Comparative geochemistry of cadmium, rhenium, uranium, and molybdenum in continental margin sediments

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.     

Early diagenesis of redox-sensitive trace metals in the Peru upwelling area - response to ENSO-related oxygen fluctuations in the water column

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.     

Early diagenesis of trace metals (Cd, Cu, Co, Ni, U, Mo, and V) in the freshwater reaches of a macrotidal estuary

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.     

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     

长江口及其邻近海域表层沉积物中氧化还原敏感性微量元素的环境指示意义

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。     

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.     

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.     

Variations in the isotopic composition of molybdenum in freshwater lake systems

Variations in molybdenum isotopic composition, spanning the range of ∼ 2.3‰ in the terms of ⁹⁷Mo/⁹⁵Mo ratio, have been measured in sediment cores from three lakes in northern Sweden and north-western Russia. These variations have been produced by both isotopically variable input of Mo into the lakes due to Mo isotopic heterogeneity of bedrock in the drainage basins and fractionation in the lake systems due to temporal variations in limnological conditions. Mo isotope abundances of bedrock in the lake drainage basins have been documented by analysis of Mo isotope ratios of a suite of molybdenite occurrences collected in the studied area and of detrital fractions of the lake sediment cores. The median δ⁹⁷Mo value of the investigated molybdenites is 0.26‰ with standard deviation of 0.43‰ (n = 19), whereas the median δ⁹⁷Mo value of detrital sediment fractions from two lakes is − 0.40‰ with standard deviation of 0.36‰ (n = 15).The isotopic composition of Mo in the sediment cores has been found to be dependent on redox conditions of the water columns and the dominant type of scavenging phases. Hydrous Fe oxides have been shown to be an efficient scavenger of Mo from porewater under oxic conditions. Oxidative precipitation of Fe(II) in the sediments resulted in co-precipitation of Mo and significant authigenic enrichment at the redox boundary. In spite of a pronounced increase in Mo concentration associated with Fe oxides at the redox boundary the isotopic composition of Mo in this zone varies insignificantly, suggesting little or no isotope fractionation during scavenging of Mo by hydrous Fe oxides. In a lake with anoxic bottom water a chironomid-inferred reconstruction of O₂ conditions in the bottom water through the Holocene indicates that increased O₂ concentrations are generally associated with low δ⁹⁷Mo/⁹⁵Mo values of the sediments, whereas lowered O₂ contents of the bottom water are accompanied by relatively high δ⁹⁷Mo/⁹⁵Mo values, thus confirming the potential of Mo isotope data to be a proxy for redox conditions of overlying waters. However, it is pointed out that other processes including input of isotopically heterogeneous Mo and Mn cycling in the redox-stratified water column can be a primary cause of variations in Mo isotopic compositions of lake sediments.     

Distribution of natural uranium,thorium, lead,and polonium radionuclides in tidal phases of a Delaware salt marsh

Natural radionuclides in the uranium and thorium series were measured in solid tidal phases (suspended particles, bottom sediment, surface microlayer colloids) of a salt marsh in lower Delaware. The purpose was to identify potential processes responsible for trace element cycling (sources, redistribution and exchange) in salt water marshes and with their coastal waters. Generally, concentrations of U, Th,²¹⁰Pb, and²¹⁰Po on the tidal solid phases suggest a general mechanism by which tidal marshes appear to be trapping the nuclides into their interiors. The processes may include transport of enriched fine particles into the marsh, capture by salt marsh grass and chemical fixation by redox processes at the sediment surface. Specifically, the uranium contents of most of the samples are similar with activity ratios²³⁴U²³⁸U≧1, indicating a mixture of detrital and nondetrital (authigenic) uranium inputs such as seawater or ground water. Since the²³⁰Th daughter is generally deficient by about 50%, the authigenic enrichment process appears to favor uranium and is potentially linked to the extensive diagenetic sulfur redox cycle of salt marsh sediments. The²¹⁰Po/²¹⁰Pb activity ratio is less than one on Spartina adsorbed solids, and could suggest a general process in salt marshes which favors²¹⁰Pb enrichment by atmospheric fallout over enrichment of²¹⁰Po on time scales of weeks which correspond to complete tide marsh exchange. A²²⁸Th/²³²Th activity ratio of less than unity on the solids adsorbed onto marsh grass suggests a net process whereby diffusive loss of the intermediate daughter²²⁸Ra from the adsorbed solids to tidal waters dominates over potential²²⁸Th scavenging by suspended sediment.     

Insights on geochemical cycling of U, Re and Mo from seasonal sampling in Boston Harbor, Massachusetts, USA

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.     

Remobilization of authigenic uranium in marine sediments by bioturbation

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.     

In situ adsorption of mercury,methylmercury and other elements by iron oxyhydroxides and organic matter in lake sediments

Samples of authigenic material, sediment overlying water and oxic surface sediment (0–0.5-cm depth) from a perennially oxygenated lacustrine basin were analysed to investigate which solid phases are important for binding a suite of trace elements (Ag, As, Ca, Cd, Cu, Hg, In, methylmercury (MeHg), Mg, Mo, Pb, Sb and Zn). The authigenic material, which was collected with inert Teflon sheets deployed for several years across the sediment–water interface, contained mainly poorly crystallized Fe oxyhydroxides and natural organic matter, presumably humic substances derived from the watershed. Manganese oxyhydroxides were not present in the collected authigenic material due to the slightly acidic condition (pH = 5.6) of the lake that prevents the formation and recycling of these compounds. Conditional equilibrium constants for the adsorption of cationic (K_Fe–M) and anionic (K_Fe–A) trace elements onto the authigenic Fe oxyhydroxides were estimated from their concentrations in the authigenic material and in bottom water samples. These field-derived values of K_Fe–M and K_Fe–A were compared with those predicted by the surface complexation model, using laboratory-derived intrinsic adsorption constants and the water composition at the study site. Equilibrium constants (K_POM–M) were also calculated for the adsorption of the cationic trace elements onto the humic substances contained in the diagenetic material. The field-derived values of K_POM–M were compared to those predicted by the speciation code WHAM 6 for the complexation of the trace elements by dissolved humic substances in the lake. Combining the results of the present study with those on the distributions of trace elements in the porewater and solid-phase sediments reported in previous studies at the same site, it was determined whether the trace elements bind preferentially to Fe oxyhydroxides or natural organic matter in oxic sediments. The main inferences are that the anionic trace elements As, Mo and Sb, as well as the cationic metal Pb are preferentially bound to the authigenic Fe oxyhydroxides whereas the other trace elements, and especially Hg and MeHg, are preferentially bound to the humic substances.     

新疆阿克苏地区早寒武世碳酸盐岩沉积环境:微量元素和碳同位素证据

对出露于塔里木盆地北缘阿克苏地区寒武系纽芬兰统玉尔吐斯组上部和寒武系第二统肖尔布拉克组下部海相沉积碳酸盐岩进行了氧化-还原敏感元素(Mo、V、Cd和U)及稳定C、O同位素的地球化学剖面研究,以探讨早寒武世沉积碳酸盐岩的沉积环境.研究揭示,尤尔美那克剖面肖尔布拉克组底部和下部含有两个δ13C负异常,谷值分别为-2.1‰和...     

Concentration,vertical flux,and remineralization of particulate uranium in seawater

Concentrations and fluxes of particulate U were measured throughout the water column at several locations in the Atlantic and Pacific Oceans with in situ filtration systems and sediment traps. The results indicate that dissolved U is fixed to particles in surface seawater. Organic matter appears to be the carrier phase. Formation of particulate authigenic U below the surface waters could not be detected. Authigenic U is remineralized within the bathypelagic layers at the open ocean sites studied. In the Panama Basin, an upwelling area with high biological productivity, remineralization of authigenic U in the deep water column was not observed. The rate of remineralization of authigenic U in the deep sea is insufficient to produce a measurable concentration gradient between surface and deep waters within the mixing time of the oceans. Formation of authigenic U in the water column in areas such as the Panama Basin is not a significant sink for U on an ocean wide basis.     

Diagenesis of oxyanions (V, U, Re, and Mo) in pore waters and sediments from a continental margin

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.     

Effects of pH fluctuations on potentially toxic metals in the water and sediment of the Dillon Reservoir,Summit County,Colorado

Potentially toxic metals exist in many reservoirs of surface water and therefore require an understanding of their occurrence, distribution, and mobility. The sediment accumulating at the bottom of the Dillon Reservoir, Colorado is contaminated with metals (Cu, Pb, Zn, Cd, Mo, etc.) that are primarily sorbed to Fe and Al hydroxides present in the sediment. The metals are derived from weathering of mineralized bedrock and mine tailings in the surrounding drainage basins. Sediment samples from the Dillon Reservoir were analyzed for major and trace elements and acidification experiments were performed to quantify the fraction of metals released from the sediment as a function of changes in pH. The highest percentages of metals are released from the sediment at low pH with the exception of Mo which has the highest percent released at near neutral pH. In addition, seasonal fluctuations in the concentrations of metals in the water of the Dillon Reservoir can be explained by changes in pH of as low as 0.2 pH units.     

A method for determination of the isotopic composition of authigenic uranium in Baikal bottom sediments

A simple, reliable, and high-performance method has been proposed for direct determination of the isotopic composition of authigenic uranium in silica lacustrine sediments. The method is based on studying the kinetics of the selective extraction of authigenic uranium from sediments with weak solutions of ammonium hydrocarbonate followed by the ICP-MS analysis of the nuclides. To estimate the contamination of authigenic uranium by terrigenous one, the contents of ²³²Th and some other clastogenic elements in the extracts were measured simultaneously. The selectivity of extraction of authigenic uranium from the sediments treated with a 1% NH₄HCO₃ solution appeared to be no worse than 99%. The method was used to analyze the isotopic composition of authigenic uranium at several key horizons of a core dated before. The measurements directly prove that the ²³⁴U/²³⁸U values in Baikal water varied depending on climate, which contradicts the previous statements. The measured ²³⁴U/²³⁸U ratios in paleo-Baikal water match the values reconstructed from isotopic data for total uranium in the sediments on the supposition that the U/Th ratio is constant in the terrigenous part of the sediment. Direct experimental determination of total and authigenic nuclides in sediments enhances the potentiality of the method for absolute ²³⁴U-²³⁰Th dating of carbonate-barren lacustrine sediments, including those from Lake Baikal, within the intervals corresponding to the periods of glaciation, where the sediments contain a large fraction of terrigenous component. Given the fractions of terrigenous and authigenic uranium are accurately determined, we have an opportunity to study the variability of the sources of terrigenous matter and to refine the previous model for reconstructing the climate humidity in East Siberia.     

Geochemical and anthropogenic enrichments of Mo in sediments from perennially oxic and seasonally anoxic lakes in Eastern Canada

We measured the vertical distributions of Mo, Fe, Mn, sulfide, sulfate, organic carbon, major ions, and pH in sediment porewater from one perennially oxic and three seasonally anoxic lacustrine basins in Eastern Canada, as well as those of Mo, acid volatile sulfide, Fe, Mn, Al, organic C, ²¹⁰Pb and ¹³⁷Cs in sediment cores from the same sites. The only input of anthropogenic Mo to these lakes comes from atmospheric deposition.The relatively monotonous distribution of Mo in the porewater of three seasonally anoxic basins suggests that Mo is not redistributed in the sedimentary column during periods of anoxia. In contrast, porewater Mo profiles obtained at three sampling dates in a perennially oxic basin display sharp Mo peaks below the sediment-water interface, indicating redistribution subsequent to deposition. Modeling of these latter porewater Mo profiles with a diagenetic reaction-transport equation coupled to comparisons among the various porewater and solid phase profiles reveal that Mo is released at 1-2 cm depth as a consequence of the reductive dissolution of Fe oxyhydroxides and scavenged both at the vicinity of the sediment-water interface, by re-adsorption onto authigenic Fe oxyhydroxides, and deeper in the sediments where dissolved sulfide concentrations are higher. The estimated rate constant for the adsorption of Mo onto Fe oxyhydroxides is 36 ± 45 cm³ mol⁻¹ s⁻¹.Diagenetic modeling indicates that authigenic Mo in sediments of the perennially oxic basin represents about one-third of the total solid phase Mo in the first cm below the sediment-water interface and only one tenth below this horizon. If we assume that no authigenic Mo is accumulated in the seasonally anoxic lake sediments we conclude that the sediment Mo concentrations, which are up to 3-16 times higher than the average lithogenic composition, depending on the lake, are mainly due to atmospheric deposition of anthropogenic Mo and not to the formation of authigenic Mo phases. Reconstructed historical records of the atmospheric Mo deposition indicate maximum values in the 1970s and 1980s and significant decreases since then. Emissions to the atmosphere associated with the smelting of non-ferrous ores and coal combustion appear to be the most important sources of anthropogenic Mo.