Mechanism of atmospheric organic amines reacted with ozone and implications for the formation of secondary organic aerosols

Abstract

Organic amines are one of the most important nitrogen-containing compounds in the atmosphere, and their reactions with tropospheric ozone contribute significantly to the formation of secondary organic aerosols (SOA). However, the chemical pathways of their reaction with atmospheric ozone are poorly understood. This study investigates the atmospheric ozonolysis mechanism of two typical organic amines—diethylamine and triethylamine using experimental and theoretical methods. Intermediate results from GC–MS and PTR-TOF-MS analysis confirm the formation of eight and eleven nitrogen- and oxygen-containing products during the ozonolysis of diethylamine and triethylamine, respectively. N-ethylethanimine (56.5% in average) or acetaldehyde (64.9% in average) is formed as the dominant product from the ozonolysis of each organic amine. Ozonolysis pathway results indicate that the conversion to N-ethylethanimine is the dominant pathway for diethylamine ozonolysis. At the same time, triethylamine prefers the initial transformation to diethylamine with the discharge of acetaldehyde and then converts to N-ethylethanimine. Higher SOA mass concentration is obtained from the ozonolysis of triethylamine than diethylamine, probably because the former releases a larger amount of intermediate products, especially acetaldehyde. Our results provide a deep insight into the atmospheric processing of organic amines via ozonolysis and the implications of this mechanism for SOA formation.