The kinetics of accumulation of pentachlorophenol (PCP) at various pH values were investigated to explore how pH-dependent accumulation might influence PCP toxicity. Goldfish (Carassius auratus ) were exposed to 5 mu g PCP/L in a static system buffered with 7.5 mM bicine or N,N-bis(2-hydroxyethyl)-2-aminoethane sulfonic acid (BES) at pH 7.0, 8.0, or 9.0. The amount of PCP in the fish, concentration of PCP in water, and the total amount of metabolites in the system were measured after exposure of fish from 1 to 96 hr. The distribution of PCP within the fish was altered by changes in the external pH. The pH-associated changes in distribution may have altered access of PCP to sites of metabolism, thereby altering the metabolic clearance. The pH-related changes in the pharmacokinetics of PCP resulted in a decrease in its bioconcentration factor with an increase in pH and account both for the decreased capacity of the fish to accumulated PCP and for its reduced LC50.