Direct and indirect photodegradation in aquatic systems mitigates photosensitized toxicity in screening-level substance risk assessments of selected petrochemical structures

Photochemical processes are typically not incorporated in screening-level substance risk assessments due to the complexity of modeling sunlight co-exposures and resulting interactions on environmental fate and effects. However, for many substances, sunlight exerts a profound influence on environmental degradation rates and ecotoxicities. Recent modeling advances provide an improved technical basis for estimating the effect of sunlight in modulating both substance exposure and toxicity in the aquatic environment. Screening model simulations were performed for 25 petrochemical structures with varied uses and environmental fate properties. Model predictions were evaluated by comparing the ratios of predicted exposure concentrations with and without light to the corresponding ratios of toxicity thresholds under the same conditions. The relative ratios of exposure and hazard in light vs. dark were then used to evaluate how inclusion of light modulates substance risk analysis. Results indicated that inclusion of light reduced PECs by factors ranging from 1.1- to 63-fold as a result of photodegradation, while reducing PNECs by factors ranging from 1- to 49-fold due to photoenhanced toxicity caused by photosensitization. Consequently, the presence of light altered risk quotients by factors that ranged from 0.1- to 17-fold, since the predicted increase in substance hazard was mitigated by the reduction in exposure. For many structures, indirect photodegradation decreases environmental exposures independently of the direct photolysis pathway which is associated with enhanced phototoxicity. For most of the scenarios and chemicals in the present work, photosensitization appears to be mitigated by direct and indirect degradation from sunlight exposure.