Photodegradation kinetics, products and mechanism of timolol under simulated sunlight.

The photodegradation of β-blocker timolol in fulvic acid (FA) solution was investigated under simulated sunlight. The triplet excited state of FA ((3)FA()) and singlet oxygen ((1)O2) were the main reactive species responsible for the degradation of timolol in the aerated FA solutions. Both dissolved oxygen and iodide ions (I(-)) are the efficient quenchers of (3)FA(). The photodegradation was drastically accelerated after removing the dissolved oxygen. The presence of I(-) inhibited the photosensitized degradation of timolol in the deoxygenated FA solutions, whereas the role of I(-) in the reaction was concentration-dependent in the aerated solutions. The other halide ions such as chloride (Cl(-)) and bromide (Br(-)) exhibited less effect on the photodegradation of timolol in both aerated and deoxygenated solutions. By LC-DAD/ESI-MS/MS analysis, the photoproducts of timolol in both aerated and deoxygenated FA solutions were identified. Electron transfer interaction occurred between (3)FA(*) and amine moiety of timolol, leading to the cleavage of C-O bond in the side chain and oxidation of the hexatomic ring. These findings suggest the photosensitized degradation was a significant pathway for the elimination of timolol in natural waters.