This study aims to identify the highly non-specific toxic by-products during ozonation of three cresols in wastewater.In ozonated effluents,biotoxicity increased along with increasing reaction time,followed by a gradu...This study aims to identify the highly non-specific toxic by-products during ozonation of three cresols in wastewater.In ozonated effluents,biotoxicity increased along with increasing reaction time,followed by a gradual decrease.The peak biotoxicity for ozonated o-cresol(o-C),m-cresol(m-C),and p-cresol(p-C)was estimated to be 17.4,14.8 and 5.5 times higher than that of untreated wastewater,respectively.A redox-directed approach with high-resolution mass spectrometry detection and toxicity prediction revealed that monomeric para-benzoquinones(p-BQs),hydroxylated p-BQs,and dimeric p-BQs in ozonated cresols were the primary contributors to the increased toxicity.Calculations based on density functional theory indicated formation pathways of p-BQs byproducts,e.g.,the formation of 2-methyl-p-benzoquinone was likely induced by ozone molecules rather than hydroxyl radicals in ozonated o-C and m-C,and the formation of p-BQs during ozonation of p-C was attributed to the oxidation of methyl group to carboxyl group and subsequent decarboxylation initiated by hydroxyl radicals.Electron paramagnetic resonance and spin density calculation showed that the presence of carbon-centered cresoxyl radicals was responsible for dimeric p-BQs formation.Collectively,these results underscore significant contribution of non-halogenated p-BQs to non-specific toxicity increase in ozonated effluents.展开更多
基金supported by the National Natural Science Foundation of China(Nos.52270073 and 51708292)。
文摘This study aims to identify the highly non-specific toxic by-products during ozonation of three cresols in wastewater.In ozonated effluents,biotoxicity increased along with increasing reaction time,followed by a gradual decrease.The peak biotoxicity for ozonated o-cresol(o-C),m-cresol(m-C),and p-cresol(p-C)was estimated to be 17.4,14.8 and 5.5 times higher than that of untreated wastewater,respectively.A redox-directed approach with high-resolution mass spectrometry detection and toxicity prediction revealed that monomeric para-benzoquinones(p-BQs),hydroxylated p-BQs,and dimeric p-BQs in ozonated cresols were the primary contributors to the increased toxicity.Calculations based on density functional theory indicated formation pathways of p-BQs byproducts,e.g.,the formation of 2-methyl-p-benzoquinone was likely induced by ozone molecules rather than hydroxyl radicals in ozonated o-C and m-C,and the formation of p-BQs during ozonation of p-C was attributed to the oxidation of methyl group to carboxyl group and subsequent decarboxylation initiated by hydroxyl radicals.Electron paramagnetic resonance and spin density calculation showed that the presence of carbon-centered cresoxyl radicals was responsible for dimeric p-BQs formation.Collectively,these results underscore significant contribution of non-halogenated p-BQs to non-specific toxicity increase in ozonated effluents.
