Nitrile, Aldehyde, and Halonitroalkane Formation during Chlorination/Chloramination of Primary Amines

The decreasing availability of pristine water supplies is prompting drinking water utilities to exploit waters impacted by wastewater effluents and agricultural runoff. As these waters feature elevated organic nitrogen concentra tions, the pathways responsible for transformation of organic nitrogen into toxic nitrogenous disinfection byproducts during chlorine and chloramine disinfection are of current concern. Partially degraded biomolecules likely constitute a significant fraction of organic nitrogen in these waters. As primary amines occur in important biomolecules, we investigated formation pathways for nitrile, aldehyde, and halonitroalkane byproducts during chlorination and chloramination of model primary amines. Chlorine and chloramines transformed primary amines to nitriles and aldehydes in significant yields over time scales relevant to drinking water distribution systems. Yields of halonitroalkanes were less significant yet may be important because of the high toxicity associated with these compounds. Our results indicate that chloramination should reduce nitrile concentrations compared to chlorination but may increase the formation of aldehydes and halonitroalkanes at high oxidant doses.