Indirect photodegradation of typical pyrrolizidine alkaloids in water induced by triplet states of dissolved organic matter

The occurrence of pyrrolizidine alkaloids (PAs) in the aquatic environment has received growing attention due to their persistent mutagenicity and carcinogenicity. In this study, the photooxidation processes of four representative PAs (senecionine, senecionine N-oxide, europine, and heliotrine) in the presence of dissolved organic matter (DOM) were investigated. The excited triplet DOM ((DOM)-D-3*) was demonstrated to play a dominant role in the phototransformation of PAs. The observed degradation rates of PAs largely depended on the DOM concentration. Alkaline conditions and the presence of HCO3-/CO32- were conducive to the photodegradation. Based on kinetic modeling, the second-order reaction rate constants of PAs with (DOM)-D-3* were predicted to be (1.7 similar to 5.3)x10(8) M-1 s(-1), nearly two orders of magnitude higher than those with singlet oxygen (O-1(2)). The monoester structure and electron-withdrawing substituent (e.g., -O atom) substantially affected the one-electron oxidation potential of PAs, which dictates the reaction rates of PAs with (DOM)-D-3*. Finally, a tentative degradation pathway of PAs was proposed, involving the formation of an N-centered radical cation through one-electron transfer, which then likely deprotonated and further oxidized to more persistent and toxic phototransformation products with an added oxygen atom into the pyrrole ring.