ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-1735-2011 Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene Chan M. N. 1 Surratt J. D. 2 10 Chan A. W. H. 2 11 Schilling K. 2 Offenberg J. H. 3 Lewandowski M. 3 Edney E. O. 3 Kleindienst T. E. 3 Jaoui M. 4 Edgerton E. S. 5 Tanner R. L. 6 Shaw S. L. 7 Zheng M. 8 Knipping E. M. 9 Seinfeld J. H. 1 2 Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California, USA Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California, USA National Exposure Research Laboratory, Human Exposure Atmospheric Sciences Division, United States Environmental Protection Agency, Research Triangle Park, North Carolina, USA Alion Science and Technology, P.O. Box 12313, Research Triangle Park, North Carolina, USA Atmospheric Research and Analysis, Inc., Cary, North Carolina, USA Environmental Technologies, Tennessee Valley Authority, Muscle Shoals, Alabama, USA Electric Power Research Institute, Palo Alto, California, USA School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA Electric Power Research Institute, Washington, DC, USA present address: Department of Environmental Sciences and Engineering, University of North Carolina at Chapel Hill, Chapel Hill, North Carolina, USA present address: Department of Environmental Science, Policy and Management, University of California, Berkeley, California, USA 25 02 2011 11 4 1735 1751 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/11/1735/2011/acp-11-1735-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/1735/2011/acp-11-1735-2011.pdf

The secondary organic aerosol (SOA) yield of β-caryophyllene photooxidation is enhanced by aerosol acidity. In the present study, the influence of aerosol acidity on the chemical composition of β-caryophyllene SOA is investigated using ultra performance liquid chromatography/electrospray ionization-time-of-flight mass spectrometry (UPLC/ESI-TOFMS). A number of first-, second- and higher-generation gas-phase products having carbonyl and carboxylic acid functional groups are detected in the particle phase. Particle-phase reaction products formed via hydration and organosulfate formation processes are also detected. Increased acidity leads to different effects on the abundance of individual products; significantly, abundances of organosulfates are correlated with aerosol acidity. To our knowledge, this is the first detection of organosulfates and nitrated organosulfates derived from a sesquiterpene. The increase of certain particle-phase reaction products with increased acidity provides chemical evidence to support the acid-enhanced SOA yields. Based on the agreement between the chromatographic retention times and accurate mass measurements of chamber and field samples, three β-caryophyllene products (i.e., β-nocaryophyllon aldehyde, β-hydroxynocaryophyllon aldehyde, and β-dihydroxynocaryophyllon aldehyde) are suggested as chemical tracers for β-caryophyllene SOA. These compounds are detected in both day and night ambient samples collected in downtown Atlanta, GA and rural Yorkville, GA during the 2008 August Mini-Intensive Gas and Aerosol Study (AMIGAS).

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