Sodium hydroxide-enhanced acetaminophen elimination in heat/peroxymonosulfate system: Production of singlet oxygen and hydroxyl radical

Owing to the high peroxide bond dissociation energy (377 kJ mol−1), peroxymonosulfate (PMS) is rather difficult to be activated by heat for degrading organic pollutants. This work is the first to add sodium hydroxide (NaOH) to enhance the elimination of acetaminophen in heat/PMS system. Heat/PMS system even possessed a better Performance than heat/peroxydisulfate (PDS) system with the addition of NaOH. Quenching experiments and electron paramagnetic resonance tests demonstrated that singlet oxygen and hydroxyl radical were the primary reactive oxygen species responsible for acetaminophen elimination in NaOH-enhanced heat/PMS system. Singlet oxygen mainly came from the alkaline activation of PMS, while hydroxyl radical was generated from the thermolysis of peroxide bond. Increasing PMS concentration and reaction temperature favored the production of reactive oxygen species and the elimination of acetaminophen. Nine degradation intermediates of acetaminophen were identified by LC/TOF/MS and the corresponding degradation pathways were proposed. Chloride ion significantly accelerated the elimination of acetaminophen, while humic acid and carbonate ion slightly retarded acetaminophen removal. NaOH-enhanced heat/PMS system was highly efficient in eliminating many organic pollutants and more prone to degrading electron-rich organics. This study developed a simple and efficient approach to strengthening the oxidation capacity of heat-activated PMS and highlighted the superiority of PMS to PDS in thermolysis under alkaline conditions.