Bridged-ozonolysis of mixed aromatic hydrocarbons and organic amines: Inter-inhibited decay rate, altered product yield and synergistic-effect-enhanced secondary organic aerosol formation

Abstract

Ozonolysis of aromatic hydrocarbons (AHs) or organic amines (OAs) occurs via different transformation processes, with varying rate constants and contributions to secondary organic aerosol (SOA) formation. However, to date no data is available on the ozonolysis of mixtures of AHs and OAs. This study investigated the kinetics, products and SOA yield from ozonolysis of mixture of trimethylamine with styrene, toluene or m-xylene. In the mixed system, the decay rates of styrene and trimethylamine were (1.32 ± 0.26) × 10−4 s−1 and (0.80 ± 0.02) × 10−4 s−1, decreasing up to 36.5 % and 54.4 % compared with their respective individual systems. This inter-inhibition of decay rates increased the yield of main products from styrene (i.e. benzaldehyde) by 23.5 % and trimethylamine (i.e. nitromethane) by 346.4 %. Ozonolysis of styrene or trimethylamine produced formaldehyde, which acted as a bridged product connecting the ozonolysis pathways of these two substrates, altering the yields of all products. Ozonolysis of styrene to benzaldehyde determined the increase of SOA particle number concentration (from 9.5 × 105 to 1.9 × 106 particles cm−3), while trimethylamine ozonolysis to N, N-dimethylformamide contributed to synergistic-effect-enhanced SOA yield (from (64.3 ± 3.5)% to (68.1 ± 4.8)%). The findings provide a novel insight into the kinetics and mechanism of ozonolysis, as well as the resulting SOA formation from mixtures of AHs and OAs, helping to comprehensively understand the transformation and fate of organics in real atmospheric environments.