Concentrations and composition of polychlorinated naphthalene (PCN) congeners were determined in soil, sediments, blue crab, striped mullet, and boat-tailed grackle collected near a chlor-alkali plant to determine their congener profile, bioaccumulation properties, and toxic potential. Concentrations of total PCNs as high as 23 µg/ g, dry wt, were found in sediments collected at the marsh contaminated by disposal of wastes from the chloralkali process. The spatial distribution of sediment-PCN concentrations was not related with those observed for polychlorinated biphenyls (PCBs). The PCN congener profile did not resemble those of any technical mixtures. Hepta-and octa-chloronaphthalenes were the most abundant congeners accounting for greater than 50% of the total PCN concentrations in soil and sediments. A characteristic profile of PCNs in samples collected at the chlor-alkali site suggests the formation of chloronaphthalene congeners during chlor-alkali process, as has been suggested for polychlorinated dibenzofurans (PCDFs). Concentrations of total PCNs in biota were 3-5 orders of magnitude less than in sediments. The profile of PCN congeners in biota was predominated by tetra-or penta-chloronaphthalenes, while hepta-and octa-chloronaphthalenes were not detected. Affinity of more chlorinated naphthalene congeners to sediment organic carbon and steric factors that affect membrane permeability have contributed to less bioavailability. The 2,3,7,8-TCDD equivalents (TEQs) estimated for PCNs in sediments and biota were greater than those reported for PCBs, PCDDs, or PCDFs. Our results suggest that the chloralkali process has been an important source of PCNs due to their formation in the process. The contribution of PCNs to dioxin-like toxicity in environmental media near the chlor-alkali process may overwhelm those due to PCBs, PCDDs, or PCDFs.