ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-12-11795-2012 Analysis of secondary organic aerosol formation and aging using positive matrix factorization of high-resolution aerosol mass spectra: application to the dodecane low-NO<sub>x</sub> system Craven J. S. 1 Yee L. D. 2 Ng N. L. 6 Canagaratna M. R. 3 Loza C. L. 1 Schilling K. A. 1 Yatavelli R. L. N. 4 7 Thornton J. A. 4 Ziemann P. J. 5 Flagan R. C. 1 2 Seinfeld J. H. 1 2 Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, California, USA Division of Engineering and Applied Science, California Institute of Technology, Pasadena, California, USA Aerodyne Research, Inc., Billerica, Massachusetts, USA Department of Atmospheric Sciences, University of Washington, Seattle, Washington, USA Air Pollution Research Center, Department of Environmental Sciences, and Environmental Toxicology Graduate Program, University of California, Riverside, California, USA School of Chemical and Biomolecular Engineering and School of Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, Georgia, USA current address: Cooperative Institute for Research in Environmental Sciences (CIRES), University of Colorado, Boulder, Colorado, USA 17 12 2012 12 24 11795 11817 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/12/11795/2012/acp-12-11795-2012.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/12/11795/2012/acp-12-11795-2012.pdf

Positive matrix factorization (PMF) of high-resolution laboratory chamber aerosol mass spectra is applied for the first time, the results of which are consistent with molecular level MOVI-HRToF-CIMS aerosol-phase and CIMS gas-phase measurements. Secondary organic aerosol was generated by photooxidation of dodecane under low-NO<sub>x</sub> conditions in the Caltech environmental chamber. The PMF results exhibit three factors representing a combination of gas-particle partitioning, chemical conversion in the aerosol, and wall deposition. The slope of the measured high-resolution aerosol mass spectrometer (HR-ToF-AMS) composition data on a Van Krevelen diagram is consistent with that of other low-NO<sub>x</sub> alkane systems in the same O : C range. Elemental analysis of the PMF factor mass spectral profiles elucidates the combinations of functionality that contribute to the slope on the Van Krevelen diagram.

 References 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. Allan, J D.: Quantitative sampling using an Aerodyne aerosol mass spectrometer 1. Techniques of data interpretation and error analysis, J. Geophys. Res., 108, 4090, http://dx.doi.org/10.1029/2002JD002358doi:10.1029/2002JD002358, 2003. Allan, J D., Delia, A E., Coe, H., Bower, K N., Alfarra, M R., Jimenez, J L., Middlebrook, A M., Drewnick, F., Onasch, T B., Canagaratna, M R., Jayne, J T., and Worsnop, D R.: A generalised method for the extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, 2004. 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., 11, 8827–8845, http://dx.doi.org/10.5194/acp-11-8827-2011doi:10.5194/acp-11-8827-2011, 2011. Cocker, D R., Flagan, R C., and Seinfeld, J H.: State-of-the-Art Chamber Facility for Studying Atmospheric Aerosol Chemistry, Environ. Sci. Technol., 35, 2594–2601, 2001. Crounse, J D., McKinney, K A., Kwan, A J., and Wennberg, P O.: Measurement of Gas-Phase Hydroperoxides by Chemical Ionization Mass Spectrometry, Anal. Chem., 78, 6726–6732, 2006. DeCarlo, P F., Kimmel, J R., Trimborn, A., Northway, M J., Jayne, J T., Aiken, A C., Gonin, M., Fuhrer, K., Horvath, T., Docherty, K S., Worsnop, D R., and Jimenez, J L.: Field-Deployable, High-Resolution, Time-of-Flight Aerosol Mass Spectrometer, Anal. Chem., 78, 8281–8289, 2006. Fraser, R. T M., Paul, N C., and Phillips, L.: Mass spectrometry of some alkyl peroxides, J. Chem. Soc. B, 1970, 1278–1280, http://dx.doi.org/10.1039/J29700001278doi:10.1039/J29700001278, 1970. Fry, J. L., Kiendler-Scharr, A., Rollins, A. W., Brauers, T., Brown, S. S., Dorn, H.-P., Dubé, W. P., Fuchs, H., Mensah, A., Rohrer, F., Tillmann, R., Wahner, A., Wooldridge, P. J., and Cohen, R. C.: SOA from limonene: role of NO<sub>3</sub> in its generation and degradation, Atmos. Chem. Phys., 11, 3879–3894, http://dx.doi.org/10.5194/acp-11-3879-2011doi:10.5194/acp-11-3879-2011, 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, http://dx.doi.org/10.1029/2010GL042737doi:10.1029/2010GL042737, 2010. Hersey, S. P., Craven, J. S., Schilling, K. A., Metcalf, A. R., Sorooshian, A., Chan, M. N., Flagan, R. C., and Seinfeld, J. H.: The Pasadena Aerosol Characterization Observatory (PACO): chemical and physical analysis of the Western Los Angeles basin aerosol, Atmos. Chem. Phys., 11, 7417–7443, http://dx.doi.org/10.5194/acp-11-7417-2011doi:10.5194/acp-11-7417-2011, 2011. Isaacman, G., Chan, A. W H., Nah, T., Worton, D R., Ruehl, C R., Wilson, K R., and Goldstein, A H.: Heterogeneous OH Oxidation of Motor Oil Particles Causes Selective Depletion of Branched and Less Cyclic Hydrocarbons, Environ. Sci. Technol., 46, 10632–10640, 2012. Jimenez, J L., Canagaratna, M R., Donahue, N M., Prévôt, 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., E., Dunlea, 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. 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., 11, 8913–8928, http://dx.doi.org/10.5194/acp-11-8913-2011doi:10.5194/acp-11-8913-2011, 2011. Lambe, A T., Onasch, T B., Croasdale, D R., Wright, J P., Martin, A T., Franklin, J P., Massoli, P., Kroll, J H., Canagaratna, M R., Brune, W H., Worsnop, D R., and Davidovits, P.: Transitions from Functionalization to Fragmentation Reactions of Laboratory Secondary Organic Aerosol (SOA) Generated from the OH Oxidation of Alkane Precursors, Environ. Sci. Technol., 46, 5430–5437, 2012. Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Prévôt, A. S. H.: Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra, Atmos. Chem. Phys., 7, 1503–1522, http://dx.doi.org/10.5194/acp-7-1503-2007doi:10.5194/acp-7-1503-2007, 2007. Loza, C. L., Chhabra, P. S., Yee, L. D., Craven, J. S., Flagan, R. C., and Seinfeld, J. H.: Chemical aging of $m$-xylene secondary organic aerosol: laboratory chamber study, Atmos. Chem. Phys., 12, 151–167, http://dx.doi.org/10.5194/acp-12-151-2012doi:10.5194/acp-12-151-2012, 2012. 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., 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., 11, 6465–6474, http://dx.doi.org/10.5194/acp-11-6465-2011doi:10.5194/acp-11-6465-2011, 2011. Paatero, P.: Interactive comment on Atmos. Chem. Phys. Discuss., 12, 16647, 2012. Paatero, P. and Hopke, P K.: Discarding or downweighting high-noise variables in factor analytic models, Anal. Chim. Acta, 490, 277–289, 2003. Paatero, P. and Tapper, U.: Positive Matrix Factorization – a Nonnegative Factor Model with Optimal Utilization of Error-Estimates of Data Values, Environmetrics, 5, 111–126, 1994. Paatero, P., Hopke, P K., Song, X H., and Ramadan, Z.: Understanding and controlling rotations in factor analytic models, Chemometr. Intell. Lab., 60, 253–264, 2002. Paulot, F., Crounse, J. D., Kjaergaard, H. G., Kroll, J. H., Seinfeld, J. H., and Wennberg, P. O.: Isoprene photooxidation: new insights into the production of acids and organic nitrates, Atmos. Chem. Phys., 9, 1479–1501, http://dx.doi.org/10.5194/acp-9-1479-2009doi:10.5194/acp-9-1479-2009, 2009. Pye, H. O T. and Pouliot, G A.: Modeling the Role of Alkanes, Polycyclic Aromatic Hydrocarbons, and Their Oligomers in Secondary Organic Aerosol Formation, Environ. Sci. Technol., 46, 6041–6047, 2012. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of Emissions from Air Pollution Sources. 3. C1–C29 Organic Compounds from Fireplace Combustion of Wood, Environ. Sci. Technol., 35, 1716–1728, 2001. Schauer, J J., Kleeman, M J., Cass, G R., and Simoneit, B. R T.: Measurement of Emissions from Air Pollution Sources. 5. C1–C32 Organic Compounds from Gasoline-Powered Motor Vehicles, Environ. Sci. Technol., 36, 1169–1180, 2002. St Clair, J M., McCabe, D C., Crounse, J D., Steiner, U., and Wennberg, P O.: Chemical ionization tandem mass spectrometer for the in situ measurement of methyl hydrogen peroxide, Rev. Sci. Instrum., 81, 094102, http://dx.doi.org/10.1063/1.3480552doi:10.1063/1.3480552, 2010. Tobias, H J. and Ziemann, P J.: Thermal Desorption Mass Spectrometric Analysis of Organic Aerosol Formed from Reactions of 1-Tetradecene and O<sub>3</sub> in the Presence of Alcohols and Carboxylic Acids, Environ. Sci. Technol., 34, 2105–2115, 2000. Ulbrich, I. M., Canagaratna, M. R., Zhang, Q., Worsnop, D. R., and Jimenez, J. L.: Interpretation of organic components from Positive Matrix Factorization of aerosol mass spectrometric data, Atmos. Chem. Phys., 9, 2891–2918, http://dx.doi.org/10.5194/acp-9-2891-2009doi:10.5194/acp-9-2891-2009, 2009. Van~Krevelen, D W.: Graphical-statistical method for the study of structure and reaction processes of coal, Fuel, 24, 269–284, 1950. Yatavelli, R. L N. and Thornton, J A.: Particulate Organic Matter Detection Using a Micro-Orifice Volatilization Impactor Coupled to a Chemical Ionization Mass Spectrometer (MOVI-CIMS), Aerosol Sci. Tech., 44, 61–74, 2010. Yatavelli, R. L N., Lopez-Hilfiker, F D., Wargo, J., Kimmel, J R., Cubison, M J., Bertram, T H., Jimenez, J., Gonin, M., Worsnop, D R., and Thornton, J A.: Analysis of Gas and Particle-phase Organic Matter Using a Chemical Ionization High-Resolution Time-of-Flight Mass Spectrometer (HTOF-CIMS) Coupled to a Micro Orifice Volatilization Impactor (MOVI), Aerosol Sci. Tech., 46, 1313–1327, http://dx.doi.org/10.1080/02786826.2012.712236doi:10.1080/02786826.2012.712236, 2012. Yee, L D., Craven, J S., Loza, C L., Schilling, K A., Ng, N L., Canagaratna, M R., Ziemann, P J., Flagan, R C., and Seinfeld, J H.: Secondary Organic Aerosol Formation from Low-NO$_\mathrmx$ Photooxidation of Dodecane: Evolution of Multi-Generation Gas-Phase Chemistry and Aerosol Composition, J. Phys. Chem. A, 116, 6211–6230, 2012. Zhang, Q., Jimenez, J L., Canagaratna, M R., Ulbrich, I M., Ng, N L., Worsnop, D R., and Sun, Y.: Understanding atmospheric organic aerosols via factor analysis of aerosol mass spectrometry: a review, Anal. Bioanal. Chem., 401, 3045–3067, 2011. Ziemann, P J.: Formation of Alkoxyhydroperoxy Aldehydes and Cyclic Peroxyhemiacetals from Reactions of Cyclic Alkenes with O<sub>3</sub> in the Presence of Alcohols, J. Phys. Chem. A, 107, 2048–2060, 2003.