Articles | Volume 14, issue 23
Atmos. Chem. Phys., 14, 12951–12964, 2014
Atmos. Chem. Phys., 14, 12951–12964, 2014

Research article 08 Dec 2014

Research article | 08 Dec 2014

Mechanistic study of secondary organic aerosol components formed from nucleophilic addition reactions of methacrylic acid epoxide

A. W. Birdsall*,1, C. R. Miner1, L. E. Mael1, and M. J. Elrod1 A. W. Birdsall et al.
  • 1Department of Chemistry and Biochemistry, Oberlin College, Oberlin, Ohio, USA
  • *currently at: Department of Chemistry, University of Wisconsin-Madison, Madison, Wisconsin, USA

Abstract. Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.

Short summary
We investigated how an important naturally emitted chemical, isoprene, can contribute to the formation of aerosol particles, which are a key component of air pollution that can also influence climate. Specifically, we found that a particular relative of isoprene, methacrylic acid epoxide, is capable of transforming into a number of different chemical components via reaction on existing aerosol particles. These results will help to make isoprene air quality model predictions more accurate.
Final-revised paper