Halonaphthoquinones: A group of emerging disinfection byproducts of high toxicity in drinking water

•A sensitive SPE-UPLC-MS/MS method was developed to detect halonaphoquinones (HNQs).•Five HNQs were identified as new disinfection byproducts (DBPs) in drinking water.•Polycyclic aromatic hydrocarbons (PAHs) were precursors of HNQs.•Boiling increased the concentration of dihalonaphoquinones.•Cytotoxicity of HNQs was comparable to the most toxic known C-DBP, iodoacetic acid. Aromatic halogenated disinfection byproducts (DBPs) have received particular attention in recent years due to their high toxicity. However, most relevant researches at present focused merely on halo-monocyclic DBPs, while halo-polycyclic DBPs were scarcely explored. In this study, a new group of halo-bicyclic DBPs termed as halonaphthoquinones (HNQs) was systematically studied. By coupling with vacuum centrifugal concentrator, a SPE-UPLC-MS/MS method with high accuracy and sensitivity was developed to detect five semi-volatile HNQs in drinking water, which achieved the detection limits in the range of 0.05–0.24 ng/L. Five HNQs were identified using this method with 100% detection frequency at concentrations up to 136.7 ng/L in drinking water originated from seven water treatment plants. The cytotoxicity of the five tested HNQs in CHO-K1 cells (IC50 from 3.17 to 13.18 μM) was comparable to the most toxic known carbonaceous DBP in drinking water, iodoacetic acid (IC50=2.95 μM). Meanwhile, the cytotoxicity of five tested HNQs were also higher than 2,6-dichloro-1,4-benzoquinone (IC50=21.73 μM) which is hundreds to thousands of times more toxic than regulated DBPs, indicating the significant toxicity risk of HNQ DBPs. To the best of our knowledge, this study presents the first analytical method for analysis of HNQ DBPs, and the first set of data on the occurrence and cytotoxicity of HNQ DBPs in drinking water. These findings are meaningful for probing deeply into the presence of varied halo-polycyclic DBPs in the aqueous environment. [Display omitted]