Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone

Pfrang, C., Shiraiwa, M. and Pöschl, U. (2010) Coupling aerosol surface and bulk chemistry with a kinetic double layer model (K2-SUB): oxidation of oleic acid by ozone. Atmospheric Chemistry and Physics, 10 (10). pp. 4537-4557. ISSN 1680-7316 doi: 10.5194/acp-10-4537-2010

Abstract/Summary

We present a kinetic double layer model coupling aerosol surface and bulk chemistry (K2-SUB) based on the PRA framework of gas-particle interactions (Poschl-Rudich-Ammann, 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 approximate upper limit of similar to 10(-11) cm(2) 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.

Item Type	Article
URI	https://reading-clone.eprints-hosting.org/id/eprint/17222
Identification Number/DOI	10.5194/acp-10-4537-2010
Refereed	Yes
Divisions	Interdisciplinary centres and themes > Chemical Analysis Facility (CAF) > Optical Spectroscopy (CAF) Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
Uncontrolled Keywords	GAS-PARTICLE INTERACTIONS, ACTIVITY RELATIONS SARS, POLYCYCLIC AROMATIC-HYDROCARBONS, UNSATURATED FATTY-ACIDS, PHASE RATE COEFFICIENTS, AIR-WATER-INTERFACE, REACTIVE UPTAKE, HETEROGENEOUS REACTION, ORGANIC AEROSOLS, ATMOSPHERIC IMPLICATIONS
Publisher	Copernicus Publications
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