In recent years, the UV/sulfite (S(IV)) has been proposed as a promising advanced oxidation process for water treatment in the presence of oxygen. However, the mechanism of S(IV) activation is not fully understood, as the interaction between S(IV) and photo-excited pollutants has been underexplored. In this work, an aerated UV/S(IV) system was established, and propranolol (PRO) was selected as a target pollutant. Under the irradiation at 254 nm, this system could degrade 95.6 % of PRO with 2 mM S(IV) in 60 min. The removal of PRO was positively related to the S(IV) dose, while an increasing pH exhibited a negative effect. Direct photolysis, SO4•−, and HO• collaboratively contributed to PRO removal, with SO4•− playing a primary role. Laser flash photolysis reveals that both radical cation of PRO (product of biphotonic process) and the triplet state (T1PRO) can react with HSO3− at rate constants of 5.2 × 108 M−1 s−1 and 2.1 × 107 M−1 s−1, accordingly. These reactions may offset the deficient photoactivation of S(IV) under acidic conditions. Apart from PRO, other organic pollutants could also be effectively degraded. Furthermore, this system has a great advantage over UV/persulfate due to the absence of transformation of background bromide ions to hazardous bromate. Our study significantly updates the decontaminating mechanism of organic pollutants in the aerated UV/sulfite system.
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