The Roles of Reactive Species in Micropollutant Degradation in the UV/Free Chlorine System

Abstract

The UV/free chlorine process forms reactive species such as hydroxyl radicals (HO(•)), chlorine atoms (Cl(•)), Cl2(•-), and O(•-). The specific roles of these reactive species in aqueous micropollutant degradation in the UV/chlorine process under different conditions were investigated using a steady-state kinetic model. Benzoic acid (BA) was chosen as the model micropollutant. The steady-state kinetic model developed fitted the experimental data well. The results showed that HO(•) and Cl(•) contributed substantially to BA degradation, while the roles of the other reactive species such as Cl2(•-) and O(•-) were negligible. The overall degradation rate of BA decreased as the pH increased from 6 to 9. In particular, the relative contributions of HO(•) and Cl(•) to the degradation changed from 34.7% and 65.3% respectively at pH 6 to 37.9% and 62% respectively at pH 9 under the conditions evaluated. Their relative contributions also changed slightly with variations in chlorine dosage, BA concentration and chloride concentration. The scavenging effect of natural organic matter (NOM) on Cl(•) was relatively small compared to that on HO(•), while bicarbonate preferentially reduced the contribution of Cl(•). This study is the first to demonstrate the contributions of different reactive species to the micropollutant degradation in the UV/chlorine system under environmentally relevant conditions.