Formation and Occurrence of <i>N‑Chloro</i>-2,2-dichloroacetamide, a Previously Overlooked Nitrogenous Disinfection Byproduct in Chlorinated Drinking Waters

Haloacetamides (HAMs) are a class of newly identified nitrogenous disinfection byproducts (N-DBPs) whose occurrence in drinking waters has recently been reported in several DBP surveys. As the most prominent HAM species, it is commonly acknowledged that 2,2-dichloroacetamide (DCAM) is mainly generated from dichloroacetonitrile (DCAN) hydrolysis because the concentrations of these two compounds are often well correlated. Instead of DCAM, a previously unreported N-DBP, <i>N</i>-<i>chloro</i>-2,2-dichloroacetamide (<i>N-Cl</i>-DCAM), was confirmed in this study as the actual DCAN degradation product in chlorinated drinking waters. It is suspected that <i>N-Cl</i>-DCAM has been erroneously identified as DCAM, because its nitrogen-bound chlorine is readily reduced by most commonly used quenching agents. This hypothesis is supported by kinetic studies that indicate almost instantaneous <i>N</i>-chlorination of DCAM even at low chlorine residuals. Therefore, it is unlikely that DCAM can persist as a long-lived DCAN decomposition product in systems using free chlorine as a residual disinfectant. Instead, chlorination of DCAM will lead to the formation of an equal amount of <i>N-Cl</i>-DCAM by forming a hydrogen bond between hypochlorite oxygen and amino hydrogen. Alternatively, <i>N-Cl</i>-DCAM can be produced directly from DCAN chlorination via nucleophilic addition of hypochlorite on the nitrile carbon. Due to its relatively low p<i>K</i>_a value, <i>N-Cl</i>-DCAM tends to deprotonate under typical drinking water pH conditions, and the anionic form of <i>N-Cl</i>-DCAM was found to be very stable in the absence of chlorine. <i>N-Cl</i>-DCAM can, however, undergo acid-catalyzed decomposition to form the corresponding dichloroacetic acid (DCAA) when chlorine is present, although those acidic conditions that favor <i>N-Cl</i>-DCAM degradation are generally atypical for finished drinking waters. For these reasons, <i>N-Cl</i>-DCAM is predicted to have very long half-lives in most distribution systems that use free chlorine. Furthermore, an analytical method using ultra performance liquid chromatography (UPLC)/negative electrospray ionization (ESI^–)/quadrupole time-of-flight mass spectrometry (qTOF) was developed for the detection of a family of seven <i>N-chloro</i>-haloacetamides (<i>N-Cl</i>-HAMs). Combined with solid phase extraction (SPE), the occurrence of <i>N-Cl</i>-DCAM and its two brominated analogues (i.e., <i>N-chloro</i>-2,2-bromochloroacetamide and <i>N-chloro</i>-2,2-dibromoacetamide) was quantitatively determined for the first time in 11 real tap water samples. The discovery of <i>N-Cl</i>-DCAM or, more broadly speaking, <i>N-Cl</i>-HAMs in chlorinated drinking waters is of significance because they are organic chloramines, a family of compounds that is perceived to be more toxicologically potent than halonitriles (e.g., DCAN) and haloamides (e.g., DCAM), and therefore they may pose greater risks to drinking water consumers given their widespread occurrence and high stability