UV/H2O2 produced degradation of 2,4-D and 4-CPA

2,4-dichlorophenoxyacetic (2,4-D) acid and 4-chlorophenoxyacetic acid (4-CPA), as widely utilized organochlorine pesticides, are normally detected in wastewater and atmosphere. Their harmfulness to the ecosystem cannot be ignored. UV/H2O2 is one of the most conventional advanced oxidation processes, which has remarkable advantages for the removal of refractory organic pollutants in wastewater. However, the reaction mechanisms and pathways of pollutants with reactive radicals are still unclear. In this study, the degradation efficacy and mechanisms during the photodegradation of 2,4-D and 4-CPA in UV/H2O2 processes were investigated by experiments and density functional theory calculations. The results showed that 2,4-D was more likely to be degraded by UV/H2O2 treatment than UV photolysis alone. In contrast, 4-CPA can be degraded effectively and rapidly under UV irradiation alone. By LC-MS analysis, the degradation products of 2,4-D and 4-CPA in the UV/H2O2 processes were identified and they were produced by hydroxylation and photolysis. Therefore, we speculated a competition mechanism presented between direct photolysis and indirect photolysis in the UV/H2O2 degradation of 2,4-D and 4-CPA. The OH-initiated reaction mechanisms of 2,4-D and 4-CPA in aqueous environments were investigated using quantum chemical methods SMD/M06-2X/6-311++G(3df,2p)//SMD/M06-2X/6-311+G(d,p). The pH dependence of the reaction mechanisms and rate constants in their degradation process induced by ·OH was also investigated. The calculation results showed that the ionic forms (2,4-D- and 4-CPA-) were more prone to react with ·OH in comparison to the corresponding molecular forms (2,4-D and 4-CPA). The total rate constants of 2,4-D and 4-CPA with OH increased with the pH from 1 to 10, and decreased with continued pH increase. The toxicities of 2,4-D, 4-CPA and their products were assessed by the QSAR-based toxicity evaluation software. The results showed that several products were more toxic than their parent compounds, such as 2,4-dichlorophenol, 3,5-dichlorocatechol, 4-chlorophenol and hydroquinone. This work can contribute to clarifying the environmental risks of 2,4-D and 4-CPA and offer a complete understanding for the photodegradation behavior of 2,4-D and 4-CPA in aqueous ecosystems.