Nitrogen origins and the role of ozonation in the formation of haloacetonitriles and halonitromethanes in chlorine water treatment

Nitrogenous disinfection byproducts (N-DBPs) such as haloacetonitriles (HANs) and halonitromethanes (HNMs) are formed during water chlorination. Preozonation is sometimes applied to control trihalomethane (THM) formation, but this may risk promoting the formation of HNMs and HANs. The role of ozone in the formation of HANs and HNMs in natural waters remains unclear. The nitrogen sources involved in HAN and HNM formation during the chloramination of dissolved organic matter (DOM) with and without preozonation were evaluated using ¹⁵N-labeled monochloramine. The origin of the nitrogen involved in HAN formation was found to depend on the ratio of dissolved organic carbon to nitrogen. In nitrogen-rich solutions HAN nitrogen was mainly from DOM constituents. The formation of ¹⁵N-labeled dichloroacetontrile (DCAN) accounted for approximately 30% of the DCAN produced from all hydrophilic acidic and neutral isolates, which have low carbon to nitrogen ratios, while it reached over 50% for the hydrophobic acidic, basic, and neutral isolates with high carbon to nitrogen ratios. Unlabeled trichloronitromethane (TCNM) accounted for over 90% of the total TCNM produced from most of the isolates. The remaining less than 10% of the TCNM was probably generated through an aldehyde pathway. Preozonation reduced DCAN but enhanced the yield of TCNM. The destruction of amino acids and amine structures and subsequent formation of nitro groups by preozonation may help explain the reduced DCAN and increased TCNM formation.