Degradation of saccharin by UV/H₂O₂ and UV/PS processes: A comparative study

Artificial sweeteners have raised emerging concern due to their potential threats to human health, which were frequently detected in aquatic environment with median concentrations. Although current researches have widely reported that ultraviolet light-activated persulfate process (UV/PS) was superior to UV/H₂O₂ process for the degradation of refractory organic contaminants, UV/H₂O₂ process presented a more satisfactory saccharin (SAC) removal efficiency than UV/PS process, completely degraded 20 mg/L SAC within 45 min. Hence, quenching and probe experiments were employed to investigate the difference between hydroxyl radical (OH)- and sulfate radical (SO₄^-)-mediated oxidation mechanisms, which revealed the higher reactivity of OH (1.37-1.56 × 10⁹ M^-1 s^-1) toward SAC than SO₄^- (3.84-4.13 × 10⁸ M^-1 s^-1). A combination of density functional theory calculation and transformation products identification disclosed that OH preferred to attack the benzene ring of SAC via hydrogen atom transfer pathway, whereas SO₄^- oxidation was conducive to the cleavage of -C-NH₂ bond. Increasing oxidant concentration significantly accelerated SAC degradation in both processes, while UV/H₂O₂ process consumed lower electrical energy with respect to UV/PS process. Additionally, UV/H₂O₂ system presented excellent adaptability and stability under various water matrices parameters (e.g. pH, anions and humic acid). While both UV/H₂O₂ and UV/PS processes promoted the generation of disinfection by-products (DBPs) during subsequent chlorination, and prolonging pretreatment time posed positive effect on reducing the formation of DBPs. Overall, the results clearly demonstrate the high efficiency, economy and practicality of UV/H₂O₂ process in the remediation of SAC-contaminated water.