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As part of the BAQS-Met 2007 field campaign, Aerodyne time-of-flight aerosolmass spectrometers (ToF-AMS) were deployed at two sites in southwesternOntario from 17 June to 11 July 2007. One instrument was located at Harrow,ON, a rural, agriculture-dominated area approximately 40 km southeast of theDetroit/Windsor/Windsor urban area and 5 km north of Lake Erie. The secondinstrument was located at Bear Creek, ON, a rural site approximately 70 km northeast of the Harrow site and 50 km east of Detroit/Windsor. Positivematrix factorization analysis of the combined organic mass spectral datasetyields factors related to secondary organic aerosol (SOA), direct emissions,and a factor tentatively attributed to the reactive uptake of isopreneand/or condensation of its early generation reaction products. This is thefirst application of PMF to simultaneous AMS measurements at differentsites, an approach which allows for self-consistent, direct comparison ofthe datasets. Case studies are utilized to investigate processing of SOAfrom (1) fresh emissions from Detroit/Windsor and (2) regional aerosolduring periods of inter-site flow. A strong correlation is observed betweenSOA/excess CO and photochemical age as represented by the NOx/NOyratio for Detroit/Windsor outflow. Although this correlation is not evidentfor more aged air, measurements at the two sites during inter-site transportnevertheless show evidence of continued atmospheric processing by SOAproduction. However, the rate of SOA production decreases with airmass agefrom 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 anaged airmass (i.e. after several days). The initial SOA production rate iscomparable to the observed rate in Mexico City over similar timescales

Photochemical processing of organic aerosol at nearby continental sites: contrast between urban plumes and regional aerosol