References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-11-6465-2011

Changes in organic aerosol composition with aging inferred from aerosol mass spectra

N. L.

¹ Canagaratna

M. R.

¹ Jimenez

J. L.

² ³ Chhabra

P. S.

⁴ Seinfeld

J. H.

⁴ Worsnop

D. R.

Aerodyne Research, Inc. Billerica, MA, USA

Department of Chemistry and Biochemistry, University of Colorado, Boulder, CO, USA

CIRES, University of Colorado, Boulder, CO, USA

Department of Chemical Engineering, California Institute of Technology, Pasadena, CA, USA

07 07 2011

11 13 6465 6474

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.

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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 for 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) (Van Krevelen, 1950). Heald et al. (2010) examined the evolution of total OA in the Van Krevelen diagram. In this work total OA is deconvolved into components that correspond to primary (HOA and others) and secondary (OOA) organic aerosols. By deconvolving total OA into different components, we remove physical mixing effects between secondary and primary aerosols which allows for examination of the evolution of OOA components alone in the Van Krevelen space. This provides a unique means of following ambient secondary OA evolution that is analogous to and can be compared with trends observed in chamber studies of secondary organic aerosol formation. The triangle plot in Ng et al. (2010) indicates that f44 of OOA components increases with photochemical age, suggesting the importance of acid formation in OOA evolution. Once they are transformed with the new parameterization, the triangle plot of the OOA components from all sites occupy an area in Van Krevelen space which follows a ΔH:C/ΔO:C slope of ~ −0.5. This slope suggests that ambient OOA aging results in net changes in chemical composition that are equivalent to the addition of both acid and alcohol/peroxide functional groups without fragmentation (i.e. C-C bond breakage), and/or the addition of acid groups with fragmentation. These results provide a framework for linking the bulk aerosol chemical composition evolution to molecular-level studies.

References 1

Aiken, A. C., DeCarlo, P. F., and Jimenez, J. L.: Elemental Analysis of Organic Species with Electron Ionization High-Resolution Mass Spectrometry, Anal. Chem., 79, 8350–8358, doi:8310.1021/ac071150w, 2007.

Aiken, A. C., DeCarlo, P. F., Kroll, J. H., Worsnop, D. R., Huffman, J. A., Docherty, K. S., Ulbrich, I. M., Mohr, C., Kimmel, J. R., Sueper, D., Sun, Y., Zhang, Q., Trimborn, A., Northway, M., Ziemann, P. J., Canagaratna, M. R., Onasch, T. B., Alfarra, M. R., Prevot, A. S. H., Dommen, J., Duplissy, J., Metzger, A., Baltensperger, U., and Jimenez, J. L.: O/C and OM/OC ratios of primary, secondary, and ambient organic aerosols with high-resolution time-of-flight aerosol mass spectrometry, Environ. Sci. Technol., 42, 4478–4485, 2008.

Aiken, A. C., Salcedo, D., Cubison, M. J., Huffman, J. A., DeCarlo, P. F., Ulbrich, I. M., Docherty, K. S., Sueper, D., Kimmel, J. R., Worsnop, D. R., Trimborn, A., Northway, M., Stone, E. A., Schauer, J. J., Volkamer, R. M., Fortner, E., de Foy, B., Wang, J., Laskin, A., Shutthanandan, V., Zheng, J., Zhang, R., Gaffney, J., Marley, N. A., Paredes-Miranda, G., Arnott, W. P., Molina, L. T., Sosa, G., and Jimenez, J. L.: Mexico City aerosol analysis during MILAGRO using high resolution aerosol mass spectrometry at the urban supersite (T0) – Part 1: Fine particle composition and organic source apportionment, Atmos. Chem. Phys., 9, 6633–6653, http://dx.doi.org/10.5194/acp-9-6633-2009doi:10.5194/acp-9-6633-2009, 2009.

Chhabra, P. S., Flagan, R. C., and Seinfeld, J. H.: Elemental analysis of chamber organic aerosol using an aerodyne high-resolution aerosol mass spectrometer, Atmos. Chem. Phys., 10, 4111–4131, http://dx.doi.org/10.5194/acp-10-4111-2010doi:10.5194/acp-10-4111-2010, 2010.

Chhabra, P. S., Ng, N. L., Canagaratna, M. R., Corrigan, A. L., Russell, L. M., Worsnop, D. R., Flagan, R. C., and Seinfeld, J. H.: Elemental composition and oxidation of chamber organic aerosol, Atmos. Chem. Phys. Discuss., 11, 10305–10342, http://dx.doi.org/10.5194/acpd-11-10305-2011doi:10.5194/acpd-11-10305-2011, 2011.

Cubison, M. J., Ortega, A. M., Hayes, P. L., Farmer, D. K., Day, D., Lechner, M. J., Brune, W. H., Apel, E., Diskin, G. S., Fisher, J. A., Fuelberg, H. E., Hecobian, A., Knapp, D. J., Mikoviny, T., Riemer, D., Sachse, G. W., Sessions, W., Weber, R. J., Weinheimer, A. J., Wisthaler, A., and Jimenez, J. L.: Effects of aging on organic aerosol from open biomass burning smoke in aircraft and lab studies, Atmos. Chem. Phys. Discuss., 11, 12103–12140, http://dx.doi.org/10.5194/acpd-11-12103-2011doi:10.5194/acpd-11-12103-2011, 2011.

DeCarlo, P. F., Ulbrich, I. M., Crounse, J., de Foy, B., Dunlea, E. J., Aiken, A. C., Knapp, D., Weinheimer, A. J., Campos, T., Wennberg, P. O., and Jimenez, J. L.: Investigation of the sources and processing of organic aerosol over the Central Mexican Plateau from aircraft measurements during MILAGRO, Atmos. Chem. Phys., 10, 5257–5280, http://dx.doi.org/10.5194/acp-10-5257-2010doi:10.5194/acp-10-5257-2010, 2010.

Decesari, S., Mircea, M., Cavalli, F., Fuzzi, S., Moretti, F., Tagliavini, E., and Facchini, M. C.: Source attribution of water-soluble organic aerosol by nuclear magnetic resonance spectroscopy, Environ. Sci. Technol., 41, 2479–2484, 2007.

Docherty, K. S., Stone, E. A., Ulbrich, I. M., DeCarlo, P. F., Snyder, D. C., Schauer, J. J., Peltier, R. E., Weber, R. J., Murphy, S. M., Seinfeld, J. H., Grover, B. D., Eatough, D. J., and Jiimenez, J. L.: Apportionment of Primary and Secondary Organic Aerosols in Southern California during the 2005 Study of Organic Aerosols in Riverside (SOAR-1), Environ. Sci. Technol., 42, 7655–7662, 2008.

Duplissy, J., DeCarlo, P. F., Dommen, J., Alfarra, M. R., Metzger, A., Barmpadimos, I., Prevot, A. S. H., Weingartner, E., Tritscher, T., Gysel, M., Aiken, A. C., Jimenez, J. L., Canagaratna, M. R., Worsnop, D. R., Collins, D. R., Tomlinson, J., and Baltensperger, U.: Relating hygroscopicity and composition of organic aerosol particulate matter, Atmos. Chem. Phys., 11, 1155–1165, http://dx.doi.org/10.5194/acp-11-1155-2011doi:10.5194/acp-11-1155-2011, 2011.

Heald, C. L., Kroll, J. H., Jimenez, J. L., Docherty, K. S., DeCarlo, P. F., Aiken, A. C., Chen, Q., Martin, S. T., Farmer, D. K., and Artaxo, P.: A simplified description of the evolution of organic aerosol composition in the atmosphere, Geophys. Res. Lett., 37, L08803, doi:08810.01029/02010GL042737, 2010.

Huang, X.-F., He, L.-Y., Hu, M., Canagaratna, M. R., Sun, Y., Zhang, Q., Zhu, T., Xue, L., Zeng, L.-W., Liu, X.-G., Zhang, Y.-H., Jayne, J. T., Ng, N. L., and Worsnop, D. R.: Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer, Atmos. Chem. Phys., 10, 8933–8945, http://dx.doi.org/10.5194/acp-10-8933-2010doi:10.5194/acp-10-8933-2010, 2010.

Huang, X.-F., He, L.-Y., Hu, M., Canagaratna, M. R., Kroll, J. H., Ng, N. L., Zhang, Y.-H., Lin, Y., Xue, L., Sun, T.-L., Liu, X.-G., Shao, M., Jayne, J. T., and Worsnop, D. R.: Characterization of submicron aerosols at a rural site in Pearl River Delta of China using an Aerodyne High-Resolution Aerosol Mass Spectrometer, Atmos. Chem. Phys., 11, 1865–1877, http://dx.doi.org/10.5194/acp-11-1865-2011doi:10.5194/acp-11-1865-2011, 2011.

Jaoui, M. and Kamens, R. M.: Mass balance of gaseous and particulate products analysis from α-pinene/NOx/air in the presence of natural sunlight, J. Geophys. Res.-Atmos., 106, 12541–12558, 2001.

Jimenez, J. L., Canagaratna, M. R., Donahue, N. M., Prevot, A. S. H., Zhang, Q., Kroll, J. H., DeCarlo, P. F., Allan, J. D., Coe, H., Ng, N. L., Aiken, A. C., Docherty, K. S., Ulbrich, I. M., Grieshop, A. P., Robinson, A. L., Duplissy, J., Smith, J. D., Wilson, K. R., Lanz, V. A., Hueglin, C., Sun, Y. L., Tian, J., Laaksonen, A., Raatikainen, T., Rautiainen, J., Vaattovaara, P., Ehn, M., Kulmala, M., Tomlinson, J. M., Collins, D. R., Cubison, M. J., Dunlea, E. J., Huffman, J. A., Onasch, T. B., Alfarra, M. R., Williams, P. I., Bower, K., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K., Salcedo, D., Cottrell, L., Griffin, R., Takami, A., Miyoshi, T., Hatakeyama, S., Shimono, A., Sun, J. Y., Zhang, Y. M., Dzepina, K., Kimmel, J. R., Sueper, D., Jayne, J. T., Herndon, S. C., Trimborn, A. M., Williams, L. R., Wood, E. C., Middlebrook, A. M., Kolb, C. E., Baltensperger, U., and Worsnop, D. R.: Evolution of Organic Aerosols in the Atmosphere, Science, 326, 1525–1529, 2009.

Johnson, D., Jenkin, M. E., Wirtz, K., and Martin-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of toluene, Environ. Chem., 1, 150–165, 2004.

Johnson, D., Jenkin, M. E., Wirtz, K., and Martin-Reviejo, M.: Simulating the formation of secondary organic aerosol from the photooxidation of aromatic hydrocarbons, Environ. Chem., 2, 35–48, 2005.

Kroll, J. H., Smith, J. D., Che, D. L., Kessler, S. H., Worsnop, D. R., and Wilson, K. R.: Measurement of fragmentation and functionalization pathways in the heterogeneous oxidation of oxidized organic aerosol, Phys. Chem. Chem. Phys., 11, 8005–8014, 2009.

Kroll, J. H., Donahue, N. M., Jimenez, J. L., Kessler, S. H., Canagaratna, M. R., Wilson, K. R., Altieri, K. E., Mazzoleni, L. R., Wozniak, A. S., Bluhm, H., Mysak, E. R., Smith, J. D., Kolb, C. E., and Worsnop, D. R.: Carbon oxidation state as a metric for describing the chemistry of atmospheric organic aerosol, Nat. Chem., 3, 133–139, doi:110.1038/NCHEM.1948, 2011.

Lambe, A. T., Onasch, T. B., Massoli, P., Croasdale, D. R., Wright, J. P., Ahern, A. T., Williams, L. R., Worsnop, D. R., Brune, W. H., and Davidovits, P.: Laboratory studies of the chemical composition and cloud condensation nuclei (CCN) activity of secondary organic aerosol (SOA) and oxidized primary organic aerosol (OPOA), Atmos. Chem. Phys. Discuss., 11, 13617–13653, http://dx.doi.org/10.5194/acpd-11-13617-2011doi:10.5194/acpd-11-13617-2011, 2011.

Massoli, P., Lambe, A. T., Ahern, A. T., Williams, L. R., Ehn, M., Mikkila, J., Canagaratna, M. R., Brune, W. H., Onasch, T. B., Jayne, J. T., Petaja, T., Kulmala, M., Laaksonen, A., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles, Geophys. Res. Lett., 37, L24801, doi:24810.21029/22010GL045258, 2010.

Morgan, W. T., Allan, J. D., Bower, K. N., Highwood, E. J., Liu, D., McMeeking, G. R., Northway, M. J., Williams, P. I., Krejci, R., and Coe, H.: Airborne measurements of the spatial distribution of aerosol chemical composition across Europe and evolution of the organic fraction, Atmos. Chem. Phys., 10, 4065–4083, http://dx.doi.org/10.5194/acp-10-4065-2010doi:10.5194/acp-10-4065-2010, 2010.

Ng, N. L., Canagaratna, M. R., Zhang, Q., Jimenez, J. L., Tian, J., Ulbrich, I. M., Kroll, J. H., Docherty, K. S., Chhabra, P. S., Bahreini, R., Murphy, S. M., Seinfeld, J. H., Hildebrandt, L., Donahue, N. M., DeCarlo, P. F., Lanz, V. A., Prévôt, A. S. H., Dinar, E., Rudich, Y., and Worsnop, D. R.: Organic aerosol components observed in Northern Hemispheric datasets from Aerosol Mass Spectrometry, Atmos. Chem. Phys., 10, 4625–4641, http://dx.doi.org/10.5194/acp-10-4625-2010doi:10.5194/acp-10-4625-2010, 2010.

Ng, N. L., Herndon, S. C., Trimborn, A., Canagaratna, M. R., Croteau, P., Onasch, T. M., Sueper, D., Worsnop, D. R., Zhang, Q., Sun, Y. L., and Jayne, J. T.: An Aerosol Chemical Speciation Monitor (ACSM) for routine monitoring of atmospheric aerosol composition, Aerosol Sci. Technol., 45, 770–784, 2011.

Russell, L. M., Bahadur , R., and Ziemann, P. J.: Identifying organic aerosol sources by comparing functional group composition in chamber and atmospheric particles, Proc. Natl. Acad. Sci. USA, 108, 3516–3521, http://dx.doi.org/10.1073/pnas.1006461108doi:10.1073/pnas.1006461108, 2011.

Sun, Y.-L., Zhang, Q., Schwab, J. J., Demerjian, K. L., Chen, W.-N., Bae, M.-S., Hung, H.-M., Hogrefe, O., Frank, B., Rattigan, O. V., and Lin, Y.-C.: Characterization of the sources and processes of organic and inorganic aerosols in New York city with a high-resolution time-of-flight aerosol mass apectrometer, Atmos. Chem. Phys., 11, 1581–1602, http://dx.doi.org/10.5194/acp-11-1581-2011doi:10.5194/acp-11-1581-2011, 2011.

Surratt, J. D., Murphy, S. M., Kroll, J. H., Ng, N. L., Hildebrandt, L., Sorooshian, A., Szmigielski, R., Vermeylen, R., Maenhaut, W., Claeys, M., Flagan, R. C., and Seinfeld, J. H.: Chemical composition of secondary organic aerosol formed from the photooxidation of isoprene, J. Phys. Chem. A, 110, 9665–9690, 2006.

Szmigielski, R., Surratt, J. D., Gomez-Gonzalez, Y., Van der Veken, P., Kourtchev, I., Vermeylen, R., Blockhuys, F., Jaoui, M., Kleindienst, T. E., Lewandowski, M., Offenberg, J. H., Edney, E. O., Seinfeld, J. H., Maenhaut, W., and Claeys, M.: 3-methyl-1,2,3-butanetricarboxylic acid: An atmospheric tracer for terpene secondary organic aerosol, Geophys.Res. Lett., 34, L24811, doi:24810.21029/22007GL031338, 2007.

Van Krevelen, D. W.: Graphical-statistical method for the study of structure and reaction processes of coal, Fuel, 24, 269–284, 1950.