ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-8131-2012 Characterization of submicron particles influenced by mixed biogenic and anthropogenic emissions using high-resolution aerosol mass spectrometry: results from CARES Setyan A. 1 Zhang Q. 1 Merkel M. 2 Knighton W. B. 3 Sun Y. 4 Song C. 5 Shilling J. E. 5 Onasch T. B. 6 Herndon S. C. 6 Worsnop D. R. 6 Fast J. D. 5 Zaveri R. A. 5 Berg L. K. 5 Wiedensohler A. 2 Flowers B. A. 7 Dubey M. K. 7 Subramanian R. 8 Department of Environmental Toxicology, University of California, 1 Shields Ave., Davis, CA 95616, USA Leibniz Institute for Tropospheric Research, 04318 Leipzig, Germany Montana State University, Bozeman, MT 59717, USA State Key Laboratory of Atmospheric Boundary Layer and Atmospheric Chemistry, Institute of Atmospheric Physics, Chinese Academy of Sciences, Beijing, China Pacific Northwest National Laboratory, Richland, WA 99352, USA Aerodyne Research Inc., Billerica, MA 01821, USA Los Alamos National Laboratory, Los Alamos, NM 87545, USA RTI International, RTP, NC 27709, USA 11 09 2012 12 17 8131 8156 This is an open-access article ditributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original author and source are credited. This article is available from http://www.atmos-chem-phys.net/12/8131/2012/acp-12-8131-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/8131/2012/acp-12-8131-2012.pdf

An Aerodyne high resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) was deployed during the Carbonaceous Aerosols and Radiative Effects Study (CARES) that took place in northern California in June 2010. We present results obtained at Cool (denoted as the T1 site of the project) in the foothills of the Sierra Nevada Mountains, where intense biogenic emissions are periodically mixed with urban outflow transported by daytime southwesterly winds from the Sacramento metropolitan area. During this study, the average mass loading of submicrometer particles (PM<sub>1</sub>) was 3.0 μg m<sup>−3</sup>, dominated by organics (80%) and sulfate (9.9%). The organic aerosol (OA) had a nominal formula of C<sub>1</sub>H<sub>1.38</sub>N<sub>0.004</sub>OM<sub>0.44</sub>, thus an average organic mass-to-carbon (OM/OC) ratio of 1.70. Two distinct oxygenated OA factors were identified via Positive matrix factorization (PMF) of the high-resolution mass spectra of organics. The more oxidized MO-OOA (O/C = 0.54) was interpreted as a surrogate for secondary OA (SOA) influenced by biogenic emissions whereas the less oxidized LO-OOA (O/C = 0.42) was found to represent SOA formed in photochemically processed urban emissions. LO-OOA correlated strongly with ozone and MO-OOA correlated well with two 1st generation isoprene oxidation products (methacrolein and methyl vinyl ketone), indicating that both SOAs were relatively fresh. A hydrocarbon like OA (HOA) factor was also identified, representing primary emissions mainly due to local traffic. On average, SOA (= MO-OOA + LO-OOA) accounted for 91% of the total OA mass and 72% of the PM<sub>1</sub> mass observed at Cool. Twenty three periods of urban plumes from T0 (Sacramento) to T1 (Cool) were identified using the Weather Research and Forecasting model coupled with Chemistry (WRF-Chem). The average PM<sub>1</sub> mass loading was considerably higher in urban plumes than in air masses dominated by biogenic SOA. The change in OA mass relative to CO (ΔOA/ΔCO) varied in the range of 5-196 μg m<sup>−3</sup> ppm<sup>−1</sup>, reflecting large variability in SOA production. The highest ΔOA/ΔCO was reached when air masses were dominated by anthropogenic emissions in the presence of a high concentration of biogenic volatile organic compounds (BVOCs). This ratio, which was 97 μg m<sup>−3</sup> ppm<sup>−1</sup> on average, was much higher than when urban plumes arrived in a low BVOC environment (~36 μg m<sup>−3</sup> ppm<sup>−1</sup>) or during other periods dominated by biogenic SOA (35 μg m<sup>−3</sup> ppm<sup>−1</sup>). These results demonstrate that SOA formation is enhanced when anthropogenic emissions interact with biogenic precursors.

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