Atmos. Chem. Phys. Discuss., 9, 26969-27019, 2009
www.atmos-chem-phys-discuss.net/9/26969/2009/
doi:10.5194/acpd-9-26969-2009
© Author(s) 2009. This work is distributed
under the Creative Commons Attribution 3.0 License.
Review Status
This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone
C. Pfrang1,2, M. Shiraiwa2, and U. Pöschl2
1University of Reading, Department of Chemistry, P.O. BOX 224, Whiteknights, Reading, RG6 6AD, UK
2Max Planck Institute for Chemistry, Biogeochemistry Department, 55128 Mainz, Germany

Abstract. We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Pöschl et al., 2007). K2-SUB is applied to a popular model system of atmospheric heterogeneous chemistry: the interaction of ozone with oleic acid. We show that our modelling approach allows de-convoluting surface and bulk processes, which has been a controversial topic and remains an important challenge for the understanding and description of atmospheric aerosol transformation. In particular, we demonstrate how a detailed treatment of adsorption and reaction at the surface can be coupled to a description of bulk reaction and transport that is consistent with traditional resistor model formulations.

From literature data we have derived a consistent set of kinetic parameters that characterise mass transport and chemical reaction of ozone at the surface and in the bulk of oleic acid droplets. Due to the wide range of rate coefficients reported from different experimental studies, the exact proportions between surface and bulk reaction rates remain uncertain. Nevertheless, the model results suggest an important role of chemical reaction in the bulk and an upper limit of ~1×10−11 cm2 s−1 for the surface reaction rate coefficient. Sensitivity studies show that the surface accommodation coefficient of the gas-phase reactant has a strong non-linear influence on both surface and bulk chemical reactions. We suggest that K2-SUB may be used to design, interpret and analyse future experiments for better discrimination between surface and bulk processes in the oleic acid-ozone system as well as in other heterogeneous reaction systems of atmospheric relevance.


Citation: Pfrang, C., Shiraiwa, M., and Pöschl, U.: Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone, Atmos. Chem. Phys. Discuss., 9, 26969-27019, doi:10.5194/acpd-9-26969-2009, 2009.
 
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