Bioavailability and bioaccessibility are complex issues that determine whether or not adverse effects are to be expected when organisms or plants are exposed to contaminants. Clearly, the determinants of bioavailability and bioaccessibility must be understood if one is to monitor or, ultimately, predict the effects of metals. On the basis of a dynamic conceptual model, this article offers an analysis of the physicochemical and biological determinants underlying bioavailability and bioaccessibility. This analysis is used as the basis for a general monitoring strategy for assessing potentially and actually available and accessible metal fractions in the environmental matrices of water, soil, and sediment. We conclude that, lack of a universal expression of bioavailable and bioaccessible metal fractions precludes the presentation of a detailed monitoring strategy that is broadly applicable. Instead, we recommend that a critical assessment of the endpoints of determination become the basis for a need-specific monitoring strategy.