Atmospheric condensed-phase reactions of glyoxal with methylamine

Glyoxal reacts with methylamine in drying cloud droplet/aerosol surrogates to form high molecular mass oligomers along with smaller amounts of 1,3‐dimethylimidazole and light‐absorbing compounds. The patterns observed by high‐resolution time‐of‐flight aerosol mass spectrometry indicate that oligomers form from repeated imine units. The reactions are 1st order in each reactant: rate‐limiting imine formation is followed by rapid dimer and oligomer formation. While excess methylamine evaporates from the droplet, half the glyoxal does not, due to self‐oligomerization reactions that occur in the absence of methylamine. Glyoxal irreversibly traps volatile amine compounds in the aerosol phase, converting them into oligomers. This is the first reported mechanism for the formation of stable secondary organic aerosol (SOA) material from methylamine, a substance with only one carbon, and could produce as much as 11 Tg SOA yr−1 globally if glyoxal reacts exclusively by this pathway.