Since the early 2000s, biotic ligand models and related constructs have been a dominant paradigm for risk assessment of aqueous metals in the environment. We critically review 1) the evidence for the mechanistic approach underlying metal bioavailability models; 2) considerations for the use and refinement of bioavailability-based toxicity models; 3) considerations for the incorporation of metal bioavailability models into environmental quality standards; and 4) some consensus recommendations for developing or applying metal bioavailability models. We note that models developed to date have been particularly challenged to accurately incorporate pH effects because they are unique with multiple possible mechanisms. As such, we doubt it is ever appropriate to lump algae/plant and animal bioavailability models; however, it is often reasonable to lump bioavailability models for animals, although aquatic insects may be an exception. Other recommendations include that data generated for model development should consider equilibrium conditions in exposure designs, including food items in combined waterborne-dietary matched chronic exposures. Some potentially important toxicity-modifying factors are currently not represented in bioavailability models and have received insufficient attention in toxicity testing. Temperature is probably of foremost importance; phosphate is likely important in plant and algae models. Acclimation may result in predictions that err on the side of protection. Striking a balance between comprehensive, mechanistically sound models and simplified approaches is a challenge. If empirical bioavailability tools such as multiple-linear regression models and look-up tables are employed in criteria, they should always be informed qualitatively and quantitatively by mechanistic models. If bioavailability models are to be used in environmental regulation, ongoing support and availability for use of the models in the public domain are essential.

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Abstract-The uptake of cadmium and zinc by the common carp, Cyprinus carpio, was studied in chemically defined freshwater in the presence of different organic ligands (i.e., citrate, glycine, histidine, ethylenediaminetetraacetic acid, and nitrilotriacetic acid). In most cases, metal complexation decreased Cd and Zn uptake by reducing the free Cd and Zn ion activity. However, Cd and Zn uptake did not increase linearly with the free Cd and Zn ion activity in the solution. A good fit to the data was obtained when the observations were fitted to a Michaelis-Menten-like model for carrier-mediated transport of the metal ions across the biological interface. In addition, the uptake of Cd in the presence of citrate, glycine, and histidine was markedly higher than expected on the basis of the free Cd ion activity. It was concluded that cadmium complexes of these low molecular weight, hydrophilic ligands contributed to the Cd bioavailability, probably by direct uptake of these complexes. Zinc uptake in the presence of the complexing agents could be predicted on the basis of the ambient free Zn ion activity, although uptake in the presence of citrate was lower than expected on the basis of the free Zn ion activity. These results provide a challenging test for the free ion activity model.

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