Chemical contaminants disrupt ecosystems, but specific effects may be under-appreciated when poorly known processes such as uptake mechanisms, uptake via diet, food preferences, and food web dynamics are influential. Here we show that a combination of food web structure and the physiology of trace element accumulation explain why some species in San Francisco Bay are threatened by a relatively low level of selenium contamination and some are not. Bivalves and crustacean zooplankton form the base of two dominant food webs in estuaries. The dominant bivalve Potamocorbula amurensis has a 10-fold slower rate constant of loss for selenium than do common crustaceans such as copepods and the mysid Neomysis mercedis (rate constant of loss, ke = 0.025, 0.155, and 0.25 d(-1), respectively). The result is much higher selenium concentrations in the bivalve than in the crustaceans. Stable isotope analyses show that this difference is propagated up the respective food webs in San Francisco Bay. Several predators of bivalves have tissue concentrations of selenium that exceed thresholds thought to be associated with teratogenesis or reproductive failure (liver Se >15 microg g(-1) dry weight). Deformities typical of selenium-induced teratogenesis were observed in one of these species. Concentrations of selenium in tissues of predators of zooplankton are less than the thresholds. Basic physiological and ecological processes can drive wide differences in exposure and effects among species, but such processes are rarely considered in traditional evaluations of contaminant impacts.