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34                                                         The Toxicology of Fishes








                                               96-Hour LC50 (µM Copper)

















                                                             Alkalinity (meq/L)

                       FIGURE 2.12 Observed and predicted lethality of copper to fathead minnows. (Data from Erickson et al., A Prototype
                       Toxicity Factors Model for Site-Specific Copper Water Quality Criteria, U.S. Environmental Protection Agency, Duluth, MN,
                       1987.) Solid circles denote observed LC 50  values (±95% confidence limits). Open circles denote predicted LC 50  values using
                       Biotic Ligand Model Version 2.0.0 (Hydroqual; Mahwah, NJ).

                         1.  Most model applications to date do not address effects of changes in chemistry at the gill
                           microenvironment. Tao et al. (2002) reported large effects on apparent metal–gill association
                           constants if the effects of pH changes and mucous secretions on copper binding are accounted
                           for. The implications of this to bioavailability assessments might be significant in some cases
                           and have not been determined.
                         2.  The model assumes chemical equilibria within the exposure water and between the exposure
                           water and the gill surface. In addition, there is a fixed proportionality between the metal bound
                           at the surface and the level of uptake or effect within the organism. Under some circumstances,
                           the kinetics of these processes might be important to bioavailability (Hudson, 1998); for
                           example, speciation changes in the gill microenvironment might not reach equilibrium because
                           of the short residence time of water in the gill.
                         3.  The effects of cations are not necessarily just a matter of competition with the gill sites, as
                           assumed in the model. The effect of hardness on toxicity appears to be nonlinear, whereas the
                           model predicts a linear effect. This might reflect changes in gill permeability that either affect
                           copper bioavailability in a nonlinear fashion or affect toxicity without affecting bioavailability.
                           The amelioration of copper toxicity by sodium should, to some degree, reflect direct effects
                           on sodium exchange rather than competition with copper. Merging this simple bioavailability
                           model with models for ion regulation (Paquin et al., 2002b) would address this issue.
                         4.  The role of copper species other than the free ion in uptake across, or interaction with, the gill
                           surface is poorly established. Efforts to include additional bioavailable species in model cal-
                           culations (De Schamphelaere and Janssen, 2002) require inferences from toxicity data trends
                           that are difficult, given uncertainties in the data and in model formulation. Better information
                           is needed to establish the actual role of these species.

                        Interpreting the toxicity of copper and many other cationic toxic metals is difficult because of complex
                       chemical speciation and various other processes that affect their accumulation at, and interaction with,
                       biological receptors. Although the bioavailability modeling approach described here is a rather simple
                       representation of a complex system, it addresses important aspects of the complexity by incorporating
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