Carbonate Radical Oxidation of Cylindrospermopsin (Cyanotoxin): Kinetic Studies and Mechanistic Consideration

Cylindrospermopsin (CYN) is one of the most important cyanobacterial toxins frequently found in surface waters. We reported the detailed kinetics and pathways for the reaction of CYN with carbonate radicals (CO₃^•-). The rate constants of neutral and deprotonated CYN with CO₃^•- were found to be (1.2 ± 0.7) × 10⁷ M^-1 s^-1 and (3.0 ± 0.4) × 10⁸ M^-1 s^-1, respectively. The transformation products for the oxidation of CYN by CO₃^•- were identified by high-resolution mass spectrometry, illustrating that the guanidine and bridged hydroxyl portions were the primary moieties attacked by CO₃^•-. Thus, three transformation pathways, including cleavage of the hydroxymethyluracil moiety, hydroxylation, and oxidation of the bridged hydroxyl group, are proposed for the CO₃^•- oxidation of CYN. Moreover, this study reported that dissolved organic matter (DOM) reduced the transformation rate of CYN by inhibiting the transformation of oxidation intermediates. Finally, the role of CO₃^•- in CYN degradation was estimated in both sunlit surface waters and advanced oxidation processes (AOPs), demonstrating that CO₃^•- played an important role in CYN attenuation under nonacidic environmentally relevant conditions. The kinetic parameters and product information obtained in this study will be of considerable interest for the application of AOPs and predicting the environmental fate of CYN.