Photodegradation of Fludioxonil and Other Pyrroles: The Importance of Indirect Photodegradation for Understanding Environmental Fate and Photoproduct Formation.

Fludioxonil is a pyrrole-containing pesticide whose registration as a plant protection product is currently under review in the United States and Europe. There are concerns over its potential persistence and toxicity in the aquatic environment; however, the pyrrole moiety represents a potential reaction site for indirect photodegradation. In this study, the direct and indirect photodegradation of fludioxonil, along with pyrrole, 3-cyanopyrrole, and 3-phenylpyrrole, were investigated. Results showed that pyrrole moieties are capable of undergoing direct photoionization and sensitized photooxidation to form radical cation species, which then likely deprotonate and react with dissolved oxygen. Additionally, pyrrole moieties can undergo reactions with singlet oxygen (1O2). Furthermore, the presence of electron-withdrawing or -donating substituents substantially impacted the reaction rate with 1O2 as well as the one-electron oxidation potential of the pyrrole that dictates reactions with triplet states of dissolved organic matter (3CDOM*). For fludioxonil, which can undergo both direct and indirect photodegradation, the reaction rate constant with 1O2 alone resulted in a predicted t1/2 < 2 days in waters under sunlit near-surface conditions, suggesting it will not be persistent in aquatic systems. These results are useful for evaluating the environmental fate of fludioxonil as well as other pyrrole compounds.