Metal equilibration in laboratory-contaminated (spiked) sediments used for the development of whole-sediment toxicity tests

The equilibration and bioavailability of metals in laboratory-contaminated sediments have been investigated in order to provide better guidance on acceptable procedures for spiking sediments with metals for use in the development of whole-sediment toxicity tests. The equilibration rates of Cd, Cu, Ni and Zn spiked into three estuarine surface sediments with varying properties were investigated. Changes to sediment pH, redox potential, porewater and acid-soluble metals, acid-volatile sulfide and bacterial activity during equilibration, effects of temperature and disturbances following equilibration are reported. The addition of metals to sediments caused major decreases in pH and increases in redox potential as metals displaced iron(II) into the porewaters and added metals and iron (following oxidation) were hydrolyzed. The rates of equilibration of metals in porewaters varied considerably and were dependent on sediment and metal properties. For the oxic/sub-oxic sediments studied, metal-spikes of Cd, Cu, Ni and Zn appeared near equilibrium after 25-45, 10-15, 30-70 and 20-40 days, respectively. Acid-soluble metal concentrations decreased during the equilibration period indicating that the metals become more strongly associated with the sediments with time (less bioavailable). Bacterial activity was greatest in the sediment equilibrated at pH 7 and decreased following the addition of metals. During the equilibration period, bacterial activity increased in sediments equilibrated at pH 6, remained low in sediments at pH 8 and varied erratically in sediments at pH 7. Spiked sediments were shown to equilibrate more slowly at lower temperatures resulting in high porewater metal concentrations. Disturbances to equilibrated sediments because of sample manipulation caused significant iron(II) oxidation and losses of metals from porewaters. The importance of documenting spiking and equilibration procedures and carefully measuring and reporting sediment parameters is highlighted so that contaminant bioavailability and exposure pathways can be interpreted and organism sensitivity accurately determined. Recommendations are given for the preparation of metal-spiked sediments for toxicity testing purposes.     

A study of metal and metalloid contaminant availability in Antarctic marine sediments

Previous studies of impacted sites near Casey Station, Antarctica, have revealed elevated concentrations of metals and metalloids, particularly Cd, Cu, Fe, Pb, Sn and Zn in marine sediments. However, attempts to understand the availability and mobility of contaminant elements have not provided a true understanding of speciation. The current work shows, for the first time, that sediments in Brown Bay, an embayment adjacent to the Thala Valley waste disposal site, have elevated concentrations of sulfide, well in excess of that required to bind contaminant metals such as Cd, Cu, Pb and Zn. Furthermore, sediment characterisation using the BCR sequential extraction scheme has shown metal partitioning consistent with sulfides being the controlling factor in metal availability, thus explaining the low porewater concentrations of these metals. The speciation of Sn in Brown Bay, however, is still unclear with the BCR sequential extraction scheme partitioning Sn predominantly into the residual fraction despite Sn being readily extracted by dilute HCl.     

Metal partitioning in river sediments measured by sequential extraction and biomimetic approaches

We quantified the concentrations and distributions of metals (Cd, Cr, Cu, Ni, Pb, and Zn) in the sediments of Tuen Mun River, Hong Kong. The potential bioavailability of metals was assessed with a biomimetic extraction method using the sipunculan gut juices. The sediments were characterized by relatively high concentrations of trace metals. Field collected sediments were highly anoxic and the ratio of simultaneously extractable metal (sigmaSEM) to acid volatile sulfide (AVS) was much less than one in these sediments. The majority (>67%) of Cd, Pb, and Zn were bound to AVS, thus their concentrations in the sediment porewater were low. In contrast, Ni was little bound to AVS due to its lower ratios of SEM-Ni to total Ni concentrations. For Cu, relatively high concentrations in the sediment porewater was found, and total organic carbon, AVS and other resistant sulfide phase were the controlling factors for sedimentary Cu partitioning. Net metal adsorption from gut juices to anoxic sediments was observed in metal extraction experiments, suggesting that AVS determined the bioaccumulation and potential bioavailability of most metals in these sediments. Extraction of metals from the oxidized sediments by the gut juices was mainly attributed to metal redistribution from AVS to other geochemical phases. The gut juices were the most effective solvent or extractant than the simple electrolyte solution [I (NaNO(3)) = 0.01 M] and the natural overlying water. Cd was more easily extracted from the oxidized sediments than Zn that tended to have a stronger binding affinity with Fe-Mn oxide, clay and organic matter. The application of partial removal techniques in metal extraction experiments further demonstrated the differential controls of various sediment geochemical phases in affecting metal bioavailability, with the order of TOC > Fe-Mn oxides > carbonate.     

The influence of salinity on metal uptake and effects in the midge Chironomus maddeni

The influence of different porewater salinities (up to 12 g/L) on the toxicity and bioaccumulation of copper, zinc and lead from metal-spiked sediments was assessed using the midge, Chironomus maddeni. Survival of the larvae was significantly reduced at a porewater salinity of 12 g/L, but no effects were observed at 4 or 8 g/L. Both growth and survival of C. maddeni were reduced after exposure to salt/metal spiked sediments as compared to those exposed to sediments spiked with metals or salt alone. Increased salinity resulted in increased bioaccumulation of copper and zinc, but decreased bioaccumulation of lead. The observed patterns of bioaccumulation were not entirely explained by the modelled free ion activities of the metals, indicating that factors such as osmotic stress, consumption of metal-contaminated sediments or metal interactions may have been important as well. These results highlight the need to consider the influence of existing or potential salinization when undertaking hazard assessments of freshwater systems impacted by contaminants such as trace metals.     

Effect of overlying water pH, dissolved oxygen, salinity and sediment disturbances on metal release and sequestration from metal contaminated marine sediments

Experiments were undertaken to examine the key variables affecting metal release and sequestration processes in marine sediments with metal concentrations in sediments reaching up to 86, 240, 700, and 3000 mg kg(-1) (dry weight) for Cd, Cu, Pb and Zn, respectively. The metal release and sequestration rates were affected to a much greater extent by changes in overlying water pH (5.5-8.0) and sediment disturbance (by physical mixing) than by changes in dissolved oxygen concentration (3-8 mg l(-1)) or salinity (15-45 practical salinity units). The physical disturbance of sediments was also found to release metals more rapidly than biological disturbance (bioturbation). The rate of oxidative precipitation of released iron and manganese increased as pH decreased and appeared to greatly influence the sequestration rate of released lead and zinc. Released metals were sequestered less rapidly in waters with lower dissolved oxygen concentrations. Sediments bioturbated by the benthic bivalve Tellina deltoidalis caused metal release from the pore waters and higher concentrations of iron and manganese in overlying waters than non-bioturbated sediments. During 21-day sediment exposures, T. deltoidalis accumulated significantly higher tissue concentrations of cadmium, lead and zinc from the metal contaminated sediments compared to controls. This study suggests that despite the fact that lead and zinc were most likely bound as sulfide phases in deeper sediments, the metals maintain their bioavailability because of the continued cycling between pore waters and surface sediments due to physical mixing and bioturbation.     

Processes controlling metal transport and retention as metal-contaminated groundwaters efflux through estuarine sediments

Factors affecting the transport and retention of Cd, Cr, Cu, Ni, Pb and Zn in acidic groundwaters as they pass through estuarine sediments were investigated using column experiments. Acidic groundwaters caused the rapid dissolution of iron sulfide (AVS) and other iron and manganese phases from sediments that are important for metal binding and buffering. Metal breakthrough to overlying water occurred in the order of Ni>Zn>Cd>Cu>Cr/Pb. Metal transport increased as the sediment permeability increased, reflecting the low resistance to flow caused by larger sand-sized particles and the decreased abundance of metal adsorption sites on these materials. Metal mobility increased as the groundwater pH decreased, as flow rate or metal concentrations increased, and as the exposure duration increased. Groundwater Cr and Pb were promptly attenuated by the sediments, the mobility of Cu was low and decreased rapidly as sediment pH increased above 4.5, while Cd, Ni and Zn were the most easily transported to the surface sediments and released to the overlying waters. For groundwaters of pH 3, metal migration velocities through sandy sediments were generally 0.5-2% (Cr, Pb), 1-6% (Cu) and 4-13% (Cd, Ni, Zn) of the total groundwater velocity (9-700 m/yr). The oxidative precipitation of Fe(II) and Mn(II) in the groundwaters did not affect metal mobility through the sediments. The results indicated that the efflux of acidic and metal-contaminated groundwater through estuarine sediments would affect organisms resident in sandy sediments more greatly than organisms resident in fine-grained, silty, sediments.     

Metal solubility as a function of pH in a contaminated, dredged sediment affected by oxidation

The solubility as a function of pH for metals in a reduced dredged sediment, subjected to different redox conditions, was studied in a laboratory experiment. The redox conditions imposed simulated (i) the undisturbed sediment (flooded), (ii) a dredged material stored in a confined pond (aerated once and then flooded), (iii) an upland stored dredged material (drained and dried), and (iv) an upland stored sediment subjected to tillage (drained, dried and mixed). Minor differences in the solubility as a function of pH were observed between the treatments after two weeks. After three months, the solubility of Cd, Cu, Pb and Zn increased strongly in the oxidized sediments. Leachability of Fe decreased, while Mn, Ni and Co were mostly unaffected. Both short- and long-term mobility of metals (except Fe) is expected to be lowest when a reduced sediment remains in reduced conditions. Studying the solubility as a function of pH may provide additional information on the chemical association of metals in sediments.     

Evaluation of diffusive gradients in thin film (DGT) samplers for measuring contaminants in the Antarctic marine environment

This work has been the first application of DGT samplers for measuring metals in water and sediment porewater in the Antarctic environment, and whilst DGT water sampling was restricted to quantification of Cd, Fe and Ni, preconcentration using Empore chelating disks provided results for an additional nine elements (Sn, Pb, Al, Cr, Mn, Co, Cu, Zn, As). Although higher concentrations were measured for some metals (Cd, Ni, Pb) using the Empore technique, most likely due to particulate-bound or colloidal species becoming entrapped in the Empore chelating disks, heavy metal concentrations in the impacted Brown Bay were found to be comparable with the non-impacted O'Brien Bay. Sediment porewater sampling using DGT also indicated little difference between Brown Bay and O'Brien Bay for many metals (Cd, Al, Cr, Co, Ni, Cu), however, greater amounts of Pb, Mn, Fe and As were accumulated in DGT probes deployed in Brown Bay compared with O'Brien Bay, and a higher accumulation of Sn was observed in Brown Bay inner than any of the other three sites sampled. Comparison of DGT derived porewater concentrations with actual porewater concentrations showed limited resupply of Cd, Pb, Al, Cr, Mn, Co, Ni, Cu, Zn and As from the solid phase to porewater, with these metals appearing to be strongly bound to the sediment, however, resupply of Fe and Sn was apparent. Based upon our observations here, we suggest that Sn, and to a lesser extent Pb, are critical contaminants.     

Effects of a chelating resin on metal bioavailability and toxicity to estuarine invertebrates: Divergent results of field and laboratory tests

Benthic invertebrates can uptake metals through diffusion of free ion solutes, or ingestion of sediment-bound forms. This study investigated the efficacy of the metal chelating resin SIR 300™ in adsorbing porewater metals and isolating pathways of metal exposure. A field experiment (Botany Bay, Sydney, Australia) and a laboratory toxicity test each manipulated the availability of porewater metals within contaminated and uncontaminated sediments. It was predicted that within contaminated sediments, the resin would adsorb porewater metals and reduce toxicity to invertebrates, but in uncontaminated sediments, the resin would not significantly affect these variables. Whereas in the laboratory, the resin produced the predicted results, in the field the resin increased porewater metal concentrations of contaminated sediments for at least 34 days and decreased abundances of four macroinvertebrate groups, and richness in all sediments. These contrasting findings highlight the limits of extrapolating the results of laboratory experiments to the field environment.     

Multivariate statistical study of heavy metal enrichment in sediments of the Pearl River Estuary

The concentrations and chemical partitioning of heavy metals in the sediment cores of the Pearl River Estuary were studied. Based on Pearson correlation coefficients and principal component analysis results, Al was selected as the concentration normalizer for Pb, while Fe was used as the normalizing element for Co, Cu, Ni and Zn. In each profile, sections with metal concentrations exceeding the upper 95% prediction interval of the linear regression model were regarded as metal enrichment layers. The heavy metal accumulation mainly occurred at sites in the western shallow water areas and east channel, which reflected the hydraulic conditions and influence from riparian anthropogenic activities. Heavy metals in the enrichment sections were evaluated by a sequential extraction method for possible chemical forms in sediments. Since the residual, Fe/Mn oxides and organic/sulfide fractions were dominant geochemical phases in the enriched sections, the bioavailability of heavy metals in sediments was generally low. The 206Pb/207Pb ratios in the metal-enriched sediment sections also revealed the influence of anthropogenic sources. The spatial distribution of cumulative heavy metals in the sediments suggested that the Zn and Cu mainly originated from point sources, while the Pb probably came from non-point sources in the estuary.     

Physico-chemical changes in metal-spiked sediments deployed in the field: implications for the interpretation of in situ studies

Manipulative field studies are useful for investigating cause-effect relationships between contamination and benthic community health. However, there are many challenges for creating environmentally relevant exposures and determining what measurements are necessary to correctly interpret the results. This study describes the physical and chemical changes in the properties of metal-spiked marine sediments deployed in four different locations for up to 11 months. The test sediments lost between 20% and 75% of their volume during the deployment period, with the greatest losses occurring at sites affected by strong hydrodynamic activity. More sediment was lost from clean treatments than those spiked with high metal concentrations and corresponded with differential recruitment of infauna to these treatments. In general, a greater proportion of spiked-metals remained at lower energy sites (48-85%) than at higher energy sites (15-48%). The decreased metal concentrations were attributed mostly to the loss of the metal-spiked sediments (through resuspension) and their dilution with sediments depositing from the surrounding environment. A range of recommendations are made for optimising the information gained from field-based studies using metal-spiked sediments. These include the careful documentation of physico-chemical sediment properties pre- and post-deployment, the use of co-located sediment traps and knowledge of site-specific hydrodynamic processes.     

Long-term copper partitioning of metal-spiked sediments used in outdoor mesocosms

Understanding the effects of sediment contaminants is pivotal to reducing their impact in aquatic environments. Outdoor mesocosms enable us to decipher the effects of these contaminants in environmentally realistic scenarios, providing a valuable link between laboratory and field experiments. However, because of their scale, mesocosm experiments are often complex to set up and manage. The creation of environmentally realistic conditions, particularly when using artificially contaminated sediment, is one issue. Here, we describe changes in geochemistry over 1.5 years of a sediment spiked with four different concentrations of copper, within a large freshwater mesocosm facility. The spiking procedure included proportional amendments with garden lime to counteract the decreases in pH caused by the copper additions. The majority of copper within the spiked mesocosm sediments partitioned to the particulate phase with low microgram per liter concentrations measured in the pore waters and overlying waters. The minimum partition coefficient following equilibration between pore waters and sediments was 1.5?×?10⁴ L/kg, which is well within the range observed for field-contaminated sediments (1?×?10⁴ to 1?×?10⁶ L/kg). Recommendations are made for the in situ spiking of sediments with metals in large outdoor mesocosms. These include selecting an appropriate sediment type, adjusting the pH, allowing sufficient equilibration time, and regular mixing and monitoring of metal partitioning throughout the experimental period.     

Geochemical partitioning of Co, Cr, Fe, Sc and Zn in polluted and non-polluted marine sediments

The partitioning of Co, Cr, Fe, Sc and Zn into three fractions (reducible by acidified hydroxylamine hydrochloride, oxidizable by acidified hydrogen peroxide, and the residual after the previous extractions) of Saronikos Gulf surface sediments was determined by using a sequential extraction technique. The metal concentrations were determined by Instrumental Neutron Activation Analysis. With the exception of Sc, the metal content in the reducible and oxidizable fractions increases in the polluted sediments near the Athens Sewage Outfall (ASO) and a Fertilizer Plant (FP). In the non-polluted sediments, the residual fraction is the most important carrier for all metals examined. Oxidizable Cr and Zn correlate well with the organic carbon content of the sediments, but the reducible fraction (mainly Fe/Mn hydroxides) is the most important sink for Co, Cr, Fe and Zn in the polluted sediments near the ASO. The pyrite-rich wastes from the FP are influencing the geochemical partitioning of the metals examined in the sediments in front of the FP and, partially, in the sediments near the ASO.     

Consequences and implication of heavy metal spatial variations in sediments of the Keelung River drainage basin, Taiwan

A great deal of effort was enforced to reduce the pollution of the Keelung River in the past 20 years. A set of sediments covering most of the Keelung River drainage basin was analyzed for bulk sediment heavy metal concentrations, grain size content and Pb-210 dating in order to understand the spatial variations of sediment heavy metal contents as well as to evaluate the effectiveness of pollution control. The results showed that anthropogenic pollution and grain size are two of the most important factors in controlling spatial variations of metals in the Keelung River sediments. In addition, little reduction of sediment heavy metal concentrations was observed in the Keelung River drainage basin. Large spatial variations of metals and grain size were observed. High concentrations of zinc, copper, lead and cadmium were found in sediments near the main outlets of the adjacent Da-Wu-Lun Industrial Park and municipal waste drainage systems. Anthropogenic sources of heavy metal have altered the natural sediment heavy metal distributions. Positive linear relationships between aluminum, iron and fine-grained sediments showed that spatial grain size variations controlled the natural aluminum and iron concentrations in sediments. Zinc, copper, lead and cadmium contents were much higher than those measured 15 years ago. The unusually high concentrations of heavy metals, high enrichment factors and their rapid increases with time in Pb-210 dated core showed that the efforts in heavy metal reduction were futile. A proper regulation to prevent further heavy metals from entering into the river is urgently needed.     

Distribution and relationships of selected trace metals in molluscs and associated sediments from the Gulf of Aden, Yemen

Concentrations of Cd, Pb, Zn, Cu, Ni, Co, Cr, Mn and Fe in the soft tissue of Turbo coronatus, Acanthopleura haddoni, Ostrea cucullata and Pitar sp., as well as in associated surface sediments (bulk and bioavailable metal concentrations) from the Gulf of Aden, Yemen, were determined by atomic absorption spectrophotometry method. Large differences between size-classes of molluscs in metal concentrations were recorded. Significant spatial differences in metal concentrations in both the soft tissue of the molluscs and associated sediments studied were mostly identified. Statistically significant correlations (p<0.01) between concentrations of selected metals were observed. A slope of the linear regression is significantly higher than unity for Fe (9.91) and Cd (3.45) in A. haddoni and for Ni (4.15) in T. coronatus, suggesting that the bioavailability of these metals is disproportionally increased with a degree of enrichment of the sediments in Fe, Cd and Ni, respectively. A slope constant approximating to unity (1.14) for Cu in A. haddoni relative to its concentration in sediment extract implies that bioavailability of this metal proportionally increased with growing concentrations of its labile forms in the associated sediment. The degree of contamination of Gulf of Aden waters by the metals studied is discussed and the potential ability of molluscs, especially A. haddoni and T. coronatus, as biomonitors of metallic pollutants is postulated.     

Resuspension of contaminated field and formulated reference sediments Part I: Evaluation of metal release under controlled laboratory conditions

In aquatic systems where metal contaminated sediments are present, the potential exists for metals to be released to the water column when sediment resuspension occurs. The release and partitioning behavior of sediment-bound heavy metals is not well understood during resuspension events. In this study, the release of Cd, Cu, Hg, Ni, Pb and Zn from sediments during resuspension was evaluated using reference sediments with known physical and chemical properties. Sediment treatments with varying quantities of acid volatile sulfide (AVS), total organic carbon (TOC), and different grain size distributions were resuspended under controlled conditions to evaluate their respective effects on dissolved metal concentrations. AVS had the greatest effect on limiting release of dissolved metals, followed by grain size and TOC. Predictions of dissolved concentrations of Cd, Ni, Pb and Zn were developed based on the formulated sediment Σ_metal/AVS ratios with Σ_metal being the total sediment metal concentration. Predicted values were compared to measured dissolved metal concentrations in contaminated field sediments resuspended under identical operating conditions. Metal concentrations released from the field sediments were low overall, in most cases lower than predicted values, reflecting the importance of other binding phases. Overall, results indicate that for sulfidic sediments, low levels of the study metals are released to the dissolved phase during short-term resuspension.     

Transformation of N-, O-, and S- heterocycles (NOSHs) in estuarine sediments: Effects of redox potential and sediment particle size

The transformation of 19 N-, O-, and S- heterocycles (NOSHs) was examined in estuarine sediment-water microcosms. The effects of redox potential (Eh) and sediment particle size on compound transformation rates were evaluated, and stable products were identified. Results from stirred, controlled Eh/pH microcosms (CEPMs) showed that most of the NOSHs were significantly transformed under oxidized and reduced conditions over 15 week incubations, and the resulting product distributions were similar. In general, the rates and extent of transformation were greater in oxidized sediments of low surface area vs. those with high particle surface area and reduced redox conditions. Further experiments in sealed, unstirred microcosms also showed that NOSH transformation proceeded more slowly and on fewer compounds in fine vs. coarser grained sediments under oxidized conditions. Unlike the stirred systems, however, NOSH transformation rates were similar or greater under reduced vs. oxidized conditions. Thus, reduced, methanogenic clay of high surface area displayed some of the fastest rates of NOSH transformation. Data from liquid-liquid partitioning experiments suggested that this effect was related to the formation of NOSH complexes with iron and perhaps other redox-active metals in sediments.     

Heavy metal in sediments of Ziya River in northern China: distribution,potential risks,and source apportionment

The concentration partitioning between the sediment particle and the interstitial water phase plays an important role in controlling the toxicity of heavy metals in aquatic systems. The aim of this study was to assess the sediment quality in a polluted area of the Ziya River, Northern China. The contamination potential and bioavailability of six metals were determined from the concentrations of total metals and the bioavailable fractions. The results showed that the concentrations of Cr, Cu, Ni, Zn, and Pb exceeded the probable effect concentration at several sites. The high geoaccumulation indices showed that the sediments were seriously contaminated by Cd. The ratio of acid-volatile sulfide (AVS) to simultaneously extracted metal (SEM) was higher than 1, which indicated that the availability of metals in sediments was low. The risk assessment of interstitial waters confirmed that there was little chance of release of metals associated with acid-volatile sulfide into the water column. Values of the interstitial water criteria toxicity unit indicated that none of the concentrations of the studied metals exceeded the corresponding water quality thresholds of the US Environmental Protection Agency. Positive matrix factorization showed that the major sources of metals were related to anthropogenic activities. Further, if assessments are based on total heavy metal concentrations, the toxicity of heavy metals in sediment may be overestimated.     

Accumulation and distribution of heavy metals in the grey mangrove,Avicennia marina (Forsk)Vierh: biological indication potential

The accumulative partitioning of the heavy metals Cu, Pb and Zn in the grey mangrove, Avicennia marina, were studied under field conditions. Copper and Pb were accumulated in root tissue to levels higher than surrounding sediment levels. Zinc was accumulated to levels reflecting sediment concentrations. Strong linear relationships existed for all metals in sediments with metals in root tissue. Accumulation of Cu in leaf tissue followed a linear relationship at lower sediment concentrations, with an exclusion or saturation mechanism at higher sediment concentrations. Lead showed little mobility to leaf tissue. Zn showed restricted accumulation in leaf tissue, which correlated with sediment concentrations. Decreases in sediment pH were found to increase Zn accumulation to root tissue. Increasing concentrations of Pb and Zn in sediments resulted in a greater accumulation of Pb to both root and leaf tissue. A. marina roots may be employed as a biological indicator of environmental exposure of Cu, Pb and Zn and leaves for Zn, with temporal monitoring.     

Relationships between river sediment characteristics and trace metal concentrations in tubificid worms and chironomid larvae

Surficial sediments, midge larvae (Chironomidae, Diptera) and tubificid worms (Tubificidae, Oligochaeta) were collected at 65 sampling sites located in four different river basins in Flanders (Belgium). Concentrations of the trace metals Cu, Zn, Cd and Pb were measured in organisms and sediments by atomic absorption spectrophotometry. Sediments were subjected to a simultaneous extraction scheme to identify trace metal partitioning among various geochemical phases. Three geochemical characteristics of the sediment were analysed; Total Organic Carbon (TOC), Fe oxides and Mn oxides. Non-linear regression models were constructed to determine the relative importance of the different sediment factors contributing to the variation in metal accumulation by the tubificid worms and chironomids. Generally, the amount of variation that could be explained by these models was limited, with coefficients of determination ranging from 0.05 to 0.66. In most cases, metal levels in organisms were positively related to the easily reducible and reducible metal fractions, and negatively related to the TOC and Fe sediment content. The correlations between metal concentrations in tubificid worms and chrinomid larvae were also rather poor, with coefficients of determinations ranging from 0.01 to 0.52. This indicates that understanding the chemistry of the environment does not suffice to predict the concentrations in organisms. Differences in the structural and functional organisation of the organisms, which among others determine the route of exposure, are at least equally important causes of variability in metal availability and accumulation.