Understanding how animals are exposed to the large repository of metal pollutants in aquatic sediments is complicated and is important in regulatory decisions. Experiments with four types of invertebrates showed that feeding behavior and dietary uptake control bioaccumulation of cadmium, silver, nickel, and zinc. Metal concentrations in animal tissue correlated with metal concentrations extracted from sediments, but not with metal in porewater, across a range of reactive sulfide concentrations, from 0.5 to 30 micromoles per gram. These results contradict the notion that metal bioavailability in sediments is controlled by geochemical equilibration of metals between porewater and reactive sulfides, a proposed basis for regulatory criteria for metals.
An 18-day microcosm study was conducted to evaluate the influence of acid volatile sulfides (AVS) and metal additions on bioaccumulation from sediments of Cd, Ni, and Zn in two clams (Macoma balthica and Potamocorbula amurensis) and three marine polychaetes (Neanthes arenaceodentata, Heteromastus filiformis, and Spiophanes missionensis). Manipulation of AVS by oxidation of naturally anoxic sediments allowed use of metal concentrations typical of nature and evaluation of processes important to chronic metal exposure. A vertical sediment column similar to that often found in nature was used to facilitate realistic biological behavior. Results showed that AVS or porewater (PW) metals controlled bioaccumulation in only 2 of 15 metal-animal combinations. Bioaccumulation of all three metals by the bivalves was related significantly to metal concentrations extracted from sediments (SEM) but not to [SEM -AVS] or PW metals. SEM predominantly influenced bioaccumulation of Ni and Zn in N. arenaceodentata, but Cd bioaccumulation followed PW Cd concentrations. SEM controlled tissue concentrations of all three metals in H. filiformis and S. missionensis, with minor influences from metal-sulfide chemistry. Significant bioaccumulation occurred when SEM was only a small fraction of AVS in several treatments. Three factors appeared to contribute to the differences between these bioaccumulation results and the results from toxicity tests reported previously: differences in experimental design, dietary uptake, and biological attributes of the species, including mode and depth of feeding.
The influence of acid volatile sulfide (AVS) on the partitioning of Cd, Ni, and Zn in porewater (PW) and sediment as reactive metals (SEM, simultaneously extracted metals) was investigated in laboratory microcosms. Two spiking procedures were compared, and the effects of vertical geochemical gradients and infaunal activity were evaluated. Sediments were spiked with a Cd-Ni-Zn mixture (0.06, 3, 7.5 µmol/g, respectively) containing four levels of AVS (0.5, 7.5, 15, 35 µmol/g). The results were compared to sediments spiked with four levels of Cd-Ni-Zn mixtures at one AVS concentration (7.5 µmol/g). A vertical redox gradient was generated in each treatment by an 18-d incubation with an oxidized water column. [AVS] in the surface sediments decreased by 65-95% due to oxidation during incubation; initial [AVS] was maintained at 0.5-7.5 cm depth. PW metal concentrations were correlated with [SEM -AVS] among all data. But PW metal concentrations were variable, causing the distribution coefficient, Kd pw (the ratio of [SEM] to PW metal concentrations) to vary by 2-3 orders of magnitude at a given [SEM -AVS]. One reason for the variability was that vertical profiles in PW metal concentrations appeared to be influenced by diffusion as well as [SEM -AVS]. The presence of animals appeared to enhance the diffusion of at least Zn. The generalization that PW metal concentrations are controlled by [SEM -AVS] is subject to some important qualifications if vertical gradients are complicated, metal concentrations vary, or equilibration times differ.
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