Reactions of Atmospheric Particulate Stabilized Criegee Intermediates Lead to High-Molecular-Weight Aerosol Components

Environ Sci Technol. 2016 Jun 7;50(11):5702-10. doi: 10.1021/acs.est.6b02114. Epub 2016 May 26.

Abstract

Aging of organic aerosol particles is one of the most poorly understood topics in atmospheric aerosol research. Here, we used an aerosol flow tube together with an iodide-adduct high-resolution time-of-flight chemical-ionization mass spectrometer equipped with a Filter Inlet for Gases and AEROsols (FIGAERO-HRToF-CIMS) to investigate heterogeneous ozonolysis of oleic acid (OL), developing a comprehensive oxidation mechanism with observed products. In addition to the well-known first-generation C9 products including nonanal, nonanoic acid, azelaic acid, and 9-oxononanoic acid, the iodide-adduct chemical ionization permitted unambiguous determination of a large number of high-molecular-weight particulate products up to 670 Da with minimum amounts of fragmentation. These high-molecular-weight products are characterized by a fairly uniform carbon oxidation state but stepwise addition of a carbon backbone moiety, and hence continuous decrease in the volatility. Our results demonstrate that heterogeneous oxidation of organic aerosols has a significant effect on the physiochemical properties of organic aerosols and that reactions of particulate SCIs from ozonolysis of an unsaturated particulate species represent a previously underappreciated mechanism that lead to formation of high-molecular-weight particulate products that are stable under typical atmospheric conditions.

Publication types

  • Research Support, U.S. Gov't, Non-P.H.S.
  • Research Support, Non-U.S. Gov't

MeSH terms

  • Aerosols / chemistry*
  • Gases / chemistry
  • Oleic Acid / chemistry
  • Oxidation-Reduction
  • Particle Size*

Substances

  • Aerosols
  • Gases
  • Oleic Acid