Photosensitized degradation of acetaminophen in natural organic matter solutions: The role of triplet states and oxygen

The photolysis of acetaminophen, a widely used pharmaceutical, in simulated natural organic matter solutions was investigated. The triplet states of natural organic matter (3NOM*) were found to play the dominant role in its photodegradation, while the contributions from hydroxyl radicals and singlet oxygen were negligible. Dissolved oxygen (DO) plays a dual role. From anaerobic to microaerobic (0.5 mg/L DO) conditions, the degradation rate of acetaminophen increased by 4-fold. That suggests the involvement of DO in reactions with the degradation intermediates. With increasing oxygen levels to saturated conditions (26 mg/L DO), the degradation rate became slower, mainly due to DO's quenching effect on 3NOM*. Superoxide radical (O2-) did not react with acetaminophen directly, but possibly quenched the intermediates to reverse the degradation process. The main photochemical pathways were shown to involve phenoxyl radical and N-radical cations, finally yielding hydroxylated derivatives, dimers and nitrosophenol. A reaction mechanism involving 3NOM*, oxygen and O2- is proposed.