Atmos. Chem. Phys. Discuss., 11, 7095-7112, 2011
© Author(s) 2011. This work is distributed
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This discussion paper has been under review for the journal Atmospheric Chemistry and Physics (ACP). Please refer to the corresponding final paper in ACP.
Changes in organic aerosol composition with aging inferred from aerosol mass spectra
N. L. Ng1, M. R. Canagaratna1, J. L. Jimenez2,3, P. S. Chhabra4, J. H. Seinfeld4, and D. R. Worsnop1
1Aerodyne Research, Inc. Billerica, MA, USA
2Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA
3CIRES, University of Colorado, Boulder, CO, USA
4Department of Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

Abstract. Organic aerosols (OA) can be separated with factor analysis of aerosol mass spectrometer (AMS) data into hydrocarbon-like OA (HOA) and oxygenated OA (OOA). We develop a new method to parameterize H:C of OOA in terms of f43 (ratio of m/z 43, mostly C2H3O+, to total signal in the component mass spectrum). Such parameterization allows the transformation of large database of ambient OOA components from the f44 (mostly CO2+, likely from acid groups) vs. f43 space ("triangle plot") (Ng et al., 2010) into the Van Krevelen diagram (H:C vs. O:C). Heald et al. (2010) suggested that the bulk composition of OA line up in the Van Krevelen diagram with a slope ~ −1; such slope can potentially arise from the physical mixing of HOA and OOA, and/or from chemical aging of these components. In this study, we find that the OOA components from all sites occupy an area in the Van Krevelen space, with the evolution of OOA following a shallower slope of ~ −0.5, consistent with the additions of both acid and alcohol functional groups without fragmentation, and/or the addition of acid groups with C-C bond breakage. The importance of acid formation in OOA evolution is consistent with increasing f44 in the triangle plot with photochemical age. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies.

Citation: Ng, N. L., Canagaratna, M. R., Jimenez, J. L., Chhabra, P. S., Seinfeld, J. H., and Worsnop, D. R.: Changes in organic aerosol composition with aging inferred from aerosol mass spectra, Atmos. Chem. Phys. Discuss., 11, 7095-7112, doi:10.5194/acpd-11-7095-2011, 2011.
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