Azaarenes are a group of heterocyclic PACs in which one carbon atom has been replaced by one nitrogen atom. Heterocyclic PACs commonly occur in the environment, but risk assessment for PACs is solely based on (a small number of) homocyclic compounds. In order to examine whether the present risk assessment accurately protects against a broader range of PACs, the aim of this study was to compare the toxicity of an analogue series of homocyclic and heterocyclic PACs to a representative benthic invertebrate, the midge Chironomus riparius. The present study focused on generating toxicity data (96 h LC 50 ) for naphthalene, anthracene, phenanthrene, and pyrene to allow a comparison with previously obtained results for azaarenes. Since photoenhanced toxicity was expected for some of the compounds tested, experiments were carried out with and without a UV filter in order to obtain a complete assessment of the toxic mechanisms involved. Toxicity of homocyclic PAHs and azaarenes increased with increasing number of rings. In general, homocyclic PAHs were more toxic than their N-heterocyclic analogues, but homocyclic PAHs also are more lipophilic than their heterocyclicThe authors thank the Dutch Ministry of Housing, Spatial Planning and the Environment for its financial support.