Dominance of dietary intake of metals in marine elasmobranch and teleost fish

Metal accumulation in marine fish is a global public health concern, because the consumption of seafood provides the largest dose of many toxic metals to humans. While water quality criteria often rely on aqueous exposures of metals to fish in developing safety guidelines, it is increasingly recognized that marine fish obtain an important fraction of their metal body burden from their diet. Using experimental data, we modeled the accumulation of six metals (Am, Cd, Cs, Co, Mn, Zn) from diet and from the aqueous phase in two marine fish species, the teleost Psetta maxima and elasmobranch Scyliorhinus canicula. We estimated steady-state metal concentrations and calculated the relative contributions of dietary and aqueous intake in both species. For both species > 60% and often > 90% of Mn, Cd, and Zn derives from dietary intake in these species, even at the lowest ingestion rates reported for these fish. At low ingestion rates, Am was obtained predominantly from the aqueous phase and Cs varied considerably depending on prey selection. Inter-specific differences were noted, especially in Co uptake. Model predictions of steady-state tissue metal concentrations are within the range of field measurements for these species. Our findings underscore the importance of including dietary exposure in understanding metal accumulation in marine fish.     

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.     

The impact of increased oxygen conditions on metal-contaminated sediments part II: effects on metal accumulation and toxicity in aquatic invertebrates

The present study evaluated the effect of increasing oxygen concentrations in overlying surface water on the accumulation and toxicity of sediment-bound metals in the aquatic invertebrates Lumbriculus variegatus, Asellus aquaticus and Daphnia magna. A 54 days experiment using three experimental treatments (90% O₂ in overlying surface water, 40% O₂ and a non-polluted control) was conducted. At 6 different time points (after 0, 2, 5, 12, 32 and 54 days) acid volatile sulfides (AVS), simultaneously extracted metals (SEM) and total organic carbon (TOC) were measured in the superficial sediment layer (0-1 cm). At each time point, accumulated metal levels as well as the available energy stores were measured in L. variegatus and A. aquaticus and each time D. magna was exposed to surface water in a 24 h toxicity test. Additionally metallothionein-like protein (MTLP) induction was quantified in L. variegatus. Oxygen induced changes in sediment AVS resulted in faster accumulation of metals from contaminated sediments in A. aquaticus, while no differences in toxicity in this species were observed. Ag, Cr, As and Co accumulation as well as toxicity in water exposed D. magna were clearly enhanced after 54 days, caused by oxidation of metal-sulfide complexes. Due to their feeding and burrowing behaviour, metal accumulation and toxicity in L. variegatus was not influenced by geochemical characteristics. Nevertheless, a rapid induction of MTLP was observed in both the 90% O₂ and the 40% O₂ treatment. The present study showed that elevated oxygen concentrations in overlying surface water can directly enhance metal accumulation and toxicity in aquatic invertebrates, however this is highly dependent on the organisms ecology and most dominant metal exposure route (water vs. sediment).     

Phylogenetic consistencies among chondrichthyan and teleost fishes in their bioaccumulation of multiple trace elements from seawater

Multi-tracer experiments determined the accumulation from seawater of selected radioactive trace elements (Mn-54, Co-60, Zn-65, Cs-134, Am-241, Cd-109, Ag-110m, Se-75 and Cr-51) by three teleost and three chondrichthyan fish species to test the hypothesis that these phylogenetic groups have different bioaccumulation characteristics, based on previously established contrasts between the carcharhiniform chondrichthyan Scyliorhinus canicula (dogfish) and the pleuronectiform teleost Psetta maxima (turbot). Discriminant function analysis on whole body: water concentration factors (CFs) separated dogfish and turbot in two independent experiments. Classification functions grouped the perciform teleosts, seabream (Sparus aurata) and seabass (Dicentrarchus labrax), with turbot and grouped the chondrichthyans, undulate ray (Raja undulata; Rajiformes) and spotted torpedo (Torpedo marmorata; Torpediniformes), with dogfish, thus supporting our hypothesis. Hierarchical classificatory, multi-dimensional scaling and similarity analyses based on the CFs for the nine radiotracers, also separated all three teleosts (that aggregated lower in the hierarchy) from the three chondrichthyan species. The three chondrichthyans were also more diverse amongst themselves compared to the three teleosts. Particular trace elements that were more important in separating teleosts and chondrichthyans were Cs-134 that was elevated in teleosts and Zn-65 that was elevated in chondrichthyans, these differences being due to their differential rates of uptake rather than loss. Chondrichthyans were also higher in Cr-51, Co-60, Ag-110m and Am-241, whereas teleosts were higher only in Mn-54. These contrasts in bioaccumulation patterns between teleosts and chondrichthyans are interpreted in the context of both proximate causes of underlying differences in physiology and anatomy, as well as the ultimate cause of their evolutionary divergence over more than 500 million years before present (MyBP). Our results and interpretation point to the possibility that radiation exposure regimes may be influenced by phylogeny, with implications for the adequacy of the marine reference organism approach in marine environmental protection.     

Selenium accumulation in aquatic biota downstream of a uranium mining and milling operation

Uranium mining and milling operations have the potential to release trace elements such as arsenic, molybdenum, nickel, selenium and uranium and ions (e.g., sulfate, ammonium) into the receiving aquatic ecosystem. The major implication of elevated environmental selenium is its propensity to accumulate in the aquatic food chain, potentially impairing fish reproduction. The objective of this study was to investigate the accumulation of selenium in the major compartments of aquatic ecosystems (lakes) upstream and downstream of a uranium mine in northern Saskatchewan, Canada. Selenium concentrations in aquatic biota were elevated in the exposure lake although water and sediment concentrations were low (0.43 μg/L and 0.54 μg/g dry weight, respectively). Biomagnification of selenium resulted in approximately 1.5 to 6 fold increase in the selenium concentration between plankton, invertebrates and fish. However, no biomagnification was observed between forage and predatory fish. Although some aquatic biota (e.g., forage fish) exceeded the lower limit of the proposed 3 to 11 μg/g (dry weight) dietary toxicity threshold for fish, no adverse effects of selenium could be identified in this aquatic system. Continued environmental monitoring is recommended to avoid potential selenium impacts.     

Distribution and bioaccumulation of microcystins in water columns: a systematic investigation into the environmental fate and the risks associated with microcystins in Meiliang Bay, Lake Taihu

For the purpose of understanding the environmental fate of microcystins (MCs) and the potential health risks caused by toxic cyanobacterial blooms in Lake Taihu, a systematic investigation was carried out from February 2005 to January 2006. The distribution of MCs in the water column, and toxin bioaccumulations in aquatic organisms were surveyed. The results suggested that Lake Taihu is heavily polluted during summer months by toxic cyanobacterial blooms (with a maximum biovolume of 6.7x10(8)cells/L) and MCs. The maximum concentration of cell-bound toxins was 1.81mg/g (DW) and the dissolved MCs reached a maximum level of 6.69mug/L. Dissolved MCs were always found in the entire water column at all sampling sites throughout the year. Our results emphasized the need for tracking MCs not only in the entire water column but also at the interface between water and sediment. Seasonal changes of MC concentrations in four species of hydrophytes (Eichhornic crassipes, Potamogeton maackianus, Alternanthera philoxeroides and Myriophyllum spicatum) ranged from 129 to 1317, 147 to 1534, 169 to 3945 and 124 to 956ng/g (DW), respectively. Toxin accumulations in four aquatic species (Carassius auratus auratu, Macrobrachium nipponensis, Bellamya aeruginosa and Cristaria plicata) were also analyzed. Maximum toxin concentrations in the edible organs and non-edible visceral organs ranged from 378 to 730 and 754 to 3629ng/g (DW), respectively. Based on field studies in Lake Taihu, risk assessments were carried out, taking into account the WHO guidelines and the tolerable daily intake (TDI) for MCs. Our findings suggest that the third largest lake in China poses serious health threats when serving as a source of drinking water and for recreational use. In addition, it is likely to be unsafe to consume aquatic species harvested in Lake Taihu due to the high-concentrations of accumulated MCs.     

Patterns of metal bioaccumulation in two filter-feeding macroinvertebrates: Exposure distribution, inter-species differences and variability across developmental stages

This study focused on the metal bioaccumulation of two aquatic insects (Ephoron virgo and Hydropsyche spp.) in order to evaluate the spatial distribution of metals, the interspecific differences between both filter-feeders and the bioaccumulation dynamics during E. virgo development stages. Hg, Cd, Ni, Cr, As, Pb, Cu, Ti, Zn and Mn were quantified in insects and in suspended particulate matter (SPM) sampled downstream and upstream of a chemical plant, where more than 300,000 t of polluted sediments are deposited. Hg concentrations were one order of magnitude higher downstream of the sediment dump, which showed that the Hg pollution originated in the chemical plant. Cd, Ni, Cr, Pb, Ti, Zn and Mn in invertebrates revealed that metal pollution was present upstream in other parts of the river. Interspecific differences were observed for all metals but Mn; significantly higher concentrations were observed in E. virgo over Hydropsyche exocellata, except for Cd, which showed 10-fold higher values. Hg and Cd increased until E. virgo nymphs reached 11 mm and decreased afterwards in late instars when nymphs were about to emerge. Cr, Pb, Ti and Mn decreased along early instars followed by a steady state in late instars. Similar values were obtained for Cu, As and Zn along all instars. Sexual differences between males and females of E. virgo were observed for Cd, Cu and Mn. Hg and Cd persistence was strong across developmental stages since high concentrations were found in eggs and emerging adults. Because the behavior of different metals varied for the two species and during the developmental stages of E. virgo, care should be taken in the interpretation of insect metal concentrations when analyzing the food chain transfer of metals in river ecosystems.     

Modeling of heterotrophic bacteria counts in a water distribution system

Heterotrophic plate count (HPC) constitutes a common indicator for monitoring of microbiological water quality in distribution systems (DS). This paper aims to identify factors explaining the spatiotemporal distribution of heterotrophic bacteria and model their occurrence in the distribution system. The case under study is the DS of Quebec City, Canada. The study is based on a robust database resulting from a sampling campaign carried out in about 50 DS locations, monitored bi-weekly over a three-year period. Models for explaining and predicting HPC levels were based on both one-level and multi-level Poisson regression techniques. The latter take into account the nested structure of data, the possible spatiotemporal correlation among HPC observations and the fact that sampling points, months and/or distribution sub-systems may represent clusters. Models show that the best predictors for spatiotemporal occurrence of HPC in the DS are: free residual chlorine that has an inverse relation with the HPC levels, water temperature and water ultraviolet absorbance, both having a positive impact on HPC levels. A sensitivity analysis based on the best performing model (two-level model) allowed for the identification of seasonal-based strategies to reduce HPC levels.     

Removal of metal ions by modified Pinus radiata bark and tannins from water solutions

Pinus radiata bark and tannins, chemically modified with an acidified formaldehyde solution were used for removing metal ions from aqueous solutions and copper mine acidic residual waters. The adsorption ability to different metal ions [V(V), Re(VII), Mo(VI), Ge(IV), As(V), Cd(II), Hg(II), Al(III), Pb(II), Fe(II), Fe(III), Cu(II)] and the factors affecting their removal from solutions were investigated. Effect of pH on the adsorption, desorption, maximum adsorption capacity of the adsorbents, and selectivity experiments with metal ion solutions and waste waters from copper mine were carried out. The adsorbents considerably varied in the adsorption ability to each metal ion. The adsorption depends largely upon the pH of the solution. Modified tannins showed lower adsorption values than the modified bark. For the same adsorbent, the maximum capacity at pH 3 for the different ions were very different, ranging for modified bark from 6.8 meqg⁻¹ for V to 0.93 meqg⁻¹ for Hg. Waste waters were extracted with modified bark as adsorbent and at pH 2. The ions Cu(II) (35.2 mgL⁻¹), Fe(III) (198 mgL⁻¹), Al(III) (83.5 mgL⁻¹) and Cd(II) (0.15 mgL⁻¹) were removed in 15.6%, 46.9%, 83.7% and 3.3%, respectively, by using 1 g of adsorbent/10 mL of waste water. In general, a continuous adsorption on a packed column gave higher adsorbed values than those observed in the batchwise experiment.     

Dietary exposure and biomarkers of arsenic in consumers of fish and shellfish from France

Seafood, especially fish, is considered as a major dietary source of arsenic (As). Seafood consumption is recommended for nutritional properties but contaminant exposure should be considered. The objectives were to assess As intake of frequent French seafood consumers and exposure via biomarkers. Consumptions of 996 high consumers (18 and over) of 4 coastal areas were assessed using a validated food frequency questionnaire. Seafood samples were collected according to a total diet study (TDS) sampling method and analyzed for total As, arsenite (AsIII), arsenate (AsV), arsenobetaïne (AsB), monomethylarsonic acid (MMA) and dimethylarsinic acid (DMA). The average As dietary exposure is 94.7 ± 67.5 μg/kg bw/week in females and 77.3 ± 54.6 μg/kg bw/week in males (p < 0.001) and the inorganic As dietary exposure is respectively 3.34 ± 2.06 μg/kg bw/week and 3.04 ± 1.86 μg/kg bw/week (p < 0.05).Urine samples were collected from 382 of the subjects. The average urinary As concentration is 94.8 ± 250 μg/g creatinine for females and 59.7 ± 81.8 μg/g for males (p < 0.001). Samples having an As concentration above 75 μg/g creatinine (n = 101) were analyzed for inorganic As (As(III), As(V), MMA(V) and DMA(V)) which was 24.6 ± 27.9 μg/g creatinine for males and 27.1 ±20.6 μg/g for females. Analyses do not show any correlation between dietary exposure and urinary As.These results show that biological results should be interpreted cautiously. Diet recording seems to be the best way to assess dietary As exposure. Seafood is a high source of As exposure but even among high consumers it is not the main source of toxic As. From a public health point of view these results should be interpreted carefully in the absence of international consensus on the health-based guidance value.     

Modeling DBPs formation in drinking water in residential plumbing pipes and hot water tanks

Disinfection byproducts (DBPs) in municipal supply water are a concern because of their possible risks to human health. Risk assessment studies often use DBP data in water distribution systems (WDS). However, DBPs in tap water may be different because of stagnation of the water in plumbing pipes (PP) and heating in hot water tanks (HWT). This study investigated occurrences and developed predictive models for DBPs in the PP and the HWT of six houses from three municipal water systems in Quebec (Canada) in a year-round study. Trihalomethanes (THMs) in PP and HWT were observed to be 1.4-1.8 and 1.9-2.7 times the THMs in the WDS, respectively. Haloacetic acid (HAAs) in PP and HWT were observed to be variable (PP/WDS = 0.23-2.24; HWT/WDS = 0.53-2.61). Using DBPs occurrence data from these systems, three types of linear models (main factors; main factors, interactions and higher orders; logarithmic) and two types of nonlinear models (three parameters Logistic and four parameters Weibull) were investigated to predict DBPs in the PP and HWT. Significant factors affecting DBPs formation in the PP and HWT were identified through numerical and graphical techniques. The R² values of the models varied between 0.77 and 0.96, indicating excellent predictive ability for THMs and HAAs in the PP and the HWT. The models were found to be statistically significant. The models were validated using additional data. These models can be used to predict DBPs increase from WDS (water entry point of house) to the PP and HWT, and could thereby help gain a better understanding of human exposure to DBPs and their associated risks.     

Modeling water flow and bacterial transport in undisturbed lysimeters under irrigations of dairy shed effluent and water using HYDRUS-1D

HYDRUS-1D was used to simulate water flow and leaching of fecal coliforms and bromide (Br) through six undisturbed soil lysimeters (70 cm depth by 50 cm diameter) under field conditions. Dairy shed effluent (DSE) spiked with Br was applied to the lysimeters, which contained fine sandy loam layers. This application was followed by fortnightly spray or flood water irrigation. Soil water contents were measured at four soil depths over 171 days, and leachate was collected from the bottom. The post-DSE period simulations yielded a generally decreased saturated water content compared to the pre-DSE period, and an increased saturated hydraulic conductivity and air-entry index, suggesting that changes in soil hydraulic properties (e.g. via changes in structure) can be induced by irrigation and seasonal effects. The single-porosity flow model was successful in simulating water flow under natural climatic conditions and spray irrigation. However, for lysimeters under flood irrigation, when the effect of preferential flow paths becomes more significant, the good agreement between predicted and observed water contents could only be achieved by using a dual-porosity flow model. Results derived from a mobile-immobile transport model suggest that compared to Br, bacteria were transported through a narrower pore-network with less mass exchange between mobile and immobile water zones. Our study suggests that soils with higher topsoil clay content and soils under flood irrigation are at a high risk of bacteria leaching through preferential flow paths. Irrigation management strategies must minimize the effect of preferential flow to reduce bacterial leaching from land applications of effluent.     

Bioaccumulation of As, Cd, Cr, Hg(II), and MeHg in killifish (Fundulus heteroclitus) from amphipod and worm prey

Elevated metal levels in fish are a concern for the fish themselves, their predators, and possibly humans who consume contaminated seafood. Metal bioaccumulation models often rely on assimilation efficiencies (AEs) of ingested metals and loss rate constants after dietary exposure (k_efs). These models can be used to better understand processes regulating metal accumulation and can be used to make site-specific predictions of metal concentrations in animal tissues. Fish often consume a varied diet, and prey choice can influence these two parameters. We investigated the trophic transfer of As, Cd, Cr, Hg(II), and methylmercury (MeHg) from a benthic amphipod (Leptocheirus plumulosus) and an oligochaete (Lumbriculus variegatus) to killifish (Fundulus heteroclitus) using gamma-emitting radioisotopes. Except for MeHg, AEs varied between prey type. AEs were highest for MeHg (92%) and lowest for Cd (2.9-4.5%) and Cr (0.2-4%). Hg(II) showed the largest AE difference between prey type (14% amphipods, 24% worms). For Cd and Hg(II) k_efs were higher after consuming amphipods than consuming worms. Tissue distribution data shows that Cd and Hg(II) were mainly associated with the intestine, whereas As and MeHg were transported throughout the body. Calculated trophic transfer factors (TTFs) suggest that MeHg is likely to biomagnify at this trophic step at all ingestion rates, whereas As, Cd, Cr, and Hg(II) will not. Data collected in this study and others indicate that using one prey item to calculate AE and k_ef could lead to an over- or underestimation of these parameters.     

Spatial and historical variation in sediment phosphorus fractions and mobility in a shallow lake

Temporal and spatial variation in sediment P composition and mobility were investigated in Loch Leven. Little change was observed in total sediment P (surface sediment at 4m depth), in comparison to a previous study (1990), despite significant reduction of external point sources of P. Labile P and residual P have both increased (0.007-0.039 mg PO(4)-P and 0.121-0.420 mg PO(4)-P per gram dry weight of sediment, respectively) since 1990. An analysis of P fractions, along a depth transect, indicated elevated labile P concentrations in shallow water sediment (<12 m overlying water depth). Regression analysis showed that spatial variability in reductant-adsorbed P was significantly related to sediment chlorophyll a concentration (R(2)=0.733, p<0.05). This may be linked to the production of oxygen, by benthic algae, resulting in the maintenance of an oxygenated layer at the sediment surface. Variation in labile P was best explained by overlying water temperature and equilibrium phosphate concentration (EPC0).     

Levels and patterns of Persistent Organic Pollutants (POPS) in selected food items from Northwest Russia (1998-2002) and implications for dietary exposure

Residues of persistent organic pollutants (POPs) were analysed in 70 selected food items from Northwest Russia in 1998-2002. Levels of PCBs ranged from 0.2 to 16 ng/g wet weight (ww) in dairy products and fats, 0.2 to 23 ng/g ww in meat products, 0.5 to 16 ng/g ww in eggs and 0.3 to 30 ng/g ww in fish. High levels of DDT (16 ng/g ww) were found in locally produced butter from Kola Peninsula, in pork fat from Arkhangels region (10 to 130 ng/g ww) and in some fish samples from White Sea and Kargopol region (17 and 30 ng/g ww). Findings of low DDE/DDT ratios in many of the studied food items indicated recent contamination to DDTs. Mean levels of sum TEQs_WHO1998 of dioxin-like mono-ortho PCBs: PCBs 105, 118, 156 and 157 (∑ mo-PCBs-TEQs_WHO1998) were highest in dairy products, chicken eggs and fish, with levels of 0.292, 0.245 and 0.254 pg/g ww, respectively. The estimated daily intake (EDI) for ∑ mo-PCBs-TEQs_WHO1998 was 0.74 pg/kgbw/day and in the same range as in Sweden and Denmark. Fish, dairy products, eggs and meat were the main contributors to the EDI of ∑ mo-PCBs-TEQs_WHO1998. The EDIs of DDTs, HCHs and HCB were several times higher than in Sweden and Denmark. Consumption of meat and poultry were important sources for intake of DDTs and HCHs, respectively. Contamination of animal feed and agricultural practice were assumed the most important causes for the results in the present study. However, increased control on maximum residue levels in food and feed may have resulted in large changes on levels and patterns of POPs in food in the studied areas.     

Inventory of aquatic contaminant flux arising from historical metal mining in England and Wales

The impact of discharges from abandoned metal and ironstone mines has been a much studied form of aquatic pollution in recent decades. Few attempts however, have been made to accurately determine the overall contaminant mass flux arising from abandoned mine sites at scales above catchment level. Such assessments are critical to determine the significance of former mining to national, regional and ultimately global trace metal flux. This paper presents the most comprehensive national survey to date across England and Wales of the total pollution burden discharged at source from abandoned non-coal mine sites. 338 discharges have been identified (from 4923 known abandoned metal mines) and while concurrent flow and contaminant concentration records are only available for around 30% of these, significant quantities of metals (and As) have been quantified to be discharged. A minimum of 193 tonnes of Zn, 18.5 tonnes of Pb, 0.64 tonnes Cd, 19.1 tonnes of Cu, 551 tonnes Fe, 72 tonnes Mn and 5.1 tonnes As are released in water discharges from abandoned non-coal mines to the surface water environment of England and Wales each year. Precautionary extrapolation of mass fluxes based on the frequency distribution of measured concentration and flow data, for discharges with absent data, suggests that the actual total mass flux for these contaminants could be up to 41% higher. The mass flux of Pb released from mines exceeds that of all currently permitted discharges (e.g. active industrial sites and wastewater treatment works) to surface waters across England and Wales, while those of As, Cd and Zn are of a similar magnitude. These data put into context the enduring legacy of historic mining on the water environment, highlighting its significance relative to more highly regulated polluting sites. Comparison of the figures with estimates of global trace metal flux suggests that the national total identified here is significant on a global scale.     

Trace metal behaviour in estuarine and riverine floodplain soils and sediments: a review

This paper reviews the factors affecting trace metal behaviour in estuarine and riverine floodplain soils and sediments. Spatial occurrence of processes affecting metal mobility and availability in floodplains are largely determined by the topography. At the oxic-anoxic interface and in the anoxic layers of floodplain soils, especially redox-sensitive processes occur, which mainly result in the inclusion of metals in precipitates or the dissolution of metal-containing precipitates. Kinetics of these processes are of great importance for these soils as the location of the oxic-anoxic interface is subject to change due to fluctuating water table levels. Other important processes and factors affecting metal mobility in floodplain soils are adsorption/desorption processes, salinity, the presence of organic matter, sulphur and carbonates, pH and plant growth. Many authors report highly significant correlations between cation exchange capacity, clay or organic matter contents and metal contents in floodplain soils. Iron and manganese (hydr)oxides were found to be the main carriers for Cd, Zn and Ni under oxic conditions, whereas the organic fraction was most important for Cu. The mobility and availability of metals in a floodplain soil can be significantly reduced by the formation of metal sulphide precipitates under anoxic conditions. Ascending salinity in the flood water promotes metal desorption from the floodplain soil in the absence of sulphides, hence increases total metal concentrations in the water column. The net effect of the presence of organic matter can either be a decrease or an increase in metal mobility, whereas the presence of carbonates in calcareous floodplain soils or sediments constitutes an effective buffer against a pH decrease. Moreover, carbonates may also directly precipitate metals. Plants can affect the metal mobility in floodplain soils by oxidising their rhizosphere, taking up metals, excreting exudates and stimulating the activity of microbial symbionts in the rhizosphere.     

Transport of C-labelled PCB compounds from sediment to water and from water to air in laboratory model systems

Tetra-, hexa- and octachlorobiphenyls were added to aquatic model systems composed of undisturbed sediment cores with an overlying water phase. Using impactor plates transport of the compounds from sediment to air was observed. About one per cent of the sediment-bound PCBs recovered in the systems left the water by jet drops from bursting bubbles. The transport of PCBs from the sediment to the air was nearly constant over time, with a transport rate of 0.62 μg · dm⁻² week⁻¹ for tetrachlorobiphenyl. Tetrachlorobiphenyl was mobile in systems with and without macroinvertebrates and in those fixed with HgCl₂. Hexa- and octachlorobiphenyls were transported from sediment to water mainly by bioturbation processes. The two latter substances had a higher adsorption to particles than tetrachlorobiphenyl. Compared to tetrachlorobiphenyl, more hexa- and octachlorobiphenyls accumulated in chironomids and tubificids.     

Speciation of lead, copper, zinc and antimony in water draining a shooting range—Time dependant metal accumulation and biomarker responses in brown trout (Salmo trutta L.)

The speciation of Pb, Cu, Zn and Sb in a shooting range run-off stream were studied during a period of 23 days. In addition, metal accumulation in gills and liver, red blood cell ALA-D activity, hepatic metallothionine (Cd/Zn-MT) and oxidative stress index (GSSG/ tGSH levels) in brown trout (Salmo trutta L.) exposed to the stream were investigated. Fish, contained in cages, were exposed and sampled after 0, 2, 4, 7, 9, 11 and 23 days of exposure. Trace metals in the water were fractionated in situ according to size (nominal molecular mass) and charge properties. During the experimental period an episode with higher runoff occurred resulting in increased levels of metals in the stream. Pb and Cu were mainly found as high molecular mass species, while Zn and Sb were mostly present as low molecular mass species. Pb, Cu and Sb accumulated on gills, in addition to Al origination from natural sources in the catchment. Pb, Cu and Sb were also detected at elevated concentration in the liver. Blood glucose and plasma Na and Cl levels were significantly altered during the exposure period, and are attributed to elevated concentrations of Pb, Cu and Al. A significant suppression of ALA-D was detected after 11 days. Significant differences were detected in Cd/Zn-MT and oxidative stress (tGSH/GSSG) responses at Day 4. For Pb the results show a clear link between the HMM (high molecular mass) positively charged Pb species, followed by accumulation on gills and liver and a suppression in ALA-D. Thus, high flow episodes can remobilise metals from the catchment, inducing stress to aquatic organisms.