We report the characterization and determination of 2,6-dichloro-1,4-benzoquinone and three new disinfection byproducts (DBPs): 2,6-dichloro-3-methyl-1,4-benzoquinone, 2,3,6-trichloro-1,4-benzoquinone, and 2,6-dibromo-1,4-benzoquinone. These haloquinones are suspected bladder carcinogens and are likely produced during drinking water disinfection treatment. However, detection of these haloquinones is challenging, and consequently, they have not been characterized as DBPs until recently. We have developed an electrospray ionization tandem mass spectrometry technique based on our observation of unique ionization processes. These chloro- and bromo-quinones were ionized through a reduction step to form [M + H](-) under negative electrospray ionization. Tandem mass spectra and accurate mass measurements of these compounds showed major product ions, [M + H - HX](-), [M + H - HX - CO](-), [M + H - CO](-), and/or X(-) (where X represents Cl or Br). The addition of 0.25% formic acid to water samples was found to effectively stabilize the haloquinones in water and to improve the ionization for analysis. These improvements were rationalized from the estimates of pK(a) values (5.8-6.3) of these haloquinones. The method of tandem mass spectrometry detection, combined with sample preservation, solid phase extraction, and liquid chromatography separation, enabled the detection of haloquinones in chlorinated water samples collected from a drinking water treatment plant. The four haloquinones were detected only in drinking water after chlorination treatment, with concentrations ranging from 0.5 to 165 ng/L, but were not detectable in the untreated water. This method will be useful for future studies of occurrence, formation pathways, toxicity, and control of these new halogenated DBPs.

Formation of nine N-nitrosamines has been investigated when seven different source waters representing various qualities were each treated with eleven bench-scale disinfection processes, without addition of nitrosamine precursors. These disinfection treatments included chlorine (OCl-), chloramine (NH2Cl), chlorine dioxide (ClO2), ozone (O3), ultraviolet (UV), advanced oxidation processes (AOP), and combinations. The total organic carbon (TOC) of the seven source waters ranged from 2 to 24 mg x L(-1). The disinfected water samples and the untreated source waters were analyzed for nine nitrosamines using a solid phase extraction and liquid chromatography-tandem mass spectrometry method. Prior to any treatment, N-nitrosodimethylamine (NDMA) was detected ranging from 0 to 53 ng x L(-1) in six of the seven source waters, and its concentrations increased in the disinfected water samples (0-118 ng x L(-1)). N-nitrosodiethylamine (NDEA), N-nitrosomorpholine (NMor), and N-nitrosodiphenylamine (NDPhA) were also identified in some of the disinfected water samples. NDPhA (0.2-0.6 ng x L(-1)) was formed after disinfection with OCl-, NH2Cl, O3, and MPUV/OCl-. NMEA was produced with OCl- and MPUV/OCl-, and NMor formation was associated with O3. In addition, UVtreatment alone degraded NDMA; however, UV/ OCl- and AOP/OCl- treatments produced higher amounts of NDMA compared to UV and AOP alone, respectively. These results suggest that UV degradation or AOP oxidation treatment may provide a source of NDMA precursors. This study demonstrates that environmental concentrations and mixtures of unknown nitrosamine precursors in source waters can form NDMA and other nitrosamines.

Coming clean? Liquid chromatography–ESI tandem mass spectrometry is used to detect 2,6‐dichloro‐1,4‐benzoquinone (see picture) in drinking water treated with chlorine or chloramine.

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