PPCP degradation and DBP formation in the solar/free chlorine system: Effects of pH and dissolved oxygen

The solar/chlorine process produces multiple reactive species by solar photolysis of chlorine, which can be used as an energy-efficient technology for water treatment. This study investigated the effects of pH and dissolved oxygen (DO) on the degradation of pharmaceuticals and personal care products (PPCPs) and on the formation of disinfection byproducts (DBPs) in the solar/chlorine system. The degradation of 24 structurally diverse PPCPs was enhanced appreciably in the solar/chlorine system compared to solar irradiation and dark chlorination. The reactive species in the solar/chlorine system were identified to be hydroxyl radicals (HO), reactive chlorine species (RCS, i.e., Cl and ClO) and ozone. With increasing pH from 6 to 8, the steady-state concentrations of HO and Cl decreased from 1.23 × 10-14 M to 4.79 × 10-15 M and from 9.80 × 10-16 M to 4.31 × 10-16 M, respectively, whereas that of ClO increased from 5.30 × 10-14 M to 2.68 × 10-13 M and the exposure of ozone increased from 0.44 μM min to 1.01 μM min in 90 min. Accordingly, the removal efficiencies of 6 PPCPs decreased and 11 PPCPs increased. The decreased removal of PPCPs with increasing pH was due to the decrease in HO and Cl, while the increased removal was attributed to the increased ClO and ozone. The presence of DO enhanced the degradation of most PPCPs, indicating the role of ozone on the degradation. The formation of total organic chlorine (TOCl) and known DBPs was enhanced by 60.7% and 159.4%, respectively, in the solar/chlorine system compared to chlorination in a simulated drinking water containing 2.5 mg L-1 natural organic matter (NOM). As the pH rose from 6 to 8, TOCl formation decreased by 16.2%, while that of known DBPs increased by 58.6% in solar/chlorine. The absence of DO slightly suppressed the formation of TOCl and known DBPs. This study illustrated the significant role of RCS in the solar/chlorine system, which enhanced the degradation of micropollutants but increased the formation of chlorinated DBPs.