Activation of peroxymonosulfate by bicarbonate and acceleration of the reaction by freezing

This study demonstrates the positive effects of dissolved bicarbonate and carbonate anions on peroxymonosulfate (PMS) induced oxidation and the remarkable acceleration of the reaction by freezing. More than 90% of the initial 4-chlorophenol (4-CP) decomposed in the frozen case, whereas only less than 20% of the 4-CP was removed in the aqueous case in the same time period. This accelerated reaction is attributed to the freeze-concentration of the dissolved substrates (i.e., PMS, bicarbonate, and pollutants) in the quasi-liquid layer at the ice grain boundaries between ice crystals. The reaction between bicarbonate and PMS was found to be unique because none of the effects were observed in the phosphate and hydroxide cooperated system with freezing, although the base activation of PMS could participate under basic conditions (pH > 9). Based on electron paramagnetic resonance spectroscopy measurements and comparison with the photo-excited Rose Bengal system as a reference system for singlet oxygen (¹O₂) generation, ¹O₂ was found to have a minor effect on the oxidation of 4-CP in the frozen bicarbonate-PMS system. While, direct electron transfer from the target organic substrate to the PMS was suggested as a major mechanism of 4-CP oxidation, because the selected target organic substrates were decomposed with different tendencies, and the consumption of PMS was accelerated by the presence of an electron donating compound. The results show the potential applicability of the freezing phenomenon, which occurs naturally in the mid-latitude and polar area, to help a decomposition of water dissolved organic pollutants by the imitation of the natural purification process.