KINETICS OF SURFACE-BOUND BENZO[A]PYRENE AND OZONE ON ORGANIC AND INORGANIC AEROSOLS N.-O. A. Kwamena, J. A. Thornton, J. P. D. Abbatt Department of Chemistry, University of Toronto, Toronto, ON M5S 3H6 Canada Atmospheric Chemistry of Polycyclic Aromatic Hydrocarbons Polycyclic aromatic hydrocarbons (PAHs) are emitted to the atmosphere from combustion sources and many are known carcinogens. Larger PAHs, such as benzo[a]pyrene (BAP), may partition to fine particulate matter because of their low vapour pressures. This particulate matter can penetrate deep into the lungs resulting in allergenic, mutagenic or carcinogenic responses. Because the oxidation products of PAHs may be even more mutagenic or carcinogenic than the parent PAHs it is necessary to characterize the chemical and physical mechanisms that control the fate and transport of atmospheric PAHs. Therefore, we have undertaken a kinetic study of the oxidation of BaP bound to the surface of organic and inorganic aerosols to better understand aerosol-related health risks and improve urban air quality. This study is the first examination of the oxidation of a PAH on organic and inorganic aerosols in the sub-monolayer regime. Aerosol Flow Tube for Surface Kinetics Studies  An analytical technique was developed so studies in the sub-monolayer regime could be performed under both dry and high relative humidity conditions.  Azelaic acid (C 9 di-carboxylic acid) was used as the organic aerosol substrate.  Solid NaCl aerosols, generated by atomizing a NaCl solution and passing the output through a diffusion dryer, were used as the inorganic aerosol substrate.  Followng filter collection, the samples were extracted ultrasonically and analyzed using HPLC with fluorescence detection to monitor the BaP concentration. Figure 1: Experimental set-up for kinetics experiments of BaP on organic aerosols Figure 2: BaP surface concentration as a function of the inverse BaP coating region temperature Generating Fractional Surface Coverages of Benzo[a]pyrene on Organic Aerosols  Azelaic acid aerosols were introduced to various BaP coating region temperatures.  A BaP sublimation enthalpy of (124±3) kJ/mol was obtained for BaP on azelaic acid aerosols based on the Clasius-Clapeyron equation.  Pöschl et al. (2001) reported a sublimation enthalpy of (118±5) kJ/mol for BaP on spark discharge soot, which is in agreement with our measurement and the extrapolated literature value (118±2)kJ/mol. Kinetics of Surface-Bound BaP on Azelaic Acid Aerosols in the Presence of Ozone Under Dry and Wet Conditions  Kinetic experiments were performed at two different BaP fractional surface coverages (0.02 and 0.2 monolayers). The reaction between surface BaP and ozone is first order within experimental precision.  Preliminary results indicate that the reaction between surface-BaP and ozone is 2.5 times faster at 72% RH compared to dry conditions. This is in direct contrast to other measurements (Pöschl et al. 2001) where a suppression of this reaction under high relative humidity conditions was observed. Studies are ongoing to elucidate the reaction mechanism at high relative humidities. Kinetics of Surface-Bound BaP on Azelaic Acid Aerosols: Implications for Reaction Mechanisms Kinetics of Surface-Bound BaP on Sodium Chloride Aerosols  Kinetic experiments were performed on solid sodium chloride aerosols at high ozone concentrations (up to 31 ppm). No reaction between the surface-adsorbed BaP (submonolayer coverage) and ozone was observed.  Figure 5 suggests a Langmuir-Hinshelwood reaction mechanism, where ozone adsorbs to the surface and reacts with the surface-bound BaP.  By assuming a Langmuir isotherm, the pseudo- first order rate coefficient may be given by: Figure 5: The pseudo-first order rate coefficient as a function of gas-phase ozone concentration  The lower K O3 value for azelaic acid suggests decreased partitioning of ozone to azelaic acid than to soot.  The similarity in the pseudo-first order rate coefficients (k I max ) for this work and that done by Pöschl et al. (2001) on soot aerosols indicates that the product of k II and N surf are similar.  Anthracene oxidation on an organic film displayed behaviour consistent with a Langmuir- Hinshelwood mechanism (Mmereki and Donaldson, 2003); however the k I max is a factor of 10 lower.  The reaction between ozone and surface-bound PAHs appears to progress by the Langmuir Hinshelwood mechanism irrespective of the substrate. However, the adsorption of ozone differs from surface to surface (Pöschl et al. 2001; Mmereki and Donaldson, 2003).  Our results suggest a lifetime as long as 4 hours ([O 3 ] = 30ppb, dry conditions) with respect to ozone oxidation for BaP bound to the surface of organic aerosols under atmospherically relevant ozone concentrations. This could be a significant loss process for BaP in the atmosphere. Soot Azelaic Acid Substrate aerosol Pöschl et al (2001) This work k I max (s -1 ) K O3 ( cm 3 ) Table 1: Comparison of adsorption equilibrium constants and the maximum pseudo-first order rate coefficient Acknowledgements We would like to thank Dan Mathers and the Analest Facility for use of the HPLC with fluorescence detection. We also thank NSERC, TSRI and ASC-PRF for funding this project. Figure 3: Kinetics at 0.2 monolayers of BaP on azelaic acid aerosols under dry conditions Figure 4: Kinetics at 0.2 monolayers of BaP on azelaic acid aerosols at 72% relative humidity References Pöschl, U. et al., J. Phys. Chem. A 2001, 105, 4029 – 4041 Mmereki, B. T., Donaldson, D. J., J Phys. Chem. A 2003, 107, –  The k I max is a product of the second order rate constant (k II ) and the number of surface sites for the adsorbed species (N surf ): 0.02 monolayers 0.2 monolayers 1 monolayer