Linköping : Statens Väg- och Trafikinstitut., VTI notat T 144
Doi
Abstract
<i>N</i>-Nitrosodimethylamine
(NDMA) is a carcinogenic
disinfection byproduct from water chloramination. Despite the identification
of numerous NDMA precursors, essential parts of the reaction mechanism
such as the incorporation of molecular O<sub>2</sub> are poorly understood.
In laboratory model systems for the chloramination of secondary and
tertiary amines, we investigated the kinetics of precursor disappearance
and NDMA formation, quantified the stoichiometries of monochloramine
(NH<sub>2</sub>Cl) and aqueous O<sub>2</sub> consumption, derived <sup>18</sup>O-kinetic isotope effects (<sup>18</sup>O-KIE) for the reactions
of aqueous O<sub>2</sub>, and studied the impact of radical scavengers
on NDMA formation. Although the molar NDMA yields from five <i>N</i>,<i>N</i>-dimethylamine-containing precursors
varied between 1.4% and 90%, we observed the stoichiometric removal
of one O<sub>2</sub> per <i>N</i>,<i>N</i>-dimethylamine
group of the precursor indicating that the oxygenation of N atoms
did not determine the molar NDMA yield. Small <sup>18</sup>O-KIEs
between 1.0026 ± 0.0003 and 1.0092 ± 0.0009 found for all
precursors as well as completely inhibited NDMA formation in the presence
of radical scavengers (ABTS and trolox) imply that O<sub>2</sub> reacted
with radical species. Our study suggests that aminyl radicals from
the oxidation of organic amines by NH<sub>2</sub>Cl and <i>N</i>-peroxyl radicals from the reaction of aminyl radicals with aqueous
O<sub>2</sub> are part of the NDMA formation mechanism