Polychlorinated naphthalenes were quantified in 10 lake and sea sediment samples from sites with no known present local pollution source. Levels ranged from 0.14 to 7.6 ng/g (dry weight). The chlorinated naphthalene (CN) congener profiles showed an increased relative abundance of 1,3,5,7- and 1,4,6,7-substituted congener profiles as compared to the reported CN congener profiles of technical PCN and PCB. Further, a dominance of 1,2,3,4,5,6,7-hepta CN over 1,2,3,4,5,6,8-heptaCN was found in all samples in contrast to the ratio reported for technical PCN and PCB products. Some samples showed traces of 2,3,6,7-substituted CN congeners, indicative of thermal sources, such as municipal waste incineration. These profiles were compared with the profiles obtained from a Halowax 1014 technical mixture subject to aerobic microbial degradation and sunlight photolysis. The aerobic microbial culture gave no alteration of the CN congener profile of over a 28-day period, whereas sunlight exposure of Halowax 1014 in methanol yielded a more low chlorinated CN congener profile. Furthermore, CN congeners with chlorines in 1,8-positions were more affected than those with 1,3,5,7- or 1,4,6,7-substitutidn. These results indicate that photolysis may explain the enhancement of the relative abundance of some of the 1,3,5,7- and 1,4,6,7-substituted CN congeners in the environment but not the heptaCN profile.