Trace metal remobilization following the resuspension of estuarine sediments: Saguenay Fjord,Canada

The Saguenay Fjord sediments are characterised by high trace metal, organic matter and Fe monosulfide (AVS) concentrations. The presence of important maritime activities, dredging operations around harbour installations, and natural slumpling events contribute to the resuspension of the Fjord sediments, their exposure to an oxidising environment, and the remobilization of a variety of contaminants to the water column.In order to simulate these processes, sediments collected from various depths in a box core recovered on the landward slope of the fjord's interior basin were resuspended in aerated seawater in the laboratory at room temperature. The slurries were sampled at various time intervals over a period of nearly 2000 h and the dissolved Fe, Mn and As concentrations were determined. Results of this study indicate that the amount of Fe and As released to the solution is strongly correlated to the acid volatile sulfide (AVS) content of the resuspended sediments. The release of Mn to the water phase, however, appeared to be mainly controlled by the dissolution of a solid phase, other than the Fe monosulfides but soluble in 1 N HCl, to which Mn (II) is associated. This phase could be a Mn carbonate or a mixed Mn–Ca carbonate.The dissolved metal concentrations measured at any time during the resuspension experiments reflect the reactivity of the carrier phases and the competing kinetics of the release and removal mechanisms. Upon their release to solution, Fe, Mn and As were scavenged by the newly precipitated Fe and Mn oxyhydroxides. The differential rate of formation of these phases and removal of associated metals in solution reflects their respective oxidation kinetics. The residence time of As in solution was very similar to that of Mn, implying that it was more efficiently removed with the slowly precipitated Mn oxyhydroxides. This observation is consistent with the faster oxidation kinetics of As (III) to As (V) in the presence of Mn oxyhydroxides. Nevertheless, results of As speciation analyses also suggest that a portion of the solubilized As was adsorbed and possibly oxidised by the rapidly precipitated Fe oxyhydroxides.     

Calcium carbonate dissolution history in late quaternary deep-sea sediments,Western Gulf of Mexico

Calcium carbonate dissolution has been studied in eight piston cores from the western Gulf of Mexico ranging in depth from 965 to 3630. The degree of dissolution throughout the cores was determined by studies of foraminiferal test fragmentation, benthonic foraminiferal abudance, calcium carbonate concentration, and various relationships between solution-resistant and solution-susceptible species. The paleoclimatic history recorded in these cores is similar to those defined previously in the Gulf of Mexico and equatorial Atlantic. Two mesgascopically distinct ash layers and well-defined planktonic foraminiferal subzones permit precise intercore correlation of dissolution horizons. All cores demonstrate intense dissolution during several subzones, especially during the early-middle Y, X1, and W1. Other less consistent dissolution horizons occur in various cores. Sedimentation rates increase while calcite concentrations decrease during glacial episodes suggesting increased dilution by terrigenous materials. Despite this, glacial episodes show greater dissolution and worse preservation of foraminiferal tests. Therefore, increased dissolution of calcium carbonate during glacial episodes must be a function of some mechanism that more than compensates for the increased rate of burial by terrigenous sediments. Dissolution is dissolution processes are not responsible for the observed effects. The oxidation of organic material may be the primary mechanism controlling the dissolution of calcium carbonate in the western Gulf of Mexico.     

Geochemical features of heavy metals in core sediments of northwestern Taihu Lake, China

Sequential core sediments from northwestern Taihu Lake in China were analyzed for grain size, organic carbon and heavy metal content. The sediments are composed of organic-poor clayey-fine silts. The chemical speciations of Cu, Fe, Mn, Ni, Pb, and Zn were also analyzed using the BCR sequential extraction procedure. Cu, Fe, Ni, and Zn are mainly associated with the residue fraction; Mn is concentrated mainly in exchangeable/carbonate fraction and residue fraction; and Pb mainly in Fe/Mn oxide fraction and organic/sulfide fraction. The exchangeable/carbonate fractions of Cu, Fe, Ni, Zn and Pb are lower. The fractions of Ni, Pb and Zn bound to the Fe/Mn oxide have significant correlations with reducible Mn; the organic/sulfide fractions of Cu, Mn, Ni, Pb, and Zn have significant correlations with TOC. The extractable fractions of Cu, Mn, Ni, Pb, and Zn are high at the top 4 cm of the core sediments as compared to those in the deeper layers, showing the anthropogenic input of heavy metals is due to rapid industrial development. The heavy metal pollution history of the sediments has been recorded since the late 1970s, determined by the result of ^137Cs dating.     

Rare elements and Nd and Sr isotopic composition in micronodules from the Brazil Basin,Atlantic Ocean

The Sr isotope stratigraphy of the biogenic apatite was used to determine the age of pelagic sediments in the Brazil Basin (Station 1541) that contain ferromanganese micronodules, nodules, and coatings on the weathered volcanic rocks. The age of sediments at horizons 0–5 and 86–90 cm was estimated at 24.1 ± 0.2 Ma and 24.8 ± 0.2 Ma, respectively. The average sedimentation rate in the Late Oligocene was about 13 mm/ka. The hydrogenous Fe–Mn nodule on the sediment surface with the Mn/Fe value of 1.05–1.95 was formed at a rate of 1.2–2.4 mm/Ma, which is 1000 times lower than the growth rate of buried nodule (Mn/Fe 0.4) at depth of 83 cm. Diagenesis provoked changes in the mineral composition of the buried nodule (asbolane-buserite partially replaced by goethite), leading to the loss of a part of Mn, Ni, Li, and Tl but accumulation of trace elements linked with iron oxyhydroxides (Ce, Th, Be, As, and V) were retained. The composition of manganese micronodules at two studied depths in sediments evolved in the course of two stages of ore formation: related to the oxic and suboxic diagenesis. The Sr isotopic composition in manganese micronodules from both horizons do not differ from that of dissolved Sr in the ocean water. The ¹⁴³Nd/¹⁴⁴Nd ratio, which reflects the Nd isotopic composition in the paleocean during the micronodule formation, varies in manganese micronodules from different horizons and is constant in different size fractions.     

Remobilization of transition metals in surficial pelagic sediments from the eastern Pacific

The top thirty centimeters of sediment at two sites in the eastern equatorial Pacific contain evidence of post-depositional remobilization of Mn, Fe, Co, Ni, Cu, and Zn. Remobilization takes place as Mn and Fe oxyhydroxides are released to the pore water during the microbially-mediated decomposition of organic matter. Precipitation of the dissolved metals in near-surface more oxic strata controls the solid-phase distribution of Mn, Fe, and Zn. The solid-phase redistribution of Co and Ni requires only suitable material for readsorption. Comparison of pore water fluxes with solid-phase metal distributions in the solid sediment indicates no loss of dissolved metal to the overlying water column at the present time. Loss of Mn during the Quaternary is indicated by the composition of the sediments, however. Leaching experiments suggest that portions of the mobile Mn, Fe, Co, Ni, and Cu are fixed by incorporation in authigenic smectite in the surficial sediments.     

Geochemistry of two sediment cores from the west coast of India

Copper, Pb, Zn, Ni, Co, Mn, AI, Ca, magnetic susceptibility and loss on ignition of sediments from two cores near Mangalore along the western continental shelf of India have been studied. The sediments have high Al and organic matter contents due to the high sedimentation rate and their proximity to river mouths. Down-core variations of elements indicate a decrease of lithogenous component during probably the past few centuries. While abundance of calcareous shells in some zones has lead to the dilution of most of the metals, it appears that Pb and Mn are associated with this phase. Copper, Zn and Fe are associated with organic matter and detrital particles, whereas Ni and Co are predominantly associated with the insoluble fraction. Oxides/hydroxides of Fe and Mn are absent because of the reducing conditions and the high terrigenous influx. Geochemically, Mn and Fe are present in different phases of sediments (in the insoluble fraction and organic matter respectively). The Fe content of one of the cores is positively correlated with magnetic susceptibility.     

The importance of surface area in metal sorption by oxides and organic matter in a heterogeneous natural sediment

This study provides empirical validation of current trace metal sorption theory in a small urban river. We demonstrate that trace metal complexation reactions occur predominantly at the suspended particulate surface involving surface layers of Fe oxides and organic matter. Associated surface areas of these geochemical fractions were calculated where possible, using the total surface area (TSA) of the suspended particulate matter pool (SPM) in conjunction with estimates of suspended iculate Fe and Mn oxides (SPOX) and organic matter (SPOM) concentrations. Iron and Mn oxides concentrations were estimated using an extraction scheme. For two samples where no SPOM or Mn oxides were present, estimates of Fe oxides associated surface area were determined which compared favourably to literature estimates, providing further evidence for acceptance selectivity of extraction schemes. The utility of literature estimates of surface areas for single component sediments in heterogeneous sediments was also assessed. In mixed sediment samples, exposed surface areas of discrete phases are probably reduced due to mixed layering effects of the coatings, and the use of constants to estimate the surface areas of individual fractions does not work, since the relationship between the concentration of a given sedimentary fraction and its exposed surface area is no longer predictable.     

Composition of manganese nodules and manganese carbonates from Loch Fyne,Scotland

Manganese nodules and manganese carbonate concretions occur in the upper 10–15 cm of the Recent sediments of Loch Fyne, Argyllshire in water depths of 180–200 m. The nodules are spherical, a few mm to 3 cm in diameter, and consist of a black, Mn-rich core and a thin, red, Fe-rich rim. The carbonate occurs as irregular concretions, 0.5–8 cm in size, and as a cement in irregular nodule and shell fragment aggregates. It partially replaces some nodule material and clastic silicate inclusions, but does not affect aragonitic and calcitic shell fragments.The nodules are approximately 75% pure oxides and contain 30% Mn and 4% Fe. In the cores, the principal mineral phase is todorokite, with a Mn/Fe ratio of 17. The rim consists of X-ray amorphous Fe and Mn oxides with a Mn/Fe ratio of 0.66. The cores are enriched, relative to Al, in K, Ba, Co, Mo, Ni and Sr while the rims contain more P, Ti, As, Pb, Y and Zn.The manganese carbonate has the composition (Mn_47.7 Ca_45.1 Mg_7.2) CO₃. Apart from Cu, all minor elements are excluded from significant substitution in the carbonate lattice.Manganese nodules and carbonates form diagenetically within the Recent sediments of Loch Fyne. This accounts for the high Mn/Fe ratios in the oxide phases and the abundance of manganese carbonate concretions. Mn concentrations in the interstitial waters of sediment cores are high (ca. 10 ppm) as also, by inference, are the dissolved carbonate concentrations.     

The Association of Cobalt with Iron and Manganese (Oxyhydr)oxides in Marine Sediment

Formation and dissolution of authigenic Fe and Mn (oxyhydr)oxides influence cycling of trace metals in oxic/suboxic surface sediments. We used the diffusive gradients in thin films technique (DGT) to estimate the association of cobalt with iron and manganese oxides. We compared Co, Fe and Mn maxima measured by DGT in the pore waters of fresh and aged marine sediment cores and estimated the Co/Fe and Co/Mn ratios in the metal oxides. A Mn maximum was not visible in DGT concentration profiles of freshly collected sediment cores, but after ageing the sediment, we observed a distinct Mn peak, presumably due to broadening of the depth range over which the various electron acceptors occur. Estimated Co/Mn ratios from both experiments are within the range of literature values for marine sediments, but the value from the aged experiment is at the lower end of the range. This is attributed to stimulation of sulphate reduction and precipitation of cobalt sulphides. The good correlation between Co and Fe maxima in the fresh sediments is attributed to the similarity of their reactions with sulphide rather than Co being released during authigenic Fe oxide reduction.     

Influence of a turbidite deposit on the extent of pyritization of iron,manganese and trace metals in sediments from the Guaymas Basin,Gulf of California (Mexico)

A core collected in the Guaymas Basin contained an organic-poor, Mn oxide-rich and (relatively) Fe oxide-rich turbidite layer that affected the distribution of Fe, Mn, C, S and trace metals. Results indicate that sediments not influenced by the turbidite layer achieved a 100% degree of pyritization and, by extension, that pyrite production is Fe-limited in these sediments. In contrast, the mud slide layer apparently supplied enough reactive Fe to transfer essentially 98% of the total S present at the base of the turbidite (17–19 cm) to the pyrite reservoir. C/S ratios showed rapid decreases with depth, from a high of 38 close to the sediment-water interface, to minimum values of 2.8 at the lower limit of the turbidite layer, a ratio equal to the average C/S value of normal marine modern sediments, where concentrations of organic C and pyrite supposedly have attained quasi-steady values. A significant part of the reactive Mn was associated with carbonates (41±12%) and, to a much lower degree, with pyrite (2.7±1.2%). The turbidite layer is currently showing a depletion of Mn relative to the host sediment. It is possible that Mn, a major metal constituent in these sediments, was initially present in high concentrations in the mud slide, but was eventually mobilized and transferred either to the water column or to the sediments immediately below the turbidite layer. Metals associated with this element probably followed the same path, affecting their incorporation into pyrite. The turbidite layer apparently affected the distribution of most of the trace metals associated with pyrite, except maybe Cd, Pb and, to a certain, extent Cr. However, Cu, Cr, Zn, Ni and Co were all found to be highly pyritized (>80%) in the sediments of the Guaymas Basin.     

Calcite cementation during bacterial manganese, iron and sulphate reduction in Jurassic shallow marine carbonates

Faunally restricted argillaceous wackestones from the Middle Jurassic of eastern England contain evidence of early diagenetic skeletal aragonite dissolution and stabilization of the carbonate matrix, closely followed by precipitation of zoned calcite cements, and precipitation of pyrite. Distinctive cathodoluminescence and trace element trends through the authigenic calcites, their negative δ¹³C compositions and the location of pyrite in the paragenetic sequence indicate that calcite precipitation took place during sequential bacterial Mn, Fe and sulphate reduction. Calcite δ¹⁸O values are compatible with cementation from essentially marine pore fluids, although compositions vary owing to minor contamination with ¹⁸O-depleted ‘late’cements. Mg and Sr concentrations in the calcites are lower than those in recent marine calcite cements. This may be a result of kinetic factors associated with the shallow burial cementation microenvironments. Bicarbonate for sustained precipitation of the authigenic calcites was derived largely from aragonite remobilization, augmented by that produced through anaerobic organic matter oxidation in the metal and sulphate reduction environments. Aragonite dissolution is thought to have been induced by acidity generated during aerobic bacterial oxidation of organic matter. Distinction of post-oxic metal reduction and anoxic sulphate reduction diagenetic environments in modern carbonate sediments is uncommon outside pelagic settings, and early bacterially mediated diagenesis in modern platform carbonates is associated with extensive carbonate dissolution. High detrital Fe contents of the Jurassic sediments, and their restricted depositional environment, were probably the critical factors promoting early cementation. These precipitates constitute a unique example of calcite authigenesis in shallow water limestones during bacterial Mn and Fe reduction.     

Partitioning of heavy metals in surface Black Sea sediments

Bulk heavy metal (Fe, Mn, Co, Cr, Ni, Cu, Zn and Pb) distributions and their chemical partitioning, together with TOC and carbonate data, were studied in oxic to anoxic surface sediments (0–2 cm) obtained at 18 stations throughout the Black Sea. TOC and carbonate contents, and available hydrographic data, indicate biogenic organic matter produced in shallower waters is transported and buried in the deeper waters of the Black Sea. Bulk metal concentrations measured in the sediments can be related to their geochemical cycles and the geology of the surrounding Black Sea region. Somewhat high Cr and Ni contents in the sediments are interpreted to reflect, in part, the weathering of basic-ultrabasic rocks on the Turkish mainland. Maximum carbonate-free levels of Mn (4347 ppm), Ni (355 ppm) and Co (64 ppm) obtained for sediment from the shallow-water station (102 m) probably result from redox cycling at the socalled ‘Mn pump zone’ where scavenging-precipitation processes of Mn prevail. Chemical partitioning of the heavy metals revealed that Cu, Cr and Fe seem to be significantly bound to the detrital phases whereas carbonate phases tend to hold considerable amounts of Mn and Pb. The sequential extraction procedures used in this study also show that the metals Fe, Co, Ni, Cu, Zn and Pb associated with the ‘oxidizable phases’ are in far greater concentrations than the occurrences of these metals with detrital and carbonate phases. These results are in good agreement with the recent studies on suspended matter and thermodynamic calculations which have revealed that organic compounds and sulfides are the major metal carriers in the anoxic Black Sea basin, whereas Fe-Mn oxyhydroxides can also be important phases of other metals, especially at oxic sites. This study shows that, if used with a suitable combination of the various sequential extraction techniques, metal partitioning can provide important information on the varying geological sources and modes of occurrence and distribution of heavy metals in sediments, as well as, on the physical and chemical conditions prevailing in an anoxic marine environment.     

Particulate iron and manganese in the Santa Barbara Basin,California

Particulate Fe and Mn may be important trace metal scavengers in the water column as well as being probable indicators of biologically mediated redox processes. A study has been made of suspended particulate composition in the Santa Barbara Basin, a shallow near-shore basin off southern California with sub-oxic conditions below sill depth. Observations have revealed several interesting phenomena relating to the geochemistry of Fe and Mn. Most striking is a profound enrichment of particulate Fe in samples from the bottom two hundred meters. These particulates have a constant Fe/P mole ratio of about three and may originate at the sediment-water interface or may be transported to the basin from local marshes. For particulate Mn, enrichments are observed both in the sub-sill waters and near the base of the euphotic zone. A consideration of particle removal rates suggests that the sub-photic zone enrichment has a biogenic origin. In the sub-sill waters, enrichment in Mn is apparently due to the precipitation of dissolved Mn diffusing from the anoxic basin sediments. A simple mass balance suggests that most of the Mn lost from the sediments is transported from the Santa Barbara Basin in dissolved form.     

Early diagenetic processes in coastal marine sediments disturbed by a catastrophic sedimentation event

Following a catastrophic flash flood in July 1996, as much as 50 cm of post-glacial clays were deposited in less than 2 days in the upper reaches of the Saguenay Fjord (Quebec, Canada), disrupting the normal sedimentation and diagenetic regimes. We report detailed geochemical analyses of sediments (porosity, Eh, organic and inorganic carbon, Fe and Mn reactive solid phases, and acid volatile sulfide) and porewaters (salinity, dissolved organic carbon (DOC), Fe(II), Mn(II), nitrate, ammonium, and sulfate) for seven stations located in the Saguenay Fjord. Three of these (SAG-05, SAG-09, and SAG-30) were visited in 1996 and once per year thereafter to document the chemical evolution of the sediment toward a new steady state. The flood deposits contain less organic carbon and more inorganic carbon than the indigenous fjord sediments. The flood deposit modified the distribution patterns of reactive Mn and Fe as a result of the reduction of Mn and Fe oxides delivered with the deposit and those concentrated at the now buried former sediment-water interface. Most of the Mn(II) migrated to the new sediment-water interface, where a Mn-rich layer was formed. In contrast, much of the Fe(II) was precipitated as sulfides and remained trapped at or close to the old interface. A nitrate peak developed in the porewater at the old sediment-water interface, possibly because of the oxidation of ammonia by Mn oxides. The distributions of porewater DOC within the flood deposit correlate with the distributions of dissolved Mn(II) and Fe(II), suggesting that adsorbed DOC was released when metal oxides were reduced.     

Geochemical and Mineralogical Characteristics of Pleistocene Lignites and Associated Sediments of Marathousa Coal Field,Central Peloponnese,Greece

The mineralogy and geochemistry data are presented for thirty-seven shales,four concretions,two carbonate sediments and seven lignites from the Marathousa coal field of the Megalopolis Basin in Greece.The argillaceous rocks consist of chlorite,illite,kaolinte,albite,quartz.opal-A,calcite and dolomite;the concretions of aragonite,gypsum and pyrite;and the carbonate rocks of calcite,quartz and illite.The mineral matter in the lignites consists of gypsum,quartz,albite,chlorite,illite,opal-A,dolomite,pyrite,and rarely calcite and kaolinite Athree-factor model explains the total variaition of major and trace elements in the argillaceous sediments.The first factor is an aluminosilicate factor and involves the following elements:Al,Si,Mg,Na,K,Ti,Mn,Nb,Y,Rb,Zn,Cu,Ni,Cr,Nband V,associated with chlorite,albite and illite.The second factor involves the elements Ca,Sr,Ba,Znand Sc and is related to carbonate lithology and mainly the carbonate concretions with gypsum.The third factor involves Fe and Ce with a weak association with Mn.The diagenesis of the Marathousa sediments and lignites was not very advanced as indicated by (a) the total thickness of the sequence (500m),(b) the presence of biogenic silica(opal-A) and (c) the age of the deposit(Pleistocene).FOr these reasons the rpresence of chlorite,illite and kaolinite in the sediments and lignite is due not to diagenetic reactions but to weathering of the flysch and metamorphic rocks at the edges of the Megalopolis Basin and transport of the weathering products(illite,chlorite,kaolinite)into the basin of deposition.The diagenetic minerals of the Marathousa sequence include pyrite,gypsum,dolomite and aragonite.     

Geochemistry and specific features of manganese ore formation in sediments of oceanic bioproductive zones

Processes of authigenic manganese ore formation in sediments of the northern equatorial Pacific are considered on the basis of study of the surface layer (<2 mm) of ferromanganese nodule and four micronodule size fractions from the associated surface sediment (0–7 cm). Inhomogeneity of the nodule composition is shown. The Mn/Fe ratio is maximal in samples taken from the lateral sectors of nodule at the water-sediment interface. Compositional differences of nodules are related to the preferential accumulation of microelements in iron oxyhydroxides (P, Sr, Pb, U, Bi, Th, Y, and REE), manganese hydroxides (Co, Ni, Cu, Zn, Cd, Mo, Tl, W), and lithogenous component trapped during nodule growth (Ga, Rb, Ba, and Cs). The Ce accumulation in the REE composition is maximal in the upper and lower parts of the nodule characterized by the minimal Mn/Fe values. The compositional comparison of manganese micronodules and surface layers of the nodule demonstrated that the micronodule material was subjected to a more intense reworking during the diagenesis of sediments. The micronodules are characterized by higher Mn/Fe and P/Fe ratios but lower Ni/Cu and Co/Ni ratios. The micronodules and nodules do not differ in terms of contents of Ce and Th that are least mobile elements during the diagenesis of elements. Differences in the chemical composition of micronodules and nodules are related not only to the additional input of Mn in the process of diagenesis, but also to the transformation of iron oxyhydroxides after the removal of Mn from the close association with Fe formed in the suspended matter at the stage of sedimentation.     

Geochemistry of Rare Earth Elements and Thorium in Sediments and Ferromanganese Nodules of the Atlantic Ocean

The behavior of rare earth elements (REE) and Th is studied along the west–east transect at 22°N across the Atlantic Ocean. It is shown that both REE and Th contents, relative to Al (the most lithogenic element), increase toward the pelagic region. The increasing trend becomes more complicated due to variations in the content of biogenic carbonate that serves as a diluting component in sediments. The REE composition varies symmetrically relative to the Mid-Atlantic Ridge (MAR) emphasizing a weak hydrothermal influence on sediments of the ridge axis, although the well-known criteria for hydrothermal contribution, such as Al/(Al + Mn + Fe) and (Fe + Mn)/Ti, do not reach critical values. Variations in the REE content and composition allowed us to distinguish the following five sediment zones in the transect: (I) terrigenous sediments of the Nares abyssal plain; (II) pelagic sediments of the North American Basin; (III) carbonate ooze of the MAR axis; (IV) pelagic sediments of the Canary Basin; and (V) terrigenous clay and calcareous mud of the African continental slope and slope base. Ferromanganese nodules of the hydrogenetic type with extremely high Ce (up to 1801 ppm) and Th (up to 138 ppm) contents occur in pelagic sediments. It is ascertained that P, REE, and Th concentrations depend on Fe content in Atlantic sediments. Therefore, one can suggest that only a minor amount of phosphorus is bound in bone debris. The low concentration of bone debris phosphorus is a result of relatively high sedimentation rates in the Atlantic, as compared with those in pelagic regions of the Pacific.     

太湖MS岩芯重金属元素地球化学形态研究

采用BCR三步提取法对太湖MS岩芯沉积物中Cu、Fe、Mn、Ni、Pb和Zn等6种重金属元素的化学形态进行了研究.结果表明,有效结合态的Cu、Ni和Pb主要以有机物及硫化物结合态、Fe-Mn氧化物结合态存在,Fe和Zn主要以Fe-Mn氧化物结合态存在,Mn主要以可交换态及碳酸盐结合态存在;Fe-Mn氧化物结合态的Ni、Pb和Zn与可还原态的Mn有较好的正相关关系,有机物及硫化物结合态的Cu、Mn、Ni、Pb和Zn与有机碳含量有较好的正相关关系;重金属形态分布体现了重金属元素地球化学性质的差异,以及重金属形态含量与沉积物理化性质的关系.沉积岩芯重金属元素形态垂向变化规律及次生相富集系数表明,Cu、Mn、Ni、Pb和Zn在沉积岩芯13～4 cm有效结合态含量较稳定,为自然沉积;4～0 cm有效结合态含量明显升高,存在一定程度的人为污染.根据137Cs测年结果判断,沉积岩芯Cu、Mn、Ni、Pb和Zn等重金属污染开始于20世纪70年代末期,主要污染元素及污染历史与太湖流域污染工业类型及经济发展阶段相吻合.     

The post-depositional reactivity of iron and managanese in the sediments of a macrotidal estuarine system

Four cores of anoxic sediments were collected from the Seine estuary to assess the early diagenesis pathways leading to the formation of previously reactive phase. Pore waters were analyzed for dissolved iron (Fe) and manganese (Mn) and different ligands (e.g., sulfate, chloride, total inorganic carbon). The anoxic zone is present up to the first centimeter depth, in these conditions the reduction of Mn and Fe oxides and SO₄ ²⁻ was verified. The sulfate reduction was well established with a subsequent carbon mineralization in the NORMAI94 core. The chemical speciation of Mn and Fe in the dissolved and solid phases was determined. For the dissolved phase, thermodynamic calculations were used to characterize and illustrate the importance of carbonate and phosphate phases as sinks for Fe and Mn. The ion activity product (IAP) of Fe and Mn species was compared to the solubility products (Ks) of these species. In the solid phase, the presence of higher concentration of calcium carbonate in the Seine sediments is an important factor controlling Mn cycle. The carbonate-bound Mn can reach more than 75% of the total concentration. This result is confirmed by the use of electron spin resonance (ESR) spectroscopy. The reduction of Fe is closely coupled to the sulfate reduction by the formation of new solid phases such as FeS and FeS₂, which can be regarded as temporal sinks for sulfides. These forms were quantified in all cores as acid volatile sulfide (AVS: FeS+ free sulfide) and chromium reducible sulfide (CRS: FeS₂+elemental sulfur S⁰).     

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.