Binding of nickel and copper to fish bills predicts toxicity when water hardness varies, but free-ion activity does not

Based on a biotic-ligand model (BLM), we hypothesized that the concentration of a transition metal bound to fish gills ([M-gill]) will be a constant predictor of mortality, whereas a free-ion activity model is generally interpreted to imply that the chemical activity of the aquo ("free") ion of the metal will be a constant predictor of mortality. In laboratory tests, measured [Ni-gill] and calculated [Cu-gill] were constant predictors of acute toxicity of Ni and Cu to fathead minnows (Pimephales promelas) when water hardness varied up to 10-fold, whereas total aqueous concentrations and free-ion activities of Ni and Cu were not. Thus, the BLM, which simultaneously accounts for (a) metal speciation in the exposure water and (b) competitive binding of transition-metal ions and other cations to biotic ligands predicts acute toxicity better than does free-ion activity of Ni or Cu. Adopting a biotic-ligand modeling approach could help establish a more defensible, mechanistic basis for regulating aqueous discharges of metals.