Influence of solution pH on degradation of atrazine during UV and UV/HO oxidation: kinetics, mechanism, and degradation pathways.

The kinetics, degradation mechanism and degradation pathways of atrazine (ATZ) during sole-UV and UV/HO processes under various pH conditions were investigated; the effects of UV irradiation time and HO dose were also evaluated. A higher reaction rate was observed under neutral pH conditions in the UV only process. For the UV/HO process, a higher reaction rate was observed in acidic solution and the degradation rate of ATZ firstly increased with the increase of concentration of HO and then decreased when HO concentration exceeded 5 mg L. In addition, qualitative and quantitative analyses of oxidation intermediates of ATZ in aqueous solution during the sole-UV and UV/HO processes were conducted using UPLC-ESI-MS/MS. Ten kinds of dechlorinated intermediates were detected during sole-UV treatment under all five pH conditions. In contrast, the speciation of intermediates in the UV/HO process varied dramatically with solution pH. Based on the analysis of ATZ oxidation intermediates, ATZ degradation pathways under different pH conditions were proposed for the sole-UV and UV/HO processes. The results showed that the main degradation reactions of ATZ included dechlorination-hydroxylation, dechlorination-dealkylation, de-alkylation, deamination-hydroxylation, alkylic-oxidation of lateral chains, dehydrogenation-olefination, dechlorination-hydrogenation, dechlorination-methoxylation and dehydroxylation.