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.     

Sulfur speciation and associated trace metals (Fe,Cu) in the pore waters of Great Marsh,Delaware

The pore waters of sediments from a salt marsh along the Delaware estuary have been analyzed for sulfur species and associated trace metals. Since the sediment interface is usually in contact with the atmosphere, the sulfur species are dependent on the production of hydrogen sulfide by sulfate reduction and subsequent oxidation by diffusing oxygen. The most important species observed are hydrogen sulfide, polysulfide ions and thiosulfate. Secondary reactions of hydrogen sulfide and polysulfides with decomposing organic matter yield significant concentrations of both thiols and organic polysulfides. Upon isolation of the sediment from the atmosphere due to tidal inundation, bacterial sulfate reduction becomes the dominant process. This results in the reduction of the polysulfides in agreement with thermodynamic predictions, and suggests that the redox couple sulfide/polysulfide is a good redox indicator under such reducing environments.The concentrations of trace elements Cu and Fe in the pore waters are mainly controlled by sulfide formation. Calculations show that copper is strongly complexed probably with organo-sulfur ligands. Iron might be complexed as such sulfur species to a much lesser extent than copper.     

Deciphering As and Cu cycling in sediment pore waters in a large marina (Port Camargue,southern France) using a multi-tracer (Fe,Mn, U,Mo) approach

The sediments of the Port Camargue marina (South of France) are highly polluted by Cu and As (Briant et al., 2013). The dynamics of these pollutants in pore waters was investigated using redox tracers (sulfides, Fe, Mn, U, Mo) to better constrain the redox conditions.In summer, pore water profiles showed a steep redox gradient in the top 24 cm with the reduction of Fe and Mn oxy-hydroxides at the sediment water interface (SWI) and of sulfate immediately below. Below a depth of 24 cm, the Fe, Mn, Mo and U profiles in pore waters reflected Fe and Mn reducing conditions and, unlike in the overlying levels, sulfidic conditions were not observed. This unusual redox zonation was attributed to the occurrence of two distinct sediment layers: an upper layer comprising muddy organic-rich sediments underlain by a layer of relatively sandy and organic-poor sediments. The sandy sediments were in place before the building of the marina, whereas the muddy layer was deposited later. In the muddy layer, large quantities of Fe and Mo were removed in summer linked to the formation of insoluble sulfide phases. Mn, which can adsorb on Fe-sulfides or precipitate with carbonates, was also removed from pore waters. Uranium was removed probably through reduction and adsorption onto particles. In winter, in the absence of detectable pore water sulfides, removal of Mo was moderate compared to summer.Cu was released into solution at the sediment water interface but was efficiently trapped by the muddy layer, probably by precipitation with sulfides. Due to efficient trapping, today the Cu sediment profile reflects the increase in its use as a biocide in antifouling paints over the last 40 years.In the sandy layer, Fe, Mn, Mo and As were released into solution and diffused toward the top of the profile. They precipitated at the boundary between the muddy and sandy layers. This precipitation accounts for the high (75 μg g⁻¹) As concentrations measured in the sediments at a depth of 24 cm.     

Enrichment of redox-sensitive trace metals (U,V, Mo,As) associated with the late Hauterivian Faraoni oceanic anoxic event

The Faraoni Level is a short-lived oxygen-deficient event that took place during the latest Hauterivian. In order to improve our understanding of the palaeoenvironmental conditions that occurred during this event, we have analysed the contents of several redox-sensitive trace elements (U, V, Mo, As, Co, Cd, Cu, Zn, Ni, Pb, Cr) from bulk limestone samples of late Hauterivian–early Barremian age from three reference sections. U, V, Mo and As show consistent and significant enrichments during the Faraoni event whereas the other redox-sensitive trace elements analysed here are not systematically enriched. In order to explain this discrepant behaviour, we propose that the Faraoni Level was deposited during a period of anoxic conditions near the sediment–water interface. The distinctive peaks in U, V, Mo and As contents are traceable throughout the three studied sections and represent a good correlation tool which helps to identify the Faraoni Level and its equivalents in the western Tethyan realm and outside of the Tethys. For example, a peak in U contents in upper Hauterivian sediments of the northwestern Pacific realm (ODP leg 185, site 1149) may well be an expression of the Faraoni event in this particular basin.     

High resolution profiles of trace metals in pore waters of marine and riverine sediments assessed by DET and DGT

In polluted aquatic systems, toxic metals are often accumulated in bottom sediments. They are, however, not necessarily stored definitively because diagenetic processs can modify redox, pH and even the amount of complexing ligands, releasing the trace metals back into the pore waters and the water column. Especially the labile metal fraction in the pore waters is important since this is the bioavailable fraction determining the bio-toxicity of the sediments. The goal of our study was therefore to assess, with novel sampling techniques, this bioavailable metal fraction in the pore waters as well as the flux towards the overlying water column. High-resolution profiles of trace metals in pore waters of marine and riverine sediments were assessed by DET （diffusive equilibrium in thin films） and DGT （diffusive gradients in thin films） gel techniques. The DET technique uses a diffusive gel layer that equilibrates with the aquatic system and with this technique the concentrations of total dissolved trace metals are obtained directly. The DGT technique uses an acrylamide diffusive gel backed by a resin gel （Chelex） which binds trace metals. With the DGT technique only labile species of selected metals can be captured. According to the redox potential measurements, the marine sediments were suboxic （200 mV to -220 mV versus Ag/AgCl electrode）, while the riverine sediments were completely anoxic （-160 mV to -220 mV versus Ag/AgCl electrode）. This redox potential was apparently controlling the trace metals species in the pore waters： for example a strong correlation between Mn and Co was found in the riverine sediments （for DET and DGT sampling）, while in the marine sediments trace metals presented various behaviors.     

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.     

Removal of trace metals by coprecipitation with Fe,Al and Mn from natural waters contaminated with acid mine drainage in the Ducktown Mining District,Tennessee

This study examined the sorption of trace metals to precipitates formed by neutralization of 3 natural waters contaminated with acid mine drainage (AMD) in the former Ducktown Mining District, Tennessee. The 3 water samples were strongly acidic (pH 2.2 to 3.4) but had distinctively different chemical signatures based on the mole fractions of dissolved Fe, Al and Mn. One sample was Fe-rich (Fe=87.5%, Al=11.3%, and Mn=1.3%), another was Al-rich (Al=79.4%, Mn=18.0%, and Fe=2.5%), and the other was Mn-rich (Mn=51.4%, Al=25.7%, and Fe=22.9%). In addition, these waters had high concentrations of trace metals including Zn (37,700 to 17,400 μg/l), Cu (13,000 to 270 μg/l), Co (1,500 to 520 μg/l), Ni (360 to 75 μg/l), Pb (30 to 8 μg/l), and Cd (30 to 6 μg/l). Neutralization of the AMD-contaminated waters in the laboratory caused the formation of either schwertmannite at pH<4 or ferrihydrite at pH>4. Both phases were identified by XRD analyses of precipitates from the most Fe-rich water. At higher pH values (∼5) Al-rich precipitates were formed. Manganese compounds were precipitated at pH∼8. The removal of trace metals depended on the precipitation of these compounds, which acted as sorbents. Accordingly, the pH for 50% sorption (pH₅₀) ranged from 5.6 to 7.5 for Zn, 4.6 to 6.1 for Cu, 5.4 to 7.7 for Ni, 5.9 to 7.9 for Co, 3.1 to 4.3 for Pb, and 5.5 to 7.7 for Cd. The pH dependence of sorption arose not only because of changes in the sorption coefficients of the trace metals but also because the formation and composition of the sorbent was controlled by the pH, the chemical composition of the water, and the solubilities of the oxyhydroxide-sulfate complexes of Fe, Al, and Mn.     

Mobility of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric O2: an experimental study

 The major aim was to increase our knowledge on the behaviour of Al, Co, Cr, Cu, Fe, Mn, Ni and V in sulphide-bearing fine-grained sediments exposed to atmospheric oxygen. Samples of this type of sediment collected in a previous investigation at eight sites in western Finland were digested in HClO₄-HNO₃-HCl-HF at 200  °C and in HCl:HNO₃:H₂O at 95  °C (aqua regia), and subjected to extractions with ammonium acetate and hydrogen peroxide. Metals and S in the leachates were determined with ICP-AES. The results of the chemical analyses are compared with previously reported experimental data. The concentrations of Al and Fe in the sulphide-bearing fine-grained sediments are about 7% and 5%, respectively. Of the trace metals studied, Mn is most abundant followed in decreasing order by V>Cr>Ni>Cu>Co. On oxidation of the sediments, high proportions of Co, Mn and Ni, intermediate proportions of Cu but low proportions of Fe, Al, Cr and V are released. The extent of the release of a metal on oxidation is controlled either by (1) the level to which the pH of the sediments drops on oxidation (Al, Cu, Cr, V), (2) the amount of the metal associated with easily reduced phases (metal sulphides) in the sediments (Ni, Co) or (3) the sum of the amount associated with reduced phases and adsorbed on soil compounds (Mn). No control of the release of Fe on oxidation of the sediments was identified. Based on the results of the study it is argued that artificial drainage and the subsequent oxidation of sulphide-bearing sediments will result in extensive leaching of Co, Mn and Ni, moderate leaching of Cu and limited leaching of Cr and V into drainages. The major elements, Fe and Al, have the potential to be mobilised and leached in large amounts, though the proportions mobilised/leached will remain low. It is suggested that the identification of sulphide-bearing sediments with a high potential of metal release should be based on determination of metals in easily mobilised reduced compounds (dissolved e.g. in H₂O₂) and of the level to which the pH of the sediments drops on oxidation. Received: 16 October 1997 · Accepted: 9 March 1998     

Distribution and speciation of four heavy metals (Cd,Cr, Mn and Ni) in the surficial sediments from estuary in daliao river and yingkou bay

Heavy metal pollution in the surficial sediments derived from estuary in Daliao River and Yingkou Bay is investigated in the present work in order to assess environmental quality and pollution levels. Physicochemical parameters of surficial sediments (sediment type and TOC) and the overlying water (temperature, EC, pH and dissolved oxygen) are also studied. The total concentrations of Cd, Cr, Mn and Ni in the samples are determined using inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS). The result indicates the comparatively low concentrations of the four metals (the max. of 0.67 mg/kg of Cd, 85.80 mg/kg of Cr, 1073.00 mg/kg of Mn and 38.62 mg/kg of Ni), the distribution rule of four metals in different regions of the studying area and the sources of the pollution. The methods of index of geoaccumulation, potential ecological risk index and pollution load index are used to assess the degree of contamination, distribution character and the sequence of pollution level in different regions which reflect the overall low values and low pollution level. The six-step sequential extraction method is used to determine the chemical forms of the four metals in order to evaluate their possible mobility, bioavailability and toxicity in surficial sediments. Cd and Mn are mostly concentrated in the CARB fraction, while Ni and Cr are mostly concentrated in the RES fraction. The mobility of the metals has the following order (average value): Cd > Mn > Ni > Cr.     

Diagenetic mobility of trace elements in sediments covered by a flash flood deposit: Mn,Fe and As

The vertical distribution and concentrations of Fe, Mn, and As were measured in porewaters and sediments recovered with box-cores taken each year since the 1996 flood along the main axis of the Saguenay Fjord and in the Baie des Ha! Ha!. Time-series analyses reveal that Mn remobilization was not significantly affected by the accumulation of the flood deposit. Authigenic Mn oxi-hydroxides present at the original sediment–water interface and in the flood material were progressively reduced, and much of the Mn(II) diffused to the current interface, where it was oxidized and precipitated. First-order rate constants for the reduction and precipitation of the authigenic Mn oxi-hydroxides were estimated by fitting the time-series data to a diagenetic model. On the basis of these rate constants and given that the maximum reactive solid Mn remains concentrated in the thin, oxic layer near the sediment-water interface, an upper limit to the biodiffusion coefficient, D_B, was also evaluated. In contrast to Mn, Fe associated with the authigenic oxi-hydroxides at the original interface was mostly trapped as acid volatile sulfides (i.e., AVS) under the SO₄-reducing conditions established rapidly after the flood. Most of the As associated with the authigenic oxi-hydroxides at the original (buried) interface also appears to be trapped with the authigenic sulfides, thus limiting its diffusion through the flood deposit.     

Bottom sediments and pore waters near a hydrothermal vent in Lake Baikal (Frolikha Bay)

We discuss the redox environments and the compositions of bottom sediments and sedimentary pore waters in the region of a hydrothermal vent in Frolikha Bay, Lake Baikal. According to our results, the submarine vent and its companion nearby spring on land originate from a common source. The most convincing evidence for their relation comes from the proximity of stable oxygen and hydrogen isotope compositions in pore waters and in the spring water. The isotope composition indicates a meteoric origin of pore waters, but their major- and minor-element chemistry bears imprint of deep water which may seep through permeable faulted crust. Although pore waters near the submarine vent have a specific enrichment in major and minor constituents, hydrothermal discharge at the Baikal bottom causes a minor impact on the lake water chemistry, unlike the case of freshwater geothermal lakes in the East-African Rift and North America.     

Batch and column experiments to support heavy metals (Cu,Zn and Mn) in alluvial sediments

Laboratory batch sorption and column transport experiments were performed on heterogeneous alluvial soils with a wide range of physical characteristics from wells that are located in the region between Mogan Lake and Eymir Lake, Gölba??, Ankara. The mean values for the K _d of Cu were found to be highest in clay (32550.350 L/kg) and lowest in loamy sand (18170.76 L/kg). The minimum and maximum sorption capacity values (mean values) for Zn were found to be in clay (10985.148 mg/kg) and in silty loam (8597.14 mg/kg) units, respectively. Similarly, the minimum and maximum values for Mn were found in loamy sand (4908.695 mg/kg) and clay (7587.391 mg/kg) units. The non-linear least-squares optimization code “CXTFIT” was used to determine transport parameter values by curve-fitting. The results of the column experiments demonstrate dispersivity values within the range of 0.024–1.13 cm for soil samples.     

云南砚山晚二叠世煤中V、Cr、Mo和U的丰度与赋存状态

运用电离耦合等离子体质谱(ICP-MS)和逐级化学提取(SCEE)的方法测定了云南砚山晚二叠世煤中金属元素的含量,发现煤中高度富集V、Cr、Mo和U,含量分别为621 μg/g、315 μg/g、198 μg/g和167 μg/g.逐级化学提取结果表明,这4种元素主要赋存在有机质和硅铝化合物中,反映其是在泥炭聚集期间或成岩作用早期进入到泥炭沼泽而富集的.     

Distribution of trace elements in waters and sediments of the Seversky Donets transboundary watershed (Kharkiv region,Eastern Ukraine)

This paper reports on the aquatic chemistry of trace elements in terms of spatial and temporal distribution, but also pollution sources in the transboundary watershed of the Seversky Donets River (Ukraine/Russia). Bed sediments and filtered water were collected from the Udy and Lopan Rivers at sites from the river source in the Belgorod region (Russia) to rural and urban areas in the Kharkiv region (Ukraine) in May and August 2009. Priority trace elements (As, Cd, Cr, Cu, Hg, Ni, Pb and Zn), an urban tracer (Ag) and additional metals (Co, Mo, V) and Th were measured in stream water and sediments. The low levels and variability of Th-normalized concentrations indicated the absence of geochemical anomalies in the upstream part of the rivers and suggested that these data represent a regional baseline for trace elements in bed sediments. In contrast, water and sediments within the city of Kharkiv were contaminated by Ag, Pb, Cd, Cu, Cr and Zn, which are mainly attributed to municipal wastewater inputs and urban run-off. Results of the environmental quality assessment showed that element concentrations in the sediments can be considered as potentially toxic to aquatic organisms in sites downstream of the wastewater discharges.     

氧化还原敏感元素(Se,Cr,Mo)稳定同位素

由于同位素分析方法的改进及表面热离子质谱(TIMS)和多接收电感耦合等离子体质谱(MC-ICP-MS)的应用,近年来氧化还原敏感元素(Se、Cr、Mo)同位素地球化学得以快速发展,成为国际地学领域的一个前沿。Se同位素在自然界中的变化最大,δ82/76SeNIST为-12.77‰～3.04‰;Cr和Mo同位素变化较小,δ53/52CrNIST值为-0.07‰～0.37‰,δ97/95MoJMC值为-0.27‰～2.65‰。自然界中各种无机过程(氧化还原)和生物有机过程均能使Se、Cr、Mo产生同位素分馏。因此,这些氧化还原敏感元素同位素可以示踪环境污染源、矿床流体来源;解释古海洋与现代海洋中元素的自身循环,从而示踪古氧化还原环境的演化;解释地外撞击事件及宇宙行星演化;甚至在生物学等领域研究中取得了显著成效。虽然还存在一些问题但它们将可能成为地球科学中有巨大应用前景的一种新兴的地球化学工具。     

高压微波消解法测定醋酸纤维过滤器采集的微尘粒子中的砷镉钴铬铜铁锰镍铅钒锌

最新的流行病学研究表明,空气中较高浓度的悬浮细颗粒可能对人类的健康有不利的影响。根据该项研究显示,由于心脏病、慢性呼吸问题和肺功能指标恶化而导致死亡率的升高与细尘粒子有关。这些研究结果已经促使欧盟于1999年4月出台了限制空气中二氧化硫、二氧化氮、氧化氮、铅和颗粒物含量的法案（1999/30/EC）,对各项指标包括对可吸入PM10颗粒的浓度提出了新的限制性指标。PM10颗粒是指可以通过预分级器分离采集的气体动力学直径小于10 μm的细颗粒。目前研究的兴趣重点逐步偏向PM2.5这些更细微颗粒物,PM2.5这种颗粒物对健康有明显的不利影响。在欧盟指令2008/50/EC中,对PM10和PM2.5都提出了具体测定要求。     

Oxidation products of Mn(II) in lake waters

Oxygenation of Mn(II)-rich water samples taken from two English lakes (Esthwaite Water, Cumbria, and Rostherne Mere, Cheshire) during the summer months caused the precipitation of Mn-oxide, the process being catalysed by particulate matter. The Mnoxide formed resembles vernadite (δ-MnO₂) with regard to: (1) Mn oxidation state (> 3.6 in all but one case); and (2) its fine morphology (crumpled thin sheets) as determined by electron microscopy. The precipitates are, however, rather amorphous to X-rays, giving only very weak reflections which cannot be assigned unequivocally. Electron probe microanalysis shows the presence of a number of other elements in the Mn-containing phase. The most abundant is Ca (Ca/Mn weight ratio $\text{? 0.1}$), others are Mg, Si, P, S, Cl, K, Ba and Fe. The precipitates contain much organic matter (20–30 wt.%) but little appears to be associated directly with the Mn phase. Only small amounts (～ 1 wt.%) of humic substances are present. Some but not all of the specimens examined had the gross morphology of Metallogenium, a Mn-depositing bacterium.Naturally occurring Mn-oxides present in Esthwaite Water during the summer resemble, the products of oxygenation in their fine morphology and contents of other elements. Mn-oxides present during the winter are somewhat different morphologically. In one summer sample of particulate matter from Esthwaite Water no Mn-oxide could be found by electron microscopic examination, but Mn was found concentrated in bacteria. This observation, the rapid rates of oxidation and the high Mn oxidation states, suggest that bacteria might play a rôle in catalysing the oxidation of Mn(II).