The role of direct photolysis in the photodegradation of the herbicide bentazone in natural surface waters

The photochemical fate of the herbicide bentazone was assessed by lab experiments and modeling tools. Experimental and modeling results showed that bentazone is mainly photodegraded by direct photolysis in natural water samples, even in the presence of dissolved organic matter (DOM) that can act as light-screening agent, photosensitizer and scavenger of reactive species. Even when it was dissolved in natural water samples containing different DOM amounts, the phototransformation kinetics of bentazone was unchanged compared to irradiation runs in ultrapure water. This finding suggests that the DOM and the other components of our samples did not affect the direct photolysis of bentazone by light-absorption competition, at least at the experimental optical path lengths, and did not induce significant indirect photodegradation by producing reactive transient species. Photochemical modeling in a lake-water photoreactivity scenario corroborated the observed experimental results, showing the predominant role of direct photolysis in the overall (direct + indirect) photodegradation of bentazone at different water depths and DOM contents. However, the model predicted a minor but non-negligible contribution of indirect photochemistry (i.e., reactions triggered by HO center dot, CO3 center dot- and (CDOM)-C-3*) to the herbicide degradation. This contribution (especially by (CDOM)-C-3*) could become crucial in deep and DOM-rich water bodies. Finally, several photoproducts formed by direct photolysis and HO center dot-induced photodegradation were identified, which should not be particularly toxic for aquatic organisms and Vibrio fischeri bacteria. (C) 2019 Elsevier Ltd. All rights reserved.