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Volume 11, issue 4
Atmos. Chem. Phys., 11, 1735–1751, 2011
https://doi.org/10.5194/acp-11-1735-2011
© Author(s) 2011. This work is distributed under
the Creative Commons Attribution 3.0 License.
Atmos. Chem. Phys., 11, 1735–1751, 2011
https://doi.org/10.5194/acp-11-1735-2011
© Author(s) 2011. This work is distributed under
the Creative Commons Attribution 3.0 License.

Research article 25 Feb 2011

Research article | 25 Feb 2011

Influence of aerosol acidity on the chemical composition of secondary organic aerosol from β-caryophyllene

M. N. Chan1, J. D. Surratt2,*, A. W. H. Chan2,**, K. Schilling2, J. H. Offenberg3, M. Lewandowski3, E. O. Edney3, T. E. Kleindienst3, M. Jaoui4, E. S. Edgerton5, R. L. Tanner6, S. L. Shaw7, M. Zheng8, E. M. Knipping9, and J. H. Seinfeld1,2 M. N. Chan et al.
  • 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

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).

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