Trimethylamine Outruns Terpenes and Aromatics in Atmospheric Autoxidation.

Autoxidation in the atmosphere has been realized in the last decade as an important process that forms highly oxidized products relevant for the formation of secondary organic aerosol and likely with detrimental human health effects. It is experimentally shown that the OH radical-initiated oxidation of trimethylamine, the most highly emitted amine in the atmosphere, proceeds via rapid autoxidation steps dominating its atmospheric oxidation process. All three methyl groups are functionalized within a timescale of 10 s following the reaction with OH radicals leading to highly oxidized products. The exceptionally large density of functional groups in the oxidized products is expected to define their chemical properties. A detailed reaction mechanism based on theoretical calculations is able to describe the experimental findings. The comparison with results of the reinvestigated OH radical- and ozone-initiated autoxidation of a series of terpenes and aromatics reveals the trimethylamine process as the most efficient one discovered up to now for atmospheric conditions.