Articles | Volume 15, issue 8
Atmos. Chem. Phys., 15, 4225–4239, 2015
Atmos. Chem. Phys., 15, 4225–4239, 2015

Research article 24 Apr 2015

Research article | 24 Apr 2015

Complex chemical composition of colored surface films formed from reactions of propanal in sulfuric acid at upper troposphere/lower stratosphere aerosol acidities

A. L. Van Wyngarden1, S. Pérez-Montaño1, J. V. H. Bui1, E. S. W. Li1, T. E. Nelson1, K. T. Ha1, L. Leong1, and L. T. Iraci2 A. L. Van Wyngarden et al.
  • 1Department of Chemistry, San José State University, San José, CA 95192, USA
  • 2Atmospheric Science Branch, NASA Ames Research Center, Moffett Field, CA 94035, USA

Abstract. Particles in the upper troposphere and lower stratosphere (UT/LS) consist mostly of concentrated sulfuric acid (40–80 wt%) in water. However, airborne measurements have shown that these particles also contain a significant fraction of organic compounds of unknown chemical composition. Acid-catalyzed reactions of carbonyl species are believed to be responsible for significant transfer of gas phase organic species into tropospheric aerosols and are potentially more important at the high acidities characteristic of UT/LS particles. In this study, experiments combining sulfuric acid (H2SO4) with propanal and with mixtures of propanal with glyoxal and/or methylglyoxal at acidities typical of UT/LS aerosols produced highly colored surface films (and solutions) that may have implications for aerosol properties. In order to identify the chemical processes responsible for the formation of the surface films, attenuated total reflectance–Fourier transform infrared (ATR-FTIR) and 1H nuclear magnetic resonance (NMR) spectroscopies were used to analyze the chemical composition of the films. Films formed from propanal were a complex mixture of aldol condensation products, acetals and propanal itself. The major aldol condensation products were the dimer (2-methyl-2-pentenal) and 1,3,5-trimethylbenzene that was formed by cyclization of the linear aldol condensation trimer. Additionally, the strong visible absorption of the films indicates that higher-order aldol condensation products must also be present as minor species. The major acetal species were 2,4,6-triethyl-1,3,5-trioxane and longer-chain linear polyacetals which are likely to separate from the aqueous phase. Films formed on mixtures of propanal with glyoxal and/or methylglyoxal also showed evidence of products of cross-reactions. Since cross-reactions would be more likely than self-reactions under atmospheric conditions, similar reactions of aldehydes like propanal with common aerosol organic species like glyoxal and methylglyoxal have the potential to produce significant organic aerosol mass and therefore could potentially impact chemical, optical and/or cloud-forming properties of aerosols, especially if the products partition to the aerosol surface.

Short summary
We have observed the formation of colored organic surface films on solutions of propanal and sulfuric acid at acidities chosen to mimic the highly acidic aerosols in the upper troposphere and lower stratosphere. The films were found to be composed of aldol condensation products and polyacetals. If such species also form coatings on atmospheric aerosols, they could impact climate by changing the chemical, optical and cloud-forming properties of aerosols.
Final-revised paper