Geochemistry of trace metals in a fresh water sediment: field results and diagenetic modeling

Concentrations of Fe, Mn, Cd, Co, Ni, Pb, and Zn were determined in pore water and sediment of a coastal fresh water lake (Haringvliet Lake, The Netherlands). Elevated sediment trace metal concentrations reflect anthropogenic inputs from the Rhine and Meuse Rivers. Pore water and sediment analyses, together with thermodynamic calculations, indicate a shift in trace metal speciation from oxide-bound to sulfide-bound over the upper 20 cm of the sediment. Concentrations of reducible Fe and Mn decline with increasing depth, but do not reach zero values at 20 cm depth. The reducible phases are relatively more important for the binding of Co, Ni, and Zn than for Pb and Cd. Pore waters exhibit supersaturation with respect to Zn, Pb, Co, and Cd monosulfides, while significant fractions of Ni and Co are bound to pyrite. A multi-component, diagenetic model developed for organic matter degradation was expanded to include Zn and Ni dynamics. Pore water transport of trace metals is primarily diffusive, with a lesser contribution of bioirrigation. Reactions affecting trace metal mobility near the sediment-water interface, especially sulfide oxidation and sorption to newly formed oxides, strongly influence the modeled estimates of the diffusive effluxes to the overlying water. Model results imply less efficient sediment retention of Ni than Zn. Sensitivity analyses show that increased bioturbation and sulfate availability, which are expected upon restoration of estuarine conditions in the lake, should increase the sulfide bound fractions of Zn and Ni in the sediments.     

Influence of sediment redox conditions on release/solubility of metals and nutrients in a Louisiana Mississippi River deltaic plain freshwater lake

The influence of sediment redox conditions on solubility of selected metals and nutrients in sediment from a coastal Louisiana freshwater lake (Lake Cataouatche) receiving diverted Mississippi River water was quantified. Sediment redox was cycled step wise in 50 mV increments between oxidized (-200 to +500 mV) and reduced (+500 to -200 mV) conditions. Changes in sediment oxidation/reduction status and pH influenced solubility of both metals and nutrients. When redox potential (Eh) was increased from -200 to +500 mV, sediment pH decreased from 7.1 to 5.7. When the sediment Eh decreased from +500 to -200 mV, pH increased from 5.7 to 7.1. The increase in sediment acidity upon oxidation resulted in the release of the Pb, Ca, Mg, Al, and Zn into solution. The solution concentration of these elements was inversely proportional to Eh (P相似文献   

Decomposition of belowground litter and metal dynamics in salt marshes (Tagus Estuary, Portugal)

The concentrations of C, Fe, Mn, Zn, Cu, Pb and Cd were determined monthly in decomposing roots of Halimione portulacoides, using litterbag experiments, in two salt marshes of the Tagus estuary with different levels of contamination. Although carbon concentrations varied within a narrow interval during the experiment, litter decomposed rapidly in the first month (weight loss between 0.051 and 0.065 g d(-1)). The time variation of metals was examined in terms of Me/C ratios and metal stocks. Ratios of Fe/C and Mn/C and their metal stocks increased in spring, presumably due to the precipitation of oxides in the surface of decomposing roots. Subsequent decrease of Fe/C and Mn/C ratios suggests the use of Fe and Mn oxides, as electron acceptors, in the organic matter oxidation. Zinc, Cu, Pb and Cd ratios to C were, in general, higher than at initial conditions implying that metal that leached out was slower than carbon. However, metal stocks decreased during the experiment indicating that incorporation or sorption of metals in Fe and Mn oxides did not counterbalance the amount of Zn, Pb and Cd released from decomposing litter. An exception was observed for Cu, since stock in the less contaminated marsh (Pancas) increased during the decomposition, indicating that litter was efficient on Cu binding under more oxidising conditions. These results emphasize the importance of litter decomposition and sediment characteristics on metal cycling in salt marshes.     

A statistical assessment of the form of trace metals in oxidized estuarine sediments employing chemical extractants

The thin layer of oxidized sediment at the sediment—water interface plays an important role in the chemical and biological interactions of trace metals in estuaries. Chemical extractants can be useful in defining trace metal interactions in sediments. Extractions may aid in determining the abundance of the operationally-defined forms of substrates which are the most active in binding metals in sediments; in operationally-defining an “extractable” phase of trace metals in sediments; and in providing information necessary for determining the bioavailability of sediment-bound metals. Comparison of 10 techniques for metal and substrate extractions among the sediments of 19 estuaries from south and west England indicate substrate characterization is best accomplished by Fe and Mn extractions with acid ammonium oxalate or 1N HCl, and humic substances extraction with 0.1N NaOH or 1N ammonia. Partial fractionation of trace metals is best accomplished with 1N HCl. Statistical relationships indicate the extractable phase of Fe is more important than total Fe in binding Ag, Cd, Cu, Pb and Zn in oxidized sediments, and the operationally-defined humic substance fraction of organic materials is highly important in binding Ag and Cu. Statistical analysis within specific subsets of data indicate trace metals are partitioned among several substrates in most sediments, the substrates compete with one another for the metals, and the outcome of the competition is strongly influenced by the concentrations of the different substrates in the sediment.     

Study of heavy metal pollution and speciation in Buyak Menderes and Gediz river sediments

In this study, two economically important rivers of Turkey, Gediz and Buyuk Menderes (BM) are studied to determine their environmental pollution levels. An old analytical procedure involving sequential chemical extraction is improved and used for the partitioning of particulate trace metals (Cu, Co, Cr, Mn, Fe, Zn, Pb and Ni). Cationic and anionic Mn and Cr species with different phases are also determined by using leaching, extraction and ion exchange speciation processes.The sediment samples are analysed using graphic-furnace atomic absorption spectroscopy and differential pulse anodic stripping voltameter. Experimental results obtained on five replicate samples of fluvial bottom surface sediments at the sampling points demonstrate that the relative standard deviation of the sequential extraction procedure is generally better than +/-10%. The accuracy, determined by comparing total metal concentrations with the sum of the five sequential chemical extractions, is proved to be satisfactory. The detection limits established for three standard deviations of blank for different metals are identical and found to be 0.1mg/kg for sediment samples and 1 ppb for water samples. The results show that the pollution levels are significant especially for Pb, Cr, Mn and Zn in the Gediz river and Co, Mn, and Zn in the BM river. Comparison between our results and the measurements outlined before industrialization and the beginning of the intensive pesticide applications in agricultural fields (In: Broekaert et al., editors, Metal speciation in the environment, vol. 23. 1989. p. 601-11; A research on the environmental pollution in the agricultural fields and watering in the Aegean region, Ege University Research Project, No. 127 1988 (in Turkish); DSI Water Analyses Report, Ankara, 1985 (in Turkish)) show that the pollution in these rivers is probably originated from industrial, agricultural and domestic waste discharges.     

Speciation patterns of heavy metals in tropical estuarine anoxic and oxidized sediments by different sequential extraction schemes

The speciation patterns of Cu, Cd, Zn, Pb, Fe and Mn in sediment samples under anoxic and oxidized conditions were investigated using three-stage, four-stage and five-stage sequential extraction schemes. All the extraction schemes identify the non-residual metal among three basic operationally-defined host fractions, namely, exchangeable, reducible and organic/sulfide bound. The anoxic sediment samples were found to have been oxidized during the extraction stage for the reducible fraction under the three-stage and four-stage schemes and the moderately reducible fraction under the five-stage scheme despite the maintenance of an oxygen-free environment. This artifact has resulted in an over-representation of the reducible fraction and an under-representation of the organic/sulfide fraction in the heavy metal speciation patterns of anoxic sediment samples. For Cd, Zn and Pb which had > 70% associated with the acid volatile sulfide in the organic/sulfide fraction, this artifact has resulted in the observation of a decrease in the reducible fraction and, in some cases, an increase in the organic/sulfide fraction upon oxidation of the anoxic sediment samples.     

Effect of imposed anaerobic conditions on metals release from acid-mine drainage contaminated streambed sediments

Remediation of streams influenced by mine-drainage may require removal and burial of metal-containing bed sediments. Burial of aerobic sediments into an anaerobic environment may release metals, such as through reductive dissolution of metal oxyhydroxides. Mining-impacted aerobic streambed sediments collected from North Fork Clear Creek, Colorado were held under anaerobic conditions for four months. Eh, pH, and concentrations of Cd, Cu, Fe, Mn, and Zn (filtered at 1.5 μm, 0.45 μm, and 0.2 μm), sulfate, and dissolved organic carbon (DOC) were monitored in stream water/sediment slurries. Two sediment size fractions were examined (2 mm-63 μm and <63 μm). Sequential extractions evaluated the mineral phase with which metals were associated in the aerobic sediment. Released Cu was re-sequestered within 5 weeks, while Fe and Mn still were present at 16 weeks. Mn concentration was lower than in the initial stream water at and beyond 14 weeks for the smaller sized sediment. Cd was not released from either sediment size fraction. Zn was released at early times, but concentrations never exceeded those present in the initial stream water and all was re-sequestered over time. The greatest concentrations of Cu, Fe, Mn, and Zn were associated with the Fe/Mn reducible fraction. Sulfate and Fe were strongly correlated (r = 0.90), seeming to indicate anaerobic dissolution of iron oxy-hydroxy-sulfate minerals. DOC and sulfate were strongly correlated (r = 0.81), with iron having a moderately strong correlation with DOC (r = 0.71). Overall concentrations of DOC, sulfate, Cu, Fe, and Zn and pH were significantly higher (p < 0.05) in the water overlying the small sized sediment samples, while the concentrations of Mn released from the larger sized sediment samples were greater.     

Concentrations of heavy metals and plant nutrients in water, sediments and aquatic macrophytes of anthropogenic lakes (former open cut brown coal mines) differing in stage of acidification.

Concentration of heavy metals (Al, Ba, Cd, Co, Cr, Cu, Fe, Mn, Ni, Pb, Sr, V and Zn) as well as macronutrients (N, P, K, Ca, Mg, S) were measured in water, bottom sediments and plants from anthropogenic lakes in West Poland. The collected plants were: Phragmites australis, Potamogeton natans, Iris pseudoacorus, Juncus effusus, Drepanocladus aduncus, Juncus bulbosus, Phalaris arundinacea, Carex remota and Calamagrostis epigeios. Two reference lakes were sampled for Nymphaea alba, Phragmites australis, Schoenoplectus lacustris, Typha angustifolia and Polygonum hydropiper. These plants contained elevated levels of Cd, Co, Cr, Cu and Mn, and part of the plants contained in addition elevated levels of Mn, Fe, Pb, Ni and Zn. Analyses of water indicated pollution with sulfates, Cd, Co, Ni. Zn, Pb and Cu, and bottom sediments indicated that some of the examined lakes were polluted with Cd, Co and Cr. Strong positive correlations were found between concentrations of Co in water and in plants and between Zn in sediments and plants, indicating the potential of plants for pollution monitoring for this metal. Heavy metal accumulation seemed to be directly associated with the exclusion of Ca and Mg.     

Accumulation of metals in a horizontal subsurface flow constructed wetland treating domestic wastewater in Flanders, Belgium

This study assessed the accumulation of metals in a horizontal subsurface flow constructed wetland treating domestic wastewater of 350 PE after three years of operation. Metal concentrations in the influent wastewater, effluent, sediment, leaves, stems, and belowground biomass of Phragmites australis were analysed. Spatial variations were assessed by sampling at increasing distance from the inlet and at different positions across the width of the reed bed. All metals except Fe and Mn were efficiently removed in the CW, total metal concentrations in the effluent complied with basic environmental quality standards for surface water, and dissolved metal concentrations were often lower than analytical detection limits. Removal efficiencies varied between 49% for Ni and 93% for Al. Export of dissolved Mn and particulate Fe occurred, probably related to redox conditions in the sediment. After 3 years of operation, the sediment in the inlet area was significantly contaminated with Zn, Cu, and Cd, whereas Pb could form a contamination problem within the near future. The Cr and Ni levels in the sediment were low throughout the entire reed bed. At this stage of operation, the contamination problem was still situated within the inlet area and metal concentrations in the sediment decreased towards background values further along the treatment path. An exponential decrease of the metal mass in the sediment and belowground biomass was seen for all metals except Mn. Contrary to the other metals, Mn concentrations in the sediment increased with distance. For all metals, less than 2% of the mass removed from the wastewater after passage through the reed bed is accumulated in the aboveground reed biomass. The sediment acts as the primary sink for metals.     

The analysis of sediments from the Iowa River

The silt and clay fraction of bottom sediment was sampled from an eight-mile stretch of the Iowa River, downstream from the Coralville Reservoir. These samples were examined by means of X-ray fluorescence spectroscopy. Six heavy metals, Fe, Mn, Ba, Zr, Sr, and Rb, were found to be present in concentrations greater than 1 ppm. When compared to crustal averages, Sr and Rb were depleted by a factor of 4 and 3 respectively, probably due to preferential solution. Fe and Zr were in concentrations similar to crustal averages. Zr content could be related to content of the mineral zircon in the watershed. Barium was enriched by a factor of 2, probably reflecting a calcareous parent material. Manganese was enriched by a factor of 5 and remains unexplained.     

The character of the suspended and dissolved phases in the water cover of the flooded mine tailings at Stekenjokk, northern Sweden

Studies of the suspended and dissolved phases of the pond water, material collected from sediment traps, and surficial sediments/tailings from the flooded tailings pond at Stekenjokk have been performed. The aim was to characterise the material, to study the seasonal variations and to quantify possible resuspension of the tailings in the pond. The element concentrations in the pond at Stekenjokk seem to be largely controlled by processes controlling the precipitation and dissolution of Mn- and Fe-oxyhydroxides in both the water column and in the surficial tailings. Physiochemical processes such as weathering of silicates on the surrounding mountain slopes or dykes contributes both dissolved elements and detrital particles. The suspended phase consists of detrital silicate material as well as Fe- and Mn-oxyhydroxides. The average heavy metal concentrations are high, e.g. 0.42% Cu, 0.15% Pb and 3.1% Zn, which is probably due to sorption onto Fe- and Mn-oxyhydroxides. The suspended phase is richer in Fe, and particularly Mn, during the winter. The suspended phase resembles the material collected in sediment traps and the material in the surficial sediments. The pond water is well mixed during the ice-free season. The dissolved heavy metal concentrations are generally rather low with, e.g. maximum concentrations of 2.03 micrograms/l Cu, 0.23 microgram/l Pb and 268 micrograms/l Zn during the winter. Higher dissolved concentrations are found below the ice-cover above the sediment surface during the winter, caused by diffusion of elements from the sediment-water interface up into the pond water. Most of the metals occurring in the pond are dissolved and resuspension of tailings is negligible.     

Relationships among total recoverable and reactive metals and metalloid in St. Lawrence River sediment: bioaccumulation by chironomids and implications for ecological risk assessment

The availability and bioaccumulation of metals and metalloids, and the geochemical interactions among them, are essential to developing an ecological risk assessment (ERA) framework and determining threshold concentrations for these elements. The purpose of this study was to explore the relationships among total recoverable and reactive metals and metalloid in sediment and their bioaccumulation by chironomids. In the fall of 2004 and 2005, 58 stations located in the three fluvial lakes of the St. Lawrence River and its largest harbour area in Montreal, Canada, were sampled. Nine total recoverable and reactive metals (Al, Cd, Cr, Cu, Fe, Mn, Ni, Pb and Zn) and one metalloid (As) were measured in whole sediment using two extraction methods: HCl/HNO(3) and HCl 1N, respectively. The bioaccumulation of six metals (Cd, Cr, Cu, Ni, Pb and Zn) and As by chironomids was evaluated in a subset of 22 stations. Strong collinearities were observed between some total recoverable or reactive metal concentrations in sediment; two principal clusters, including collinear metals, were obtained. The first one included metals of mainly geological origin (Al, Cr, Fe, Mn, Ni), while the second one included As, Cd, Cu, Pb and Zn, which likely derive mainly from point sources of anthropogenic contamination. Each element also showed strong collinearity between their total recoverable and reactive forms (0.65< or =r < or =0.97). We can conclude that both chemical forms are equivalent for use in statistical models needed to explain biological responses and also in screening risk assessment. However, these relationships are not always proportional. Lower availability percentages were observed for Cd, Cu and Zn in the highly mixed-contaminated area of the Montreal Harbour, even though concentrations in sediment were higher. We observed a significant correlation (0.50< or =r < or =0.56) between concentrations in chironomids and concentrations of both total recoverable and reactive Cr and Pb in sediment. Arsenic was an exception, with accumulation by chironomids being highly related to reactive sediment concentrations. Finally, we observed variable influences of explanatory factors (e.g. sediment grain size, Al, Fe, Mn, S, TOC), depending on which metal or metalloid was being predicted in chironomids. In this context, it is difficult to choose a universal predictive method to explain the bioaccumulation of specific metals, and more research is still needed into normalization procedures that consider a combination of explanatory factors.     

Potential kinetic availability of metals in sulphidic freshwater sediments

The insolubility of metal sulphides is believed to limit the bioavailability of trace metals in sulphidic sediments. However, if non-equilibrium conditions are important, metals may be more available than simple thermodynamic calculations suggest. To investigate the possible dynamic supply of Cu, Ni and Zn in a sulphidic freshwater sediment, they were measured, along with iron, manganese and sulphide, by the technique of diffusive gradients in thin-films (DGT). DGT measures the supply of solute from sediment to solution in response to a local solute sink. Release of Mn, Cu, Zn and Ni was observed at the sediment surface and attributed to the supply from reductive dissolution of manganese oxides. The depth profile of simultaneously extractable metals (SEM) for Cu and Ni followed the shape of the Mn profile more closely than the profiles of either acid volatile sulphur (AVS) or Fe, again consistent with supply from Mn oxides. Solubility calculations for a mesocosm of homogenised sediment indicated supersaturation with respect to the sulphides of Fe, Cu, Ni and Zn, yet DGT measurements demonstrated a substantial supply of both trace metals and sulphide from the solid phase to the pore waters. Ratios of metals measured in pore waters by DGT were consistent with their release from iron and manganese oxides, indicating that supply, as much as removal processes, determines the pseudo-steady state concentrations in the pore waters. The observations suggest that trace metals are not immediately bound in an insoluble, inert form when they are in contact with sulphide. This has consequences for modelling metal processes in sediment, as well as for uptake by some biota.     

Localised remobilization of metals in a marine sediment

Trace metals and Fe and Mn were measured at vertical spatial resolutions of 2.5 and 5 mm in the top 35 cm of the profundal sediment of a Scottish sea-loch using DGT (diffusive gradients in thin films) technique. DGT probes lower adjacent metal concentrations in pore waters and induce a flux of metal from the solid phase to porewater. The concentrations of metals in porewaters at the interface of the probe were measured during its deployment in a box core. These measurements reflect porewater concentrations of metals and their rates of resupply from the local solid phase of a very small volume (25 microl) of sediment. There was pronounced horizontal and vertical structure in the interfacial concentrations. Horizontal variations were shown by results from adjacent DGT assemblies being markedly different in detail, while vertical structure was measured directly by the DGT-depth profiles. Iron and Mn varied systematically with depth, with both broad and detailed features of Co aligning with those of Mn. There was, however, evidence of additional localised sources of Co that were apparently unrelated to the redox behaviour that Mn typifies, but associated with the remobilization of Ni, possibly from mineral dissolution. Arsenic(III) was remobilized in well-defined zones. Detailed correspondence of As(II) with some Fe features suggest that its release is mechanistically-related to iron oxide dissolution, but the 3 orders of magnitude higher concentrations of Fe may sometimes obscure the association. These results demonstrate that, within sediments, metals may be released in discrete locations that are not measured by conventional porewater sampling techniques due to their horizontal averaging.     

Metal Accumulation In Sediments Of The Exclusive Economic Zone Of Qatar,Persian Gulf

The EEZ of Qatar is subjected to different landbased sources and marine activities. Twenty-three sediment samples were collected from the EEZ of Qatar, Persian Gulf and analyzed to determine the effect of increasing man-made activities on the structure and chemical composition of seabed. Grain size analysis support the predominance of sand sized sediments with patches of sandy silt at the northeastern and southeastern areas. Coarse grained sand was characterized by elevated carbonate content reaching >95%. Off the capital Doha and opposite to industrial parks, the organic matter reached >7.4%. Cu (0.8-30.3 r w g/g), Pb (2.2-22.6 r w g/g), Co (2.4-9.1 r w g/g) and Mn (36.8-746 r w g/g) levels were high compared to other Gulf values. Stations were clustered on the basis of sediment texture rather than metal accumulation. The high organic content of northeastern sediments, derived from planktonic origin is coupled by low metals concentrations. Except for Cr, Cu and Fe, the non-residual fraction of metals contributed between 56 and 92% of the total metals concentrations. Stations sampled closer to potential metal sources are characterized by increased non-residual fractions. Negligible or very low amount (<5%) of the non-residual fraction of metals appeared in the exchangeable phase. Metals are mostly associated with the easily and moderately reducible fraction (23% Fe, 17% Cr, 24% Co, 34% Mn, 14% Ni and 18% Cu) due to strong scavenging capabilities of Fe-Mn oxides. Pb is partitioned equally among easily/moderately reducible and carbonate fractions, dominating in the latter. Co (38%) and Ni (35%) are mostly associated with organic matter/sulphide phase, while Zn (27-29%) is equally partitioned between easily/moderately reducible, carbonate and organic matter phases. Cr (73%), Cu (62%) and Fe (58%) appeared mainly in the residual form. The concentrations of bioavailable metal fractions (exchangeable and easily/moderately reducible) do not put at risk the economically important living resources.     

Effect of redox potential on heavy metal binding forms in polluted canal sediments in Delft (The Netherlands)

Heavy metal binding forms for Cu, Zn and Pb were determined at four representative sediment sites in the canals of Delft (The Netherlands), using selective chemical extraction methods. Small differences (on average <5%) were found between duplicate extraction experiments. The dominant Cu binding form was always related to sulphide and organics in the sediment. Zn was mainly bound to iron+manganese (hydr)oxides, whereas Pb was rather evenly distributed over the different labile and non-labile binding fractions. A gradual (over about 1 month) increase in redox potentials of the anaerobic sediments led to a 7-37% sediment release of the above heavy metals; this could mainly be ascribed to oxidation of the heavy metal-sulphide bindings. Part of the released heavy metals was re-adsorbed by the labile binding phases ("exchangeable" and "carbonate bound"). Contrary to expectations, we found a decrease rather than an increase in the Fe+Mn (hydr)oxide binding forms. This can probably be ascribed to non-equilibrium reactions in the time span of the experiments, as well as side reactions such as complexation with humic acids and hindered precipitation reactions due to organic matter coatings.     

Distribution and mobility of arsenic in the Río Dulce alluvial aquifers in Santiago del Estero Province, Argentina

Factors controlling arsenic (As) mobilization in the aquifers of the Río Dulce alluvial cone were investigated. Groundwater analyses show severe As contamination (average concentration of 743 mug/L) from geogenic sources, but spatial variability of As concentration is considerable. Sequential leaching of sediment samples from unsaturated zone using de-ionised water, bicarbonate, acetate, and oxalate extracted As to different extents. Sediment oxalate extraction showed that Al and Mn oxide and hydroxides are more abundant than Fe oxides and hydroxides, in spite of similar total Fe, Mn, and Al concentrations in the sediment. Speciation calculations performed for saturated zone samples indicated that Fe and Al oxides and hydroxides are stable in groundwater, suggesting that As adsorption processes may be to some extent controlled by the presence of Fe and Al mineral phases. Principal Component Analysis (PCA) showed that As is related to F, V, Mo, B, Si, most likely due to their common origin in volcanic ash. This suggests the volcanic ash as the probable source of groundwater As. Locally, elevated pH values linked to carbonate dissolution, cation exchange, and dissolution of silicates promote release of adsorbed As. Another factor contributing to the release of As locally may be the input of organic matter from excessive irrigation. The conceptual model of As release includes: i) As influx from dissolution of volcanic glass in volcanic ash, ii) adsorption of As on the surface of Fe and Al mineral phases in relatively low pH zones, and iii) high mobility of As in high pH zones. Future work should be focused on the determination of mineralogical forms of As in volcanic ash and on detailed investigation on factors controlling As mobility.     

Dredging-related mobilisation of trace metals: a case study in The Netherlands

Mobilisation of contaminants is an important issue in environmental risk assessment of dredging projects. This study has aimed at identifying the effects of dredging on mobilisation of trace metals (Zn, Cu, Cd and Pb). The intensities and time scales of trace metal mobilisation were investigated during an experimental dredging project conducted under field conditions. The loss of contaminated dredge spoil is mainly reflected by increasing levels of trace metals in the suspended matter, dissolved trace metal concentrations in the water column are not significantly influenced by the dredging activities. This indicates a strong binding mechanism of trace metals to the solid phase or a fast redistribution over sorptive phases in response to oxidation of e.g. trace metal sulphides. Given the differences in levels of reactive phases (Mn, Fe, sulphides and organic matter) between the riverine suspended matter and the sediments, changes in the levels of these parameters in the suspended matter upon dredging may give information on the processes influencing the behaviour of trace metals and on the potential loss of sediment during dredging operations. Therefore, we recommend to routinely measure these parameters in studies on contaminant behaviour related to dredging activities.     

Heavy metal distribution,availability and fate in Sepetiba Bay,S.E. Brazil

The total flux, distribution and fate of Cu, Cr, Cd, Zn, Mn and Pb were studied in Sepetiba Bay, Rio de Janeiro, SE Brazil. Metal contamination in the bay is of the same order of magnitude as historically contaminated areas of Europe and North America, inspite of the recent (15–20 years) contamination of the area.The estimated metal fluxes to the bay in tons per year are: Cu, 2.7; Cr, 10.9; Cd, 0.9; Zn, 11.5; Mn, 20.4; and Pb, 4.5. For most metals, transport to the bay is mainly by suspended particulate matter; for Cd and Cr 90 and 47% of the total flux was in dissolved forms. Most metals transported by suspended particulate matter were in weakly bound forms.Analysis of bottom sediments showed two groups of metals in relation to their distribution and source in the bay. Manganese and Cu showed higher concentration along the southern parts of the bay, showing no correlation with the other metals, and probably being derived from natural sources. The other metals were present at higher concentrations along the depositional area of fluvial sediments, at the northern part of the bay, and are derived from industrial and urban sources.     

Geochemical changes in individual sediment grains during sequential arsenic extractions

High concentrations of As in groundwater frequently occur throughout the world. The dissolved concentration, however, is not necessarily determined by the amount of As in the ambient sediment but rather by the partitioning of As between different minerals and the type of fixation. Sequential extractions are commonly applied to determine associations and binding forms of As in sediments. Due to the operational nature of the extracted fractions, however, the results do not provide insight into how and where precisely As is bound within mineral grains and no information about elemental associations or involved mineral phases can be gained. Furthermore, little is known about possible geochemical alterations that actually occur within a single grain during sequential extraction. Therefore, micro-synchrotron X-ray fluorescence analysis was applied to study the micro-scale distribution of As and other elements in single sediment grains.Arsenic was found to be mainly enriched in Fe oxy-hydroxide coatings along with other heavy metals resulting in high correlations. Phosphate leached 34-66% of As from the studied grains. The release of As in this leaching step was accompanied by the disappearance of correlations between As and Fe as well as by a higher Fe/As ratio compared to untreated samples. During the Fe-leaching step the coatings were largely dissolved leading to much lower concentrations of As and Fe. The correlation between As and Fe was preserved only in association with K, indicating the presence of both elements in silicate structures.Several distinctive features were observed such as the release of Fe, Mn and Cr during phosphate leaching as well as the lowering of mean K concentrations due to the Fe-leaching which indicates that not only target mineral phases were dissolved in these extraction steps. The importance of re-precipitation processes during sequential extraction was indicated by a consistently observed increase of the Fe/As ratio from the untreated to the Fe-leached samples.