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1.
This research tests the hypothesis that trace metals respond to the extent of reducing conditions in a predictable way. We describe pore water and sediment measurements of iron (Fe), manganese (Mn), vanadium (V), uranium (U), rhenium (Re), and molybdenum (Mo) along a transect off Washington State (USA). Sediments become less reducing away from the continent, and the stations have a range of oxygen penetration depths (depth to unmeasurable O2 concentration) varying from a few millimeters to five centimeters. When oxygen penetrates ∼1 cm or less, Fe is reduced in the pore waters but reoxidized near the sediment-water interface, preventing a flux of Fe2+ to overlying waters, whereas Mn oxides are reduced and Mn2+ diffuses to overlying waters. Both Re and U authigenically accumulate in sediments. Only at the most reducing location, where the oxygen penetrates 0.3 cm below the sediment-water interface, does the surface 30 cm of sediments become reducing enough to authigenically accumulate Mo.Stations in close proximity to the Juan de Fuca Ridge crest are enriched in Mn and Fe from hydrothermal plume processes. Both V and Mo clearly associate with Mn cycling, whereas U may be associating with either Mn oxides and/or Fe oxyhydroxides. Rhenium is uncomplicated by adsorption to Mn oxides and/or Fe oxyhydroxides, and Re accumulation in sediments appears to be due solely to the extent of reducing conditions. Therefore, authigenic sediment Re enrichment appears to be the best indicator for intermediate reducing conditions, where oxygen penetrates less than ∼1 cm below the sediment-water interface, when coupled with negligible authigenic Mo enrichment.  相似文献   

2.
Suboxic trace metal geochemistry in the Eastern Tropical North Pacific   总被引:3,自引:0,他引:3  
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.  相似文献   

3.
Remobilization of authigenic uranium in marine sediments by bioturbation   总被引:1,自引:0,他引:1  
Uranium behaves as a nearly conservative element in oxygenated seawater, but it is precipitated under chemically reducing conditions that occur in sediments underlying low-oxygen bottom water or in sediments receiving high fluxes of particulate organic carbon. Sites characterized by a range of bottom-water oxygen (BWO) and organic carbon flux (OCF) were studied to better understand the conditions that determine formation and preservation of authigenic U in marine sediments. Our study areas are located in the mid latitudes of the northeast Pacific and the northwest Atlantic Oceans, and all sites receive moderate (0.5 g/cm2 kyr) to high (2.8 g/cm2 kyr) OCF to the sediments. BWO concentrations vary substantially among the sites, ranging from <3 to ∼270 μM. A mass balance approach was used to evaluate authigenic U remobilization at each site. Within each region studied, the supply of particulate nonlithogenic U associated with sinking particles was evaluated by means of sediment traps. The diffusive flux of U into sediments was calculated from pore-water U concentration profiles. These combined sources were compared with the burial rate of authigenic U to assess the efficiency of its preservation. A large fraction (one-third to two-thirds) of the authigenic U precipitated in these sediments via diffusion supply is later regenerated, even under very low BWO concentrations (∼15 μM). Bioturbating organisms periodically mix authigenic U-containing sediment upward toward the sediment-water interface, where more oxidizing conditions lead to the remobilization of authigenic U and its loss to bottom waters.  相似文献   

4.
5.
Pore water and solid phase data for redox-sensitive metals (Mn, Fe, V, Mo and U) were collected on a transect across the Peru upwelling area (11°S) at water depths between 78 and 2025 m and bottom water oxygen concentrations ranging from ∼0 to 93 μM. By comparing authigenic mass accumulation rates and diffusive benthic fluxes, we evaluate the respective mechanisms of trace metal accumulation, retention and remobilization across the oxygen minimum zone (OMZ) and with respect to oxygen fluctuations in the water column related to the El Niño Southern Oscillation (ENSO).Sediments within the permanent OMZ are characterized by diffusive uptake and authigenic fixation of U, V and Mo as well as diffusive loss of Mn and Fe across the benthic boundary. Some of the dissolved Mn and Fe in the water column re-precipitate at the oxycline and shuttle particle-reactive trace metals to the sediment surface at the lower and upper boundary of the OMZ. At the lower boundary, pore waters are not sufficiently sulfidic as to enable an efficient authigenic V and Mo fixation. As a consequence, sediments below the OMZ are preferentially enriched in U which is delivered via both in situ precipitation and lateral supply of U-rich phosphorites from further upslope. Trace metal cycling on the Peruvian shelf is strongly affected by ENSO-related oxygen fluctuations in bottom water. During periods of shelf oxygenation, surface sediments receive particulate V and Mo with metal (oxyhydr)oxides that derive from both terrigenous sources and precipitation at the retreating oxycline. After the recurrence of anoxic conditions, metal (oxyhydr)oxides are reductively dissolved and the hereby liberated V and Mo are authigenically removed. This alternation between supply of particle-reactive trace metals during oxic periods and fixation during anoxic periods leads to a preferential accumulation of V and Mo compared to U on the Peruvian shelf. The decoupling of V, Mo and U accumulation is further accentuated by the varying susceptibility to re-oxidation of the different authigenic metal phases. While authigenic U and V are readily re-oxidized and recycled during periods of shelf oxygenation, the sequestration of Mo by authigenic pyrite is favored by the transient occurrence of oxidizing conditions.Our findings reveal that redox-sensitive trace metals respond in specific manner to short-term oxygen fluctuations in the water column. The relative enrichment patterns identified might be useful for the reconstruction of past OMZ extension and large-scale redox oscillations in the geological record.  相似文献   

6.
对长江口及其邻近海域表层沉积物和底层悬浮体中氧化还原敏感元素分布规律和富集特征进行了分析与研究。结果表明氧化还原敏感元素在研究区具有明显的“离岸富集”特征,去除粒度效应、陆源碎屑来源组分和有机质的吸附作用等因素的影响之后,氧化还原敏感元素仍显示出在缺氧区的富集。通过同一站位底层悬浮体和沉积物中氧化还原敏感元素含量的分析比较,发现底层水缺氧是导致氧化还原敏感元素Mo、Cd、V等在沉积物中富集的主要原因。Mo、Cd、V等元素的不同富集程度可用来反映缺氧区的缺氧程度。因此,Mo, Cd, V等RSE在长江口外缺氧区及其邻近海域具有氧化还原环境指示意义,可以指示长江口外缺氧区的存在与大体范围,并可在一定程度上用来衡量缺氧区的缺氧程度。U理论上虽然也对环境的氧化还原条件敏感,但由于受陆源碎屑来源组分的影响较大,在长江口外缺氧区的富集并不明显,因此U在研究区不具有氧化还原环境指示意义。  相似文献   

7.
The concentrations of authigenic phases of Cd, Re, U, and Mo increase with depth in four 45-cm-long sediment box cores collected along the axis of the Laurentian Trough, Gulf of St. Lawrence. Average authigenic accumulation rates, estimated from element inventories, are similar to rates in other continental margin environments. Strong regional variations in sediment accumulation rate and sulfide concentration have little influence on the accumulation rates of Cd and Re. This suggests that slow precipitation kinetics controls the accumulation of Cd and Re in these sediments. The accumulation rate of authigenic U is more variable; it may be tied to the kinetics of microbially mediated U reduction and be controlled by the availability of reactive organic matter. Authigenic Mo is distinguished by a sharp subsurface concentration minimum, above which Mo cycles with manganese. Mo released to pore water upon reduction of Mn oxides diffuses downward and enriches the subsurface sediment. Mo accumulates most rapidly in the sediment with the highest sulfide content. Slow conversion of molybdate to thiomolybdate may explain the much slower Mo accumulation rate in the less sulfidic sediments. A component of authigenic Mo accumulates with pyrite in an approximately constant Mo:Fe ratio. The accumulation rate of pyrite and associated Mo is insensitive to AVS abundance. Pyrite formation may be limited by the reactivity of iron oxide minerals.  相似文献   

8.
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.  相似文献   

9.
沉积物微量金属元素在重建水体环境变化中的意义   总被引:7,自引:0,他引:7  
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  相似文献   

10.
Geochemistry of Peruvian near-surface sediments   总被引:6,自引:0,他引:6  
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.  相似文献   

11.
长江口氧化还原敏感元素的早期成岩过程   总被引:2,自引:0,他引:2  
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%.   相似文献   

12.
Preservation of particulate non-lithogenic uranium in marine sediments   总被引:1,自引:0,他引:1  
Particulate non-lithogenic uranium (PNU), excess U above detrital background levels found in marine particulate matter, is formed in surface waters throughout the ocean. Previous studies have shown that PNU is regenerated completely prior to burial of particles in sediments within well-oxygenated open-ocean regions. However, the fate of PNU has never been examined in ocean margin regions or in anoxic basins. Here we evaluate the preservation of PNU in ocean margin sediments and within semi-enclosed basins using samples from sediment traps deployed at multiple depths and surface sediments. Organic carbon fluxes at the sediment trap locations ranged from 0.1 to 4.3 g/cm2 kyr, while the dissolved oxygen concentration in the water column ranged from <3 μM to ∼ 270 μM. Preservation of PNU increases with decreasing dissolved oxygen concentration, approaching 100% preservation at oxygen concentration < 25 μM. PNU contributes as much as 40 to 70% of the total authigenic U in sediments in the Santa Barbara Basin and seasonally anoxic Saanich Inlet, and some 10% to 50% of the total authigenic U in sediments off the central California Margin.  相似文献   

13.
大气-海洋含氧量的演化对埃迪卡拉纪-寒武纪转折期的后生动物大爆发事件具有重要影响.为探讨寒武纪纽芬兰世中国南方海洋氧化还原性质的演化及其初级生产力、海水硫酸盐浓度等演化驱动因素, 分析了李家沱剖面纽芬兰世留茶坡组和小烟溪组微量元素、有机碳含量、有机碳同位素、总硫含量、黄铁矿硫同位素等.该剖面沉积于斜坡-盆地环境且出露齐全.该剖面上V/Sc、Th/U及Mo、U、V、Ni、Cu等元素的富集系数呈现出5个变化旋回, 其中留茶坡组中上部和小烟溪组中部各存在一氧化环境段, 其余层段处于缺氧环境, 而Re/Mo则显示仅在小烟溪组中部水体出现过短暂的氧化环境和含有游离H2S的硫化环境, 其余层段处于没有游离H2S的缺氧非硫化环境.Ba、Ni、Cu、Zn、Cd等微量元素的富集系数及TOC表明: 留茶坡组的有机质沉降量和埋藏量都明显小于上覆小烟溪组; 而在小烟溪组中, 其中部有机质的沉降量和埋藏量最低, 下部最高, 上部次之.TOC/TS、TS以及黄铁矿硫同位素的垂向演化趋势等都显示李家沱剖面纽芬兰世大都处于低海水硫酸盐浓度环境.低海水硫酸盐浓度是造成李家沱剖面纽芬兰世缺氧水体未富集游离H2S的主要原因.大气含氧量的升高是导致李家沱剖面小烟溪组中部出现短暂氧化环境以及近硫化环境的主要原因.   相似文献   

14.
This study examined the removal of U, Mo, and Re from seawater by sedimentary processes at a shallow-water site with near-saturation bottom water O2 levels (240-380 μmol O2/L), very high organic matter oxidation rates (annually averaged rate is 880 μmol C/cm2/y), and shallow oxygen penetration depths (4 mm or less throughout the year). Under these conditions, U, Mo, and Re were removed rapidly to asymptotic pore water concentrations of 2.2-3.3 nmol/kg (U), 7-13 nmol/kg (Mo), and 11-14 pmol/kg (Re). The depth order in which the three metals were removed, determined by fitting a diffusion-reaction model to measured profiles, was Re < U < Mo. Model fits also suggest that the Mo profiles clearly showed the presence of a near-interface layer in which Mo was added to pore waters by remineralization of a solid phase. The importance of this solid phase source of pore water Mo increased from January to October as the organic matter oxidation rate increased, bottom water O2 decreased, and the O2 penetration depth decreased. Experiments with in situ benthic flux chambers generally showed fluxes of U and Mo into the sediments. However, when the overlying water O2 concentration in the chambers was allowed to drop to very low levels, Mn and Fe were released to the overlying water along with the simultaneous release of Mo and U. These experiments suggest that remineralization of Mn and/or Fe oxides may be a source of Mo and perhaps U to pore waters, and may complicate the accumulation of U and Mo in bioturbated sediments with high organic matter oxidation rates and shallow O2 penetration depths.Benthic chamber experiments including the nonreactive solute tracer, Br, indicated that sediment irrigation was very important to solute exchange at the study site. The enhancement of sediment-seawater exchange due to irrigation was determined for the nonreactive tracer (Br), TCO2, , U and Mo. The comparisons between these solutes showed that reactions within and around the burrows were very important for modulating the Mo flux, but less important for U. The effect of these reactions on Mo exchange was highly variable, enhancing Mo (and, to a lesser extent, U) uptake at times of relatively modest irrigation, but inhibiting exchange when irrigation rates were faster. These results reinforce the observation that Mo can be released to and removed from pore waters via sedimentary reactions.The removal rate of U and Mo from seawater by sedimentary reactions was found to agree with the rate of accumulation of authigenic U and Mo in the solid phase. The fluxes of U and Mo determined by in situ benthic flux chamber measurements were the largest that have been measured to date. These results confirm that removal of redox-sensitive metals from continental margin sediments underlying oxic bottom water is important, and suggest that continental margin sediments play a key role in the marine budgets of these metals.  相似文献   

15.
《Applied Geochemistry》2003,18(4):539-549
This paper describes a rapid procedure that allows precise analysis of Mo, Cd, U and Th in sediment samples as small as 10 mg by using a novel approach that utilizes a “pseudo” isotope dilution for Th and conventional isotope dilution for Mo, Cd and U by ICP-MS. Long-term reproducibility of the method is between 2.5 and 5% with an advantage of rapid analysis on a single digestion of sediment sample and the potential of adding other elements of interest if so desired. Application of this method to two piston cores collected near the mouth of the Patuxent River in Chesapeake Bay showed that the accumulation of authigenic Mo and Cd varied in response to the changing bottom water redox conditions, with anoxia showing consistent oscillations throughout both pre-industrial and industrial times. Accumulation of authigenic U shows consistent oscillations as well, without any apparent increase in productivity related to anoxic trends. Degrees of Mo and Cd enrichment also inversely correlate to halophilic microfaunal assemblages already established as paleoclimate proxies within the bay indicating that bottom water anoxia is driven in part by the amount of freshwater discharge that the area receives.  相似文献   

16.
We present results from a long term geochemical cycling model, with a focus on the sensitivity of atmospheric carbon dioxide, oxygen, and the major element composition of seawater to seafloor spreading rates. This model incorporates rock weathering, basalt–seawater exchange reactions, and the formation and destruction of chemical sediments and organic matter. Hydrothermal reactions between seafloor and seawater involving calcium, magnesium, sodium, potassium, sulfate and carbon are the high temperature counterparts to low temperature redox, weathering, precipitation and diagenetic reactions. A major source of uncertainty is the extent to which these exchange fluxes are controlled by seafloor spreading rate. In addition, the return fluxes of these components to the atmospheric and primary silicate reservoirs reflect not only the overall rates of subduction and metamorphism, but the distribution of the overlying sedimentary burden and authigenic minerals formed during basalt alteration as well. In particular, we show how the stoichiometry of exchange fluxes (Mg/Ca and SO4/Ca) may buffer atmospheric CO2 and O2 concentrations.  相似文献   

17.
利用电感耦合等离子体质谱(ICP-MS)法分析了取自南沙南部陆坡的NS93-5钻孔沉积物的部分过渡金属元素含量的变化。结果表明,代表碎屑物质的量的Ti含量在不同气候时期变化明显,其中在氧同位素第4期碎屑比例最大,第2期和第3期末期,碎屑所占比例比较高,代表较大的碎屑输入通量。但与沉积速率相比较发现,NS93-5的沉积速率并不仅仅决定于碎屑的输入,自生沉积物的累积作用也极为明显。Mn、Mo、Cr、V、U、Cd、Co、Ni、Cu和Zn等元素含量变化表明,NS93-5钻孔沉积物中还原状态极低。反映出自过去15ka以来该区陆坡深度底层海水均富含氧气,并没有出现无氧状态,意味着南沙海域底层海水更新一直都比较快。  相似文献   

18.
In order to understand the fractionation of Re and Os in marine environments, their removal from artificial seawater to Tokyo Bay sediments is studied using a multitracer technique. The chemical processes of the removal of Re and Os are also estimated based on their speciation analyses by X-ray absorption fine structure (XAFS) spectroscopy. The partitioning experiments, which use the multitracer technique, provide information on Re and Os regarding (i) their distributions between artificial seawater-sediment systems, (ii) their complexation with humic acid, and (iii) their carriers in sediments. In addition, XAFS spectroscopy provides direct information on the chemical states of Re and Os in the sediments.In an artificial seawater-sediment system containing a multitracer, Re is removed from the artificial seawater only under a reducing environment. The speciation of Re by X-ray absorption near-edge structure (XANES) suggests that the majority of Re remains as in the artificial seawater even under highly reducing conditions, during laboratory time scale (about 2 weeks). Moreover, XANES simulation shows that some Re exists at a lower oxidation state, such as ReO2, in the reducing sediment. These results can be explained by the slow kinetics of the reaction which is similar to those suggested by previous geochemical studies.In contrast, Os is readily removed from the artificial seawater into sediments under various redox conditions. Even under oxic conditions, a large fraction of Os is removed from the artificial seawater to sediments without organic matter. Based on the Os XANES study, it is confirmed that the oxidation states of Os incorporated in the reducing sediment and oxic sediment are trivalent and tetravalent, respectively. Sequential extraction suggests that the main carrier of Os in the organic-rich sediment is either ferromanganese oxides or organic matter, and that the Os in these two fractions may correspond to hydrolyzed insoluble Os species and Os species interacting with organic matter, at lower valence, respectively. The results of distribution study of Os in the absence and presence of humic acid (HA) also imply that Os assumes more than one chemical species, and a small fraction of Os may interact with HA in the experimental system. Meanwhile, extended X-ray absorption fine structure (EXAFS) confirms that the first neighboring atom of Os in the reducing sediment is oxygen. If Os(VIII) is the main dissolved species in seawater, as is expected thermodynamically, reductive removal may control the enrichment of Os in the sediment. Osmium, which is removed as Os(IV), is reduced further to Os(III) by a diagenetic process and may be complexed with organic matter in the reducing sediment.The results of the removal behaviors of Re and Os obtained in the current study show that Re can be removed from the artificial seawater only under highly reducing conditions within 2 weeks, but Os removal from the artificial seawater can be found under various redox conditions. Thus, a high 187Re/188Os ratio can occur only in reducing sediments, such as black shales. The high187Re/188Os ratio, in turn, makes black shales suitable for Re-Os dating. In contrast, authigenic sediments (and minerals) under oxic environments can enrich Os, but since Re is not distributed to the sediments under oxic conditions, this will cause a much lower 187Re/188Os ratio than that of seawater. The Os isotope system of these materials can be used as a paleo-marine environmental tracer since the 187Os/188Os ratio cannot grow significantly due to its extremely low 187Re/188Os ratio.  相似文献   

19.
Vertical profiles from the water column, including the maximum turbidity zone (MTZ) to the consolidated sediment were sampled in September 2000 in the freshwater reaches of the Gironde Estuary during a complete neap tide-spring tide cycle. The vertical distributions of dissolved major redox parameters and metals (Mn, Fe, Cd, Cu, V, Co, Ni, Mo, and U) were determined. Reactive particulate metal fractions were also determined from selective leaching. The studied system is characterized by density layers functioning at different time-scales, consisting of two mobile layers, i.e., the liquid (LM) and the soft mud (SM), overlying consolidated sediments (CS). This results in a three-zone diagenetic regime where (1) O2 dynamics are fast enough to show depletion in the rapidly mixed LM sequence (tidal time-scale), (2) denitrification occurs on the weekly time-scale mixing SM sequence, and (3) the Mn, Fe, and sulfate cycling occurs in the CS layer (annual time-scale). The studied trace metals show differential behavior during early diagenesis: (1) Cd, Cu, and V are released into pore water preferentially from organic matter in the SM, (2) Co, Ni, and U are released in the CS from Mn and Fe oxides during reductive dissolution, and (3) Mo from both processes. Transient conditions (i.e., oscillations of redox fronts and reoxidation processes), due to the dynamics of the mobile layers, strongly influence the trace metal distributions as inducing resolubilization (Cd, Cu, and Mo). In the CS, authigenic metal phases accumulate, either by direct precipitation with sulfides (Cu, Cd) or co-precipitation with Fe-sulfides (Mo). Microbially mediated reduction of Fe oxides is proposed to control U removal from pore water by reduction of U(VI) to U(IV) at depth. However, a significant fraction of the trace metals is trapped in the sediment in exchangeable forms, and therefore is susceptible to be mobilized due to resuspension of estuarine sediment during strong river flood periods and/or dredging activities.  相似文献   

20.
Some comparative marine chemistries of rhenium, gold, silver and molybdenum   总被引:1,自引:0,他引:1  
Four metals, Re, Au, Ag and Mo, whose dissolved forms in seawater can potentially be reduced to insoluble states, have been measured in a variety of solids depositing under anoxic conditions: hydrothermal sulfides; coastal sediments; and phosphorites. For comparative purposes these elements have also been determined in ferromanganese minerals and pelagic sediments which have accumulated under oxidizing conditions. Rhenium appears to be a unique sentinel for identifying reducing depositional environments, where enrichments of greater than three orders of magnitude above crustal concentrations are found. Molybdenum follows Re in these sediments but Mo is enriched also in those that accumulate under oxidizing conditions. The reported Mo crustal concentrations appear low in comparison to our measured sedimentary values. Gold and Ag are concentrated in hydrothermal deposits and sulfides appear to be involved in the precipitation of these elements. Coastal sediments adjacent to a domestic outfall of Los Angeles, California contain extraordinary high accumulations of anthropogenic Au, Ag and Pt. The study seeks an understanding of the mobilities and sinks of these metals in the marine environment during the major weathering cycle. Further, anthropogenic contributions to their sedimentary concentrations are identified.  相似文献   

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