Reactive uptake of an isoprene-derived epoxydiol to submicron aerosol particles

Environ Sci Technol. 2014 Oct 7;48(19):11178-86. doi: 10.1021/es5034266. Epub 2014 Sep 24.

Abstract

The reactive uptake of isoprene-derived epoxydiols (IEPOX) is thought to be a significant source of atmospheric secondary organic aerosol (SOA). However, the IEPOX reaction probability (γIEPOX) and its dependence upon particle composition remain poorly constrained. We report measurements of γIEPOX for trans-β-IEPOX, the predominant IEPOX isomer, on submicron particles as a function of composition, acidity, and relative humidity (RH). Particle acidity had the strongest effect. γIEPOX is more than 500 times greater on ammonium bisulfate (γ ∼ 0.05) than on ammonium sulfate (γ ≤ 1 × 10(-4)). We could accurately predict γIEPOX using an acid-catalyzed, epoxide ring-opening mechanism and a high Henry's law coefficient (1.7 × 10(8) M/atm). Suppression of γIEPOX was observed on particles containing both ammonium bisulfate and poly(ethylene glycol) (PEG-300), likely due to diffusion and solubility limitations within a PEG-300 coating, suggesting that IEPOX uptake could be self-limiting. Using the measured uptake kinetics, the predicted atmospheric lifetime of IEPOX is a few hours in the presence of highly acidic particles (pH < 0) but is greater than 25 h on less acidic particles (pH > 3). This work highlights the importance of aerosol acidity for accurately predicting the fate of IEPOX and anthropogenically influenced biogenic SOA formation.

Publication types

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

MeSH terms

  • Acids / chemistry
  • Aerosols / chemistry*
  • Atmosphere / chemistry
  • Butadienes / chemistry*
  • Epoxy Compounds / chemistry*
  • Hemiterpenes / chemistry*
  • Kinetics
  • Pentanes / chemistry*
  • Water / chemistry

Substances

  • Acids
  • Aerosols
  • Butadienes
  • Epoxy Compounds
  • Hemiterpenes
  • Pentanes
  • Water
  • isoprene