Transformation of halobenzoquinones with the presence of amino acids in water: Products, pathways and toxicity

Abstract

The transformation and detoxification of halobenzoquinones (HBQs), a class of emerging disinfection byproducts (DBPs), was studied in the presence of amino acids (AAs). The reaction activity of three HBQs with AAs generally ranked as 2-chlorobenzoquinone (CBQ) < 2,6-dichlorobezoquinone (DCBQ) < tetrachloroquinone (TCBQ), consistent with their halogenation degree and the calculated electron affinity (EA) results. According to mass spectrometry and density functional theory (DFT) calculations, AAs can easily covalently incorporate into HBQs via nucleophilic addition (CBQ and DCBQ) or substitution (TCBQ) through CNC or CSC linkages. Hydroxylation, nucleophilic reaction and decarboxylation were proposed to be the three major reaction pathways for HBQs transformation with AAs. HBQs firstly underwent the spontaneous hydrolysis, resulting in OH-HBQs formation. Then, nucleophilic addition/substitution of AAs occurred on HBQs and OH-HBQs to produce AA-HBQs/AA-HBQs-OH adducts. These adducts were subsequently oxidized into their corresponding decarboxylated forms. Based on the results of Luminous bacterium Q67 acute toxicity test, the toxicity of HBQs solution greatly decreased with AAs presented. The toxicity change was well explained by the lowest unoccupied molecular orbital energy (ELUMO) of formed products. Notably, the step that AAs nucleophilic bonded with HBQs led to the highest rise of ELUMO, which should be the most effective pathway for HBQs detoxification. This study shows that binding with amino nitrogen compounds should be an important process for HBQs transformation and detoxification, which helps to better understand the fate of this typical DBP in surface water.