Oligomer and SOA formation through aqueous phase photooxidation of methacrolein and methyl vinyl ketone

This work investigates the ability of methacrolein (MACR) and methyl vinyl ketone (MVK) (the two main gas phase atmospheric oxidation products of isoprene) to form oligomers and secondary organic aerosol (SOA) upon aqueous phase OH-oxidation and subsequent water evaporation. For the two precursors, electrospray mass spectrometry (in infusion and coupled to liquid chromatography) analysis of the reacting solutions brought clear evidence for the formation of oligomer systems having a mass range of up to 1400 Da. More than 11 series of oligomers were found. For MVK, the intensity and masses of oligomers became increasingly important as MVK initial concentrations increased from 0.2 to 20 mM. For both precursors, the oligomers were responsible for the SOA formation during nebulization experiments. The evaluated SOA mass yield ranged from 3.9 to 9.9% for MVK. These yields were time dependent and were in good agreement with the range (1.6–11.7%) obtained for MACR under the same conditions by El Haddad et al. (2009).

► We show clear evidence for the formation of oligomer systems through the aqueous phase reactivity.
► Oligomers are able to form SOA upon water droplet evaporation and with the mass yield of this SOA.
► MACR and MVK can act as important contributors to SOA formation through atmospheric aqueous phase.