Photolysis of atrazine: Role of triplet dissolved organic matter and limitations of sensitizers and quenchers

Atrazine, a widely used herbicide, is susceptible to photolysis. The role of triplet excited states of chromophoric dissolved organic matter (³CDOM*) in the photolysis of atrazine, however, is not well understood. The direct photolysis of atrazine under irradiation sources (natural sunlight/environmentally relevant simulated solar light) and its indirect photochemical reactivity with model triplet photosensitizers (benzophenone, 2-acetonaphthone, 3′-methoxy-acetophenone, 4-carboxybenzophenone, rose bengal, methylene blue, and anthraquinone-2-sulphonate) was investigated. The reactivity of the model sensitizers and DOM (Suwannee River natural organic matter, river/lake water, and wastewater effluent), were compared. The direct photolysis quantum yield was determined as 0.0196 mol Einstein⁻¹ in a solar simulator and 0.00437 mol Einstein⁻¹ under natural sunlight. Considerable photosensitization was induced by triplet state (n-π*) model sensitizers, while insignificant effects on atrazine loss were discerned in natural organic matter even when oxygen, a triplet quencher, was removed. The triplet sensitizers benzophenone and 2-acetylnaphthone reacted with L-histidine and 2-propanol that were intended to quench/ scavenge ¹O₂ and hydroxyl radical ^•OH, respectively, and benzophenone reacted with NaN₃ as a ¹O₂ scavenger and furfuryl alcohol as a ¹O₂ trapping agent, indicating quenchers may have unanticipated effects when using model sensitizers. Atrazine loss via reaction with ³DOM* will be relevant only in selected conditions, and this work provides a more comprehensive view on the use of model photosensitizers to mimic triplet ³DOM*.