Atmos. Chem. Phys., 11, 2991-3006, 2011
© Author(s) 2011. This work is distributed
under the Creative Commons Attribution 3.0 License.
Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol
J. G. Slowik1,3,*, J. Brook4, R. Y.-W. Chang1,3, G. J. Evans2,3, K. Hayden4, C.-H. Jeong4, S.-M. Li4, J. Liggio4, P. S. K. Liu4, M. McGuire2,3, C. Mihele4, S. Sjostedt1,3,4, A. Vlasenko1,3,4, and J. P. D. Abbatt1,2
1Department of Chemistry, University of Toronto, Toronto, Canada
2Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Canada
3Southern Ontario Centre for Atmospheric Aerosol Research, University of Toronto, Toronto, Canada
4Science and Technology Branch, Environment Canada, Toronto, Canada
*now at: Paul Scherrer Institut, 5232 Villigen PSI, Switzerland

Abstract. As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosol mass spectrometers (ToF-AMS) were deployed at two sites in southwestern Ontario from 17 June to 11 July 2007. One instrument was located at Harrow, ON, a rural, agriculture-dominated area approximately 40 km southeast of the Detroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The second instrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positive matrix factorization analysis of the combined organic mass spectral dataset yields factors related to secondary organic aerosol (SOA), direct emissions, and a factor tentatively attributed to the reactive uptake of isoprene and/or condensation of its early generation reaction products. This is the first application of PMF to simultaneous AMS measurements at different sites, an approach which allows for self-consistent, direct comparison of the datasets. Case studies are utilized to investigate processing of SOA from (1) fresh emissions from Detroit/Windsor and (2) regional aerosol during periods of inter-site flow. A strong correlation is observed between SOA/excess CO and photochemical age as represented by the NOx/NOy ratio for Detroit/Windsor outflow. Although this correlation is not evident for more aged air, measurements at the two sites during inter-site transport nevertheless show evidence of continued atmospheric processing by SOA production. However, the rate of SOA production decreases with airmass age from an initial value of ~10.1 μg m−3 ppmvCO−1 h−1 for the first ~10 h of plume processing to near-zero in an aged airmass (i.e. after several days). The initial SOA production rate is comparable to the observed rate in Mexico City over similar timescales.

Citation: Slowik, J. G., Brook, J., Chang, R. Y.-W., Evans, G. J., Hayden, K., Jeong, C.-H., Li, S.-M., Liggio, J., Liu, P. S. K., McGuire, M., Mihele, C., Sjostedt, S., Vlasenko, A., and Abbatt, J. P. D.: Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol, Atmos. Chem. Phys., 11, 2991-3006, doi:10.5194/acp-11-2991-2011, 2011.
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