Feasibility of the solar/chlorine treatment for lipid regulator degradation in simulated and real waters: The oxidation chemistry and affecting factors.

This work investigated the feasibility and mechanisms of solar/chlorine process in the removal of a kind of emerging contaminants, lipid regulators (gemfibrozil (GFRZ), benzafibrate (BZF), and clofibric acid (CA)), in simulated and real waters. These lipid regulators could be effectively removed by solar/chlorine treatment, and their corresponding pseudo-first-order rate constants (k') increased with increasing chlorine dosage. The degradation of GFRZ and BZF was primarily ascribed to reactive chlorine species (RCS) and ozone, while that of CA was mainly attributable to hydroxyl radical (HO) and ozone. As pH rose from 5.0 to 8.4, kozone' of GFRZ and BZF increased, while kHO' decreased. However, kRCS' of GFRZ increased by 130%, while that of BZF decreased by 43.3%. These changes resulted in slight changes in the overall k's with increasing pH. k's of GFRZ, BZF, and CA by solar/chorine treatment were inhibited by natural organic matter (NOM) while the presence of bromide enhanced the degradation of GFRZ by solar/chlorine process. The degradation of lipid regulators was still effective in a secondary wastewater effluent sample and a sand-filtered water sample, although that was inhibited due to the dissolve organic matter (DOM) contained in real waters. The acute toxicity during the degradation of GFRZ by solar/chlorine treatment was comparable to that by treatment with chlorine alone. This study demonstrated that RCS played an important role in the degradation of micropollutants by the solar/chlorine treatment and the feasibility of solar/chlorine process in the application for the degradation of organic compounds in real waters.

Degradation of lipid regulators by the UV/chlorine process: Radical mechanisms, chlorine oxide radical (ClO•)-mediated transformation pathways and toxicity changes.

Degradation of three lipid regulators, i.e., gemfibrozil, bezafibrate and clofibric acid, by a UV/chlorine treatment was systematically investigated. The chlorine oxide radical (ClO•) played an important role in the degradation of gemfibrozil and bezafibrate with second-order rate constants of 4.2 (±0.3) × 108 M-1 s-1 and 3.6 (±0.1) × 107 M-1 s-1, respectively, whereas UV photolysis and the hydroxyl radical (HO•) mainly contributed to the degradation of clofibric acid. The first-order rate constants (k') for the degradation of gemfibrozil and bezafibrate increased linearly with increasing chlorine dosage, primarily due to the linear increase in the ClO• concentration. The k' values for gemfibrozil, bezafibrate, and clofibric acid degradation decreased with increasing pH from 5.0 to 8.4; however, the contribution of the reactive chlorine species (RCS) increased. Degradation of gemfibrozil and bezafibrate was enhanced in the presence of Br-, whereas it was inhibited in the presence of natural organic matter (NOM). The presence of ammonia at a chlorine: ammonia molar ratio of 1:1 resulted in decreases in the k' values for gemfibrozil and bezafibrate of 69.7% and 7%, respectively, but led to an increase in that for clofibric acid of 61.8%. Degradation of gemfibrozil by ClO• was initiated by hydroxylation and chlorine substitution on the benzene ring. Then, subsequent hydroxylation, bond cleavage and chlorination reactions led to the formation of more stable products. Three chlorinated intermediates were identified during ClO• oxidation process. Formation of the chlorinated disinfection by-products chloral hydrate and 1,1,1-trichloropropanone was enhanced relative to that of other by-products. The acute toxicity of gemfibrozil to Vibrio fischeri increased significantly when subjected to direct UV photolysis, whereas it decreased when oxidized by ClO•. This study is the first to report the transformation pathway of a micropollutant by ClO•.