (C/S-ratios) in this category of marine sediments deviate considerably from previously established empirical ratios in normal marine sediments. To clarify the discrepancies, we investigated those components of the diagenetic system that limit the formation of pyrite: sulfate concentrations and reduction rates in pore waters, availability of reactive iron, and the quantity and quality of organic matter. All three limitations are evident in our sample pools. The results suggest that C/S-ratios in recent and fossil marine sediments rich in organic matter may be unsuitable as paleoenvironmental indicators.

     

A quantitative reconstruction of organic matter and nutrient diagenesis in Mediterranean Sea sediments over the Holocene

A multicomponent diagenetic model was developed and applied to reconstruct the conditions under which the most recent sapropel, S1, was deposited in the eastern Mediterranean Sea. Simulations demonstrate that bottom waters must have been anoxic and sulphidic during the formation of S1 and that organic matter deposition was approximately three times higher than at present. Nevertheless, most present day sediment and pore water profiles — with the exception of pyrite, iron oxyhydroxides, iron-bound phosphorus and phosphate — can be reproduced under a wide range of redox conditions during formation of S1 by varying the depositional flux of organic carbon. As a result, paleoredox indicators (e.g., C_org:S ratio, C_org:P_org ratio, trace metals) are needed when assessing the contribution of oxygen-depletion and enhanced primary production to the formation of organic-rich layers in the geological record. Furthermore, simulations show that the organic carbon concentration in sediments is a direct proxy for export production under anoxic bottom waters.The model is also used to examine the post-depositional alteration of the organic-rich layer focussing on nitrogen, phosphorus, and organic carbon dynamics. After sapropel formation, remineralisation is dominated by aerobic respiration at a rate that is inversely proportional to the time since bottom waters became oxic once again. A sensitivity analysis was undertaken to identify the most pertinent parameters in regulating the oxidation of sapropels, demonstrating that variations in sedimentation rate, depositional flux of organic carbon during sapropel formation, bottom water oxygen concentration, and porosity have the largest impact. Simulations reveal that sedimentary nutrient cycling was markedly different during the formation of S1, as well as after reoxygenation of bottom waters. Accumulation of organic nitrogen in sediments doubled during sapropel deposition, representing a significant nitrogen sink. Following reventilation of deep waters, N₂ production by denitrification was almost 12 times greater than present day values. Phosphorus cycling also exhibits a strong redox sensitivity. The benthic efflux of phosphate was up to 3.5 times higher during the formation of S1 than at present due to elevated depositional fluxes of organic matter coupled with enhanced remineralisation of organic phosphorus. Reoxygenation of bottom waters leads to a large phosphate pulse to the water column that declines rapidly with time due to rapid oxidation of organic material. The oxidation of pyrite at the redox front forms iron oxyhydroxides that bind phosphorus and, thus, attenuate the benthic phosphate efflux. These results underscore the contrasting effects of oxygen-depletion on sedimentary nitrogen and phosphorus cycling. The simulations also confirm that the current conceptual paradigm of sapropel formation and oxidation is valid and quantitatively coherent.     

An interpretation of carbon and sulfur relationships in Black Sea sediments as indicators of environments of deposition

Syngenetic iron sulfides in sediments are formed from dissolved sulfide resulting from sulfate reduction and catabolism of organic matter by anaerobic bacteria. It has been shown that in recent marine sediments deposited below oxygenated waters there is a constant relationship between reduced sulfur and organic carbon which is generally independent of the environment of deposition. Reexamination of data from recent sediments from euxinic marine environments (e.g., the Black Sea) also shows a linear relationship between carbon and sulfur, but the slope is variable and the line intercepts the S axis at a value between 1 and 2 percent S. It is proposed that the positive S intercept is due to watercolumn microbial reduction of sulfate using metabolizable small organic molecules and the sulfide formed is precipitated and accumulates at the sediment-water interface. The variation in slope and intercept of the C to S plots for several cores and for different stratigraphic zones for the Black Sea can be interpreted in relation to thickness of the aqueous sulfide layer or thinness of the oxygen containing layer and to deposition rate, but also may be influenced by availability of iron, and perhaps the type of organic matter (Leventhal, 1979).     

Hydrogen sulfide and organic carbon at the sediment–water interface in coastal brackish Lake Nakaumi, SW Japan

The relationship among H₂S, total organic carbon (TOC), total sulfur (TS) and total nitrogen contents of surface sediments (0–1 cm) was examined to quantify the relationship between H₂S concentrations and TOC content at the sediment water interface in a coastal brackish lake, Nakaumi, southwest Japan. In this lake, bottom water becomes anoxic during summer due to a strong halocline. Lake water has ample dissolved SO₄ ^2? and the surface sediments are rich in planktic organic matter (C/N 7–9), which is highly reactive in terms of sulfate reduction. In this setting the amount of TOC should be a critical factor regulating the activity of sulfate reduction and H₂S production. In portions of the lake where sediment TOC content is less than 3.5 %, H₂S was very low or absent in both bottom and pore waters. However, in areas with TOC >3.5 %, H₂S was correlated with TOC content (pore water H₂S (ppm) = 13.9 × TOC (%) ? 52.1, correlation coefficient: 0.72). H₂S was also present in areas with sediment TS above 1.2 % (present as iron sulfide), which suggests that iron sulfide formation is tied to the amount of TOC. Based on this relationship, H₂S production has progressively increased after the initiation of land reclamation projects in Lake Nakaumi, as the area of sapropel sediments has significantly increased. This TOC–H₂S relationship at sediment–water interface might be used to infer H₂S production in brackish–lagoonal systems similar to Lake Nakaumi, with readily available SO₄ ^2? and reactive organic matter.     

Stable Sulfur Isotopic Evidence for Historical Changes of Sulfur Cycling in Estuarine Sediments from Northern Florida

Data on abundance and isotopic composition of porewater and sedimentary sulfur species are reported for relatively uncontaminated and highly contaminated fine-grained anoxic sediments of St. Andrew Bay, Florida. A strong contrast in amount and composition of sedimentary organic matter at the two sites allows a comparative study of the historical effects of increased organic loading on sulfur cycling and sulfur isotopic fractionation. In the contaminated sediments, an increase in organic loading caused increased sedimentary carbon/sulfur ratios and resulted in higher rates of bacterial sulfate reduction, but a lower efficiency of sulfide oxidation. These differences are well reflected in the isotopic composition of dissolved sulfate, sulfide, and sedimentary pyrite. Concentration and isotopic profiles of dissolved sulfate, organic carbon, and total sulfur suggest that the anaerobic decomposition of organic matter is most active in the upper 8cm but proceeds at very slow rates below this depth. The rapid formation of more than 90% of pyrite in the uppermost 2 cm which corresponds to about 3 years of sediment deposition allows the use of pyrite isotopic composition for tracing changing diagenetic conditions. Sediment profiles of the sulfur isotopic composition of pyrite reflect present-day higher rates of bacterial sulfate reduction and lower rates of sulfide oxidation, and record a profound change in the diagenetic cycling of sulfur in the contaminated sediments coincident with urban and industrial development of the St. Andrew Bay area.     

Geochemistry of Peruvian near-surface sediments

Sixteen short sediment cores were recovered from the upper edge (UEO), within (WO) and below (BO) the oxygen minimum zone (OMZ) off Peru during cruise 147 of R/V Sonne. Solids were analyzed for major/trace elements, total organic carbon, total inorganic carbon, total sulfur, the stable sulfur isotope composition (δ³⁴S) of pyrite, and sulfate reduction rates (SRR). Pore waters were analyzed for dissolved sulfate/sulfide and δ³⁴S of sulfate. In all cores highest SRR were observed in the top 5 cm where pore water sulfate concentrations varied little due to resupply of sulfate by sulfide oxidation and/or diffusion of sulfate from bottom water. δ³⁴S of dissolved sulfate showed only minor downcore increases. Strong ³²S enrichments in sedimentary pyrite (to −48‰ vs. V-CDT) are due to processes in the oxidative part of the sulfur cycle in addition to sulfate reduction. Manganese and Co are significantly depleted in Peruvian upwelling sediments most likely due to mobilization from particles settling through the OMZ, whereas release of both elements from reducing sediments only seems to occur in near-coastal sites. Cadmium, Mo and Re are exceptionally enriched in WO sediments (<600 m water depth). High Re and moderate Cd and Mo enrichments are seen in BO sediments (>600 m water depth). Re/Mo ratios indicate anoxic and suboxic conditions for WO and BO sediments, respectively. Cadmium and Mo downcore profiles suggest considerable contribution to UEO/WO sediments by a biodetrital phase, whereas Re presumably accumulates via diffusion across the sediment-water interface to precipitation depth. Uranium is distinctly enriched in WO sediments (due to sulfidic conditions) and in some BO sediments (due to phosphorites). Silver transfer to suboxic BO sediments is likely governed by diatomaceous matter input, whereas in anoxic WO sediments Ag is presumably trapped due to sulfide precipitation. Cadmium, Cu, Zn, Ni, Cr, Ag, and T1 predominantly accumulate via biogenic pre-concentration in plankton remains. Rhenium, Sb, As, V, U and Mo are enriched in accordance with seawater TE availability. Lead and Bi enrichment in UEO surface sediments is likely contributed by anthropogenic activity (mining). Accumulation rates of TOC, Cd, Mo, U, and V from Peruvian and Namibian sediments exceed those from the Oman Margin and Gulf of California due to enhanced preservation off Peru and Namibia.     

Biogeochemical processes of carbon and sulfur cycles in sediments of the outer shelf of the Black Sea (Russian Sector)

Within the mass of recent (unit-I) and ancient Black Sea (unit-II) sediments on the outer shelf of the Russian sector of the Black Sea, the rates of anoxic processes participating in diagenetic transformations of carbon and sulfur compounds were first measured using ³⁵S and ¹⁴C radioactive tracers. The main energy source for biogeochemical processes in (unit-I) sediments is the organic matter (OM) supplied to the bottom from the water mass. In (unit-II) sediments, this is methane in a migratory form proved by the excess of its oxidation rate over that of its generation. In recent silt, the primary microbial process is sulfate reduction; in unit-II, this is methane anoxic oxidation by the consortium of archeides and sulfate reductants. The organic matter produced in methane oxidation, in turn, acts as an energy source for the community of anaerobic heterotrophic microorganisms in the bottom sediments, which are remote from the water-sediment interface.     

Pyrite geochemistry in the Toarcian Posidonia Shale of south‐west Germany: Evidence for contrasting trace‐element patterns of diagenetic and syngenetic pyrites

Authigenic pyrite grains from a section of the Lower Toarcian Posidonia Shale were analysed for their trace‐element contents and sulphur‐isotope compositions. The resulting data are used to evaluate the relationship between depositional conditions and pyrite trace‐element composition. By using factor analysis, trace‐elements in pyrite may be assigned to four groups: (i) heavy metals (including Cu, Ni, Co, Pb, Bi and Tl); (ii) oxyanionic elements (As, Mo and Sb); (iii) elements partitioned in sub‐microscopic sphalerite inclusions (Zn and Cd); and (iv) elements related to organic or silicate impurities (Ga and V). Results indicate that trace‐element contents in pyrite depend on the site and mechanism of pyrite formation, with characteristic features being observed for diagenetic and syngenetic pyrites. Diagenetic pyrite formed within anoxic sediments generally has a high heavy metals content, and the degree of pyritization of these elements increases with increasing oxygen deficiency, similar to the degree of pyritization of reactive Fe. The highest gradient in the increase of the degree of trace element pyritization with bottom‐water oxygenation was found for the elements Ni < Cu < Mo = As < Tl. In contrast, syngenetic pyrite formed within a euxinic water column typically is enriched in As, Mo and Sb, but is low in heavy metals, and the geochemical variation reflects changes in sea water composition.     

Redox sensitivity of P cycling during marine black shale formation: Dynamics of sulfidic and anoxic, non-sulfidic bottom waters

A high-resolution geochemical record of a 120 cm black shale interval deposited during the Coniacian-Santonian Oceanic Anoxic Event 3 (ODP Leg 207, Site 1261, Demerara Rise) has been constructed to provide detailed insight into rapid changes in deep ocean and sediment paleo-redox conditions. High contents of organic matter, sulfur and redox-sensitive trace metals (Cd, Mo, V, Zn), as well as continuous lamination, point to deposition under consistently oxygen-free and largely sulfidic bottom water conditions. However, rapid and cyclic changes in deep ocean redox are documented by short-term (∼15-20 ka) intervals with decreased total organic carbon (TOC), S and redox-sensitive trace metal contents, and in particular pronounced phosphorus peaks (up to 2.5 wt% P) associated with elevated Fe oxide contents. Sequential iron and phosphate extractions confirm that P is dominantly bound to iron oxides and incorporated into authigenic apatite. Preservation of this Fe-P coupling in an otherwise sulfidic depositional environment (as indicated by Fe speciation and high amounts of sulfurized organic matter) may be unexpected, and provides evidence for temporarily non-sulfidic bottom waters. However, there is no evidence for deposition under oxic conditions. Instead, sulfidic conditions were punctuated by periods of anoxic, non-sulfidic bottom waters. During these periods, phosphate was effectively scavenged during precipitation of iron (oxyhydr)oxides in the upper water column, and was subsequently deposited and largely preserved at the sea floor. After ∼15-25 ka, sulfidic bottom water conditions were re-established, leading to the initial precipitation of CdS, ZnS and pyrite. Subsequently, increasing concentrations of H₂S in the water column led to extensive formation of sulfurized organic matter, which effectively scavenged particle-reactive Mo complexes (thiomolybdates). At Site 1261, sulfidic bottom waters lasted for ∼90-100 ka, followed by another period of anoxic, non-sulfidic conditions lasting for ∼15-20 ka. The observed cyclicity at the lower end of the redox scale may have been triggered by repeated incursions of more oxygenated surface- to mid-waters from the South Atlantic resulting in a lowering of the oxic-anoxic chemocline in the water column. Alternatively, sea water sulfate might have been stripped by long-lasting high rates of sulfate reduction, removing the ultimate source for HS⁻ production.