Ozone oxidation of 2,4,6-TCP in the presence of halide ions: Kinetics, degradation pathways and toxicity evaluation

Abstract

2,4,6-Trichlorophenol (2,4,6-TCP) is extensively consumed in industrial production and may cause environmental damages. The effect of halide ions on the decomposition of 2,4,6-TCP has often been overlooked. In this study, the bromide ion was found to have a stronger negative impact on 2,4,6-TCP degradation than chloride ion in the O₃ system, and led to the formation of adsorbable organic halogens (AOX). Kinetic modeling demonstrated that the concentration of various radicals was largely depended on the solution pH, and stronger basicity not only contributed to the mineralization of 2,4,6-TCP, but also inhibited the formation of halogenated by-products. Combining the intermediate identification and quantum chemical calculation, the degradation pathways of 2,4,6-TCP during ozone oxidation process were proposed. The toxicity test and ECOSAR simulation demonstrated that the acute toxicity of some 2,4,6-TCP degradation intermediates was relatively higher than their parent compound. With high concentrations of halide ions, the ozone-treated solution showed greater toxicity than the originator 2,4,6-TCP solution. These results illustrate that the ozone treatment of the halide-containing wastewater may cause potential ecological hazards and its application needs to be more cautious.

Keywords: Adsorbable organic halogens (AOX); Density functional theory (DFT); Halide ions; Kinetic modeling; Ozone treatment; Toxicity.