1Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California, USA
2Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California, USA
3National Exposure Research Laboratory, Human Exposure Atmospheric Sciences Division, United States Environmental Protection Agency, Research Triangle Park, North Carolina, USA
4Alion Science and Technology, P.O. Box 12313, Research Triangle Park, North Carolina, USA
5Atmospheric Research and Analysis, Inc., Cary, North Carolina, USA
6Environmental Technologies, Tennessee Valley Authority, Muscle Shoals, Alabama, USA
7Electric Power Research Institute, Palo Alto, California, USA
8School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA
9Electric 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
Received: 18 Nov 2010 – Discussion started: 30 Nov 2010
Abstract. 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).
Revised: 10 Feb 2011 – Accepted: 15 Feb 2011 – Published: 25 Feb 2011
Chan, M. N., Surratt, J. D., Chan, A. W. H., Schilling, K., Offenberg, J. H., Lewandowski, M., Edney, E. O., Kleindienst, T. E., Jaoui, M., Edgerton, E. S., Tanner, R. L., Shaw, S. L., Zheng, M., Knipping, E. M., and Seinfeld, J. H.: Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene, Atmos. Chem. Phys., 11, 1735-1751, doi:10.5194/acp-11-1735-2011, 2011.