Reactions of aliphatic amines with ozone: Kinetics and mechanisms

Aliphatic amines are common constituents in micropollutants and dissolved organic matter and present in elevated concentrations in wastewater-impacted source waters. Due to high reactivity, reactions of aliphatic amines with ozone are likely to occur during ozonation in water and wastewater treatment. We investigated the kinetics and mechanisms of the reactions of ozone with ethylamine, diethylamine, and triethylamine as model nitrogenous compounds. Species-specific second-order rate constants for the neutral parent amines ranged from 9.3 × 10⁴ to 2.2 × 10⁶ M^-1s^-1 and the apparent second-order rate constants at pH 7 for potential or identified transformation products were 6.8 × 10⁵ M^-1s^-1 for N,N-diethylhydroxylamine, ∼10⁵ M^-1s^-1 for N-ethylhydroxylamine, 1.9 × 10³ M^-1s^-1 for N-ethylethanimine oxide, and 3.4 M^-1s^-1 for nitroethane. Product analyses revealed that all amines were transformed to products containing a nitrogen-oxygen bond (e.g., triethylamine N-oxide and nitroethane) with high yields, i.e., 64-100% with regard to the abated target amines. These findings could be confirmed by measurements of singlet oxygen and hydroxyl radical which are formed during the amine-ozone reactions. Based on the high yields of nitroethane from ethylamine and diethylamine, a significant formation of nitroalkanes can be expected during ozonation of waters containing high levels of dissolved organic nitrogen, as expected in wastewaters or wastewater-impaired source waters. This may pose adverse effects on the aquatic environment and human health.