Articles | Volume 9, issue 9
Atmos. Chem. Phys., 9, 3209–3222, 2009
Atmos. Chem. Phys., 9, 3209–3222, 2009

  18 May 2009

18 May 2009

The heterogeneous reaction of hydroxyl radicals with sub-micron squalane particles: a model system for understanding the oxidative aging of ambient aerosols

J. D. Smith1, J. H. Kroll2, C. D. Cappa3, D. L. Che1,4, C. L. Liu1,4, M. Ahmed1, S. R. Leone1,4,5, D. R. Worsnop2, and K. R. Wilson1 J. D. Smith et al.
  • 1Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, CA 94720, USA
  • 2Aerosol and Cloud Chemistry, Aerodyne Research Inc., Billerica, MA 01821, USA
  • 3Department of Civil and Environmental Engineering, University of California, Davis, CA 95616, USA
  • 4Department of Chemistry, University of California, Berkeley, CA 94720, USA
  • 5Department of Physics, University of California, Berkeley, CA 94720, USA

Abstract. The heterogeneous reaction of OH radicals with sub-micron squalane particles, in the presence of O2, is used as a model system to explore the fundamental chemical mechanisms that control the oxidative aging of organic aerosols in the atmosphere. Detailed kinetic measurements combined with elemental mass spectrometric analysis reveal that the reaction proceeds sequentially by adding an average of one oxygenated functional group per reactive loss of squalane. The reactive uptake coefficient of OH with squalane particles is determined to be 0.3±0.07 at an average OH concentration of ~1×1010 molecules cm−3. Based on a comparison between the measured particle mass and model predictions it appears that significant volatilization of a reduced organic particle would be extremely slow in the real atmosphere. However, as the aerosols become more oxygenated, volatilization becomes a significant loss channel for organic material in the particle-phase. Together these results provide a chemical framework in which to understand how heterogeneous chemistry transforms the physiochemical properties of particle-phase organic matter in the troposphere.

Final-revised paper