Precursors and nitrogen origins of trichloronitromethane and dichloroacetonitrile during chlorination/chloramination

The formation of trichloronitromethane (TCNM) and dichloroacetonitrile (DCAN) was investigated during chlorination and chloramination of 31 organic nitrogen (org-N) compounds, including amino acids, amines, dipeptides, purines, pyrimidones and pyrroles. Tryptophan and alanine generated the greatest amount of TCNM during chlorination process and asparagine and tyrosine yielded the highest amount of TCNM during chloramination process. Tryptophan, tyrosine, asparagine, and alanine produced more DCAN than other org-N compounds regardless of chlorination or chloramination. TCNM and DCAN formation was higher by chlorination than by chloramination. NH2Cl:org-N molar ratios, reaction time, and pH affected N-DBPs formation in varying degrees. TCNM and DCAN yields were usually high during chloramination of tyrosine, asparagine, and methylpyrrole under the following reaction conditions: NH2Cl:org-N molar ratios greater than 10, reaction time for 1 d, and at pH 7.2. NH2Cl as a major nitrogen origin in TCNM and DCAN was confirmed via labeled 15N-monochloramine during chloramination of tyrosine, asparagine and methylpyrrole. In contrast, the majority of nitrogen in TCNM originated from glycine, and that in DCAN originated from pyrrole. Based on the intermediates identified by gas chromatography/mass spectrometry (GC/MS), a pathway scheme was proposed for TCNM and DCAN formation.

► Formation of TCNM and DCAN was evaluated from 31 organic-N compounds.
► This is the first time to show NH2Cl contributes to nitrogen source of TCNM.
► The percentages of nitrogen partition from NH2Cl varied among compounds.
► A reaction scheme is proposed for TCNM and DCAN formation.