References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-10-1969-2010

Simultaneous factor analysis of organic particle and gas mass spectra: AMS and PTR-MS measurements at an urban site

Slowik

J. G.

¹ ³ Vlasenko

¹ ³ McGuire

² ³ Evans

G. J.

² ³ Abbatt

J. P. D.

¹ ³

Department of Chemistry, University of Toronto, Toronto, Canada

Department of Chemical Engineering and Applied Chemistry, University of Toronto, Toronto, Canada

Southern Ontario Centre for Atmospheric Aerosol Research, University of Toronto, Toronto, Canada

19 02 2010

10 4 1969 1988

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/10/1969/2010/acp-10-1969-2010.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/10/1969/2010/acp-10-1969-2010.pdf

During the winter component of the SPORT (Seasonal Particle Observations in the Region of Toronto) field campaign, particulate non-refractory chemical composition and concentration of selected volatile organic compounds (VOCs) were measured by an Aerodyne time-of-flight aerosol mass spectrometer (AMS) and a proton transfer reaction-mass spectrometer (PTR-MS), respectively. Sampling was performed in downtown Toronto ~15 m from a major road. The mass spectra from the AMS and PTR-MS were combined into a unified dataset, which was analysed using positive matrix factorization (PMF). The two instruments were given balanced weight in the PMF analysis by the application of a scaling factor to the uncertainties of each instrument. A residual based metric, Δesc, was used to evaluate the instrument relative weight within each solution. The PMF analysis yielded a 6-factor solution that included factors characteristic of regional transport, local traffic emissions, charbroiling and oxidative processing. The unified dataset provides information on emission sources (particle and VOC) and atmospheric processing that cannot be obtained from the datasets of the individual instruments: (1) apportionment of oxygenated VOCs to either direct emission sources or secondary reaction products; (2) improved correlation of oxygenated aerosol factors with photochemical age; and (3) increased detail regarding the composition of oxygenated organic aerosol factors. This analysis represents the first application of PMF to a unified AMS/PTR-MS dataset.

References 1

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, doi:10.1021/es703009q, 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, 2009.

Allan, J. D., Coe, H., Bower, K. N., Alfarra, M. R., Delia, A. E., Jimenez, J. L., Middlebrook, A. M., Drewnick, F., Onasch, T. B., Canagaratna, M. R., Jayne, J. T., and Worsnop, D. R. : Technical note: A generalized method for the extraction of chemically resolved mass spectra from Aerodyne aerosol mass spectrometer data, J. Aerosol Sci., 35, 909–922, 2004.

Allan, J. D., Jimenez, J. L., Williams, P. I., Alfarra, M. R., Bower, K. N., Jayne, J. T., Coe, H., and Worsnop, D. R.: Quantitative sampling using an Aerodyne aerosol mass spectrometer 1: Techniques of data interpretation and error analysis, J. Geophys. Res., 108, 4090: doi:10.1029/2002JD002358, 2003.

Andreae, M. O. and Merlet, P. : Emission of trace gases and aerosols from biomass burning, Global Biogeochem. Cy., 15, 955–966, 2001.

Atkinson, R., Baulch, D. L., Cox, R. A., Crowley, J. N., Hampson, R. F., Hynes, R. G., Jenkin, M. E., Rossi, M. J., Troe, J., and IUPAC Subcommittee: Evaluated kinetic and photochemical data for atmospheric chemistry: Volume II – gas phase reactions of organic species, Atmos. Chem. Phys., 6, 3625–4055, 2006.

Beychok, M. R.: A Data Base for Dioxin and Furan Emissions from Municipal Refuse Incinerators, Atmos. Environ., 21, 29–36, 1987.

Buset, K. C., Evans, G. J., Leaitch, W. R., Brook, J. R., and Toom-Sauntry, D. : Use of advanced receptor modelling for analysis of an intensive 5-week aerosol sampling campaign, Atmos. Environ., 40, 482–499, 2006.

Buzcu, B. and Frazier, M. P.: Source Identification and Apportionment of Volatile Organic Compounds in Houston, TX, Atmos. Environ., 40, 2385–2400, 2006.

Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasch, T. B., Drewnick, F., Coe, H., Middlebrook, A. M., Delia, A., Williams, L. R., Trimborn, A. M., Northway, M. J., DeCarlo, P. F., Kolb, C. E., Davidovits, P., and Worsnop, D. R.: Chemical and microphysical characterization of ambient aerosols with the Aerodyne aerosol mass spectrometer, Mass Spec. Rev., 26, 185–222, 2007.

de Gouw, J. A., Goldan, P. D., Warneke, C., Kuster, W. C., Roberts, J. M., Marchewka, M., Bertman, S. B., Pszenny, A. A. P., and Keene, W. C.: Validation of proton transfer reaction-mass spectrometry (PTR-MS) measurements of gas-phase organic compounds in the atmosphere during the New England Air Quality Study (NEAQS) in 2002, J. Geophys. Res., 108, 4682, doi:10.1029/2003JD003863, 2003.

de Gouw, J. A., Middlebrook, A. M., Warneke, C., Goldan, P. D., Kuster, W. C., Roberts, J. M., Fehsenfeld, F. C., Worsnop, D. R., Canagaratna, M. R., Pszenny, A. A. P., Keene, W. C., Marchewka, M., Bertman, S. B., and Bates, T. S.: Budget of organic carbon in a polluted atmosphere: Results from the New England Air Quality Study in 2002, J. Geophys. Res., 110, D16305, doi:10.1029/2004JD005623, 2005.

de Gouw, J. A. and Warneke, C. : Measurements of volatile organic compounds in the Earth's atmosphere using proton-transfer-reaction mass spectrometry, Mass Spec. Rev., 26, 223–257, 2007.

Dockery, D. W. and Pope, C. A.: Acute respiratory effects of particulate air pollution, Annual Review of Public Health, 15, 107–132, 1994.

Donahue, N. M., Robinson, A. L., Stanier, C. O., and Pandis, S. N.: Coupled Partitioning, Dilution, and Chemical Aging of Semivolatile Organics, Environ. Sci. Technol., 40, 2635–2643, 2006.

Draxler, R. R. and Hess, G. D. : An overview of the Hysplit_4 modelling system for trajectories, dispersion, and deposition, Aust. Met. Mag., 47, 295–308, 1998.

Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD, 2003.

Drewnick, F., Hings, S. S., DeCarlo, P. F., Jayne, J. T., Gonin, M., Fuhrer, K., Weimer, S., Jimenez, J. L., Demerjian, K. L., Borrmann, S., and Worsnop, D. R. : A new Time-of-Flight Aerosol Mass Spectrometer (ToF-AMS) – Instrument description and first field deployment, Aerosol Sci. Technol., 39, 637–658, 2005.

Driscoll, C. T., Driscoll, K. M., Roy, K. M., and Mitchell, M. J.: Chemical responses of lakes in the Adirondack region of New York to declines in acidic deposition, Environ. Sci. Technol., 37, 2036–2042, 2003.

Friedfeld, S., Fraser, M., Ensor, K., Tribble, S., Rehle, D., Leleux, D., and Tittle, F.: Statistical analysis of primary and secondary atmospheric formaldehyde, Atmos. Environ., 36, 4767–4775, 2002.

Garcia, A. R., Volkamer, R., Molina, L. T., Molina, M. J., Samuelson, J., Mellqvist, J., Galle, B., Herndon, S. C., and Kolb, C. E.: Separation of emitted and photochemical formaldehyde in Mexico City using a statistical analysis and a new pair of gas-phase tracers, Atmos. Chem. Phys., 6, 4545–4557, 2006.

Godri, K. J., Evans, G. J., Slowik, J., Knox, A., Abbatt, J., Brook, J., Dann, T., and Dabek-Zlotorzynska, E.: Evaluation and application of a semi-continuous chemical characterization system for water soluble inorganic PM$_2.5$ and associated precursor gases, Atmos. Meas. Tech., 2, 65–80, 2009.

Hansel, A., Jordan, A., Holzinger, R., Prazeller, P., Vogel, W., and Lindinger, W.: Proton transfer reaction mass spectrometry: on-line trace gas analysis at ppb level, Int. J. Mass Spectrom. Ion Processes, 149/150, 609–619, 1995.

Holzinger, R., Millet, D. B., Williams, B., Lee, A., Kreisberg, N., Hering, S. V., Jimenez, J. L., Allan, J. D., Worsnop, D. R., and Goldstein, A. H.: Emission, oxidation, and secondary organic aerosol formation of volatile organic compounds as observed at Chebogue Point, Nova Scotia, J. Geophys. Res., 112, D10S24, doi:10.1029/2006JD007599, 2007.

Jacobson, M. Z.: Strong radiative heating due to the mixing state of black carbon in atmospheric aerosols, Nature, 409, 695–697, 2001.

Kanakidou, M., Seinfeld, J. H., Pandis, S. N., Barnes, I., Dentener, F. J., Facchini, M. C., Van Dingenen, R., Ervens, B., Nenes, A., Nielsen, C. J., Swietlicki, E., Putaud, J. P., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G. K., Winterhalter, R., Myhre, C. E. L., Tsigaridis, K., Vignati, E., Stephanou, E. G., and Wilson, J.: Organic aerosol and global climate modelling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005.

Kristensson, K., Johansson, C., Westerholm, R., Swietlicki, E., Gidhagen, L., Wideqvist, U., and Vesely, V.: Real-world traffic emission factors of gases and particles measured in a road tunnel in Stockholm, Sweden, Atmos. Environ., 38, 657–673, 2004.

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., and Pr�v�t, 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, 2007.

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., Szidat, S., Wehrli, M. N., Wacker, L., Weimer, S., Caseiro, A., Puxbaum, H., and Prevot, A. S. H.: Source Attribution of Submicron Organic Aerosols during Wintertime Inversions by Advanced Factor Analysis of Aerosol Mass Spectra, Environ. Sci. Technol., 42, 214–220, 2008a.

Lanz, V. A., Hueglin, C., Buchmann, B., Hill, M., Locher, R., Staehelin, J., and Reimann, S.: Receptor modelling of C2–C7 hydrocarbon sources at an urban background site in Zurich, Switzerland: changes between 1993–1994 and 2005–2006, Atmos. Chem. Phys., 8, 2313–2332, 2008b.

Lee, P. K., Brook, J. R., Dabek-Zlotorzynska, E., and Mabury, S. A.: Identification of the major sources contribution to PM$_2.5$ observed in Toronto, Environ. Sci. Technol., 37, 4831–4840, 2003.

Lee, S. H.: Emissions from Street Vendor Cooking Devices (Charcoal Grilling), US EPA, Washington, DC, 1999.

Lewis, C. W., Norris, G. A., Conner, T. L., and Henry, R. C.: Source apportionment of Phoenix PM$_2. 5$ aerosol with the UNMIX receptor model, J. Air Waste Man. Assoc., 53, 325–338, 2003.

Li, S.-M., Anlauf, K. G., Wiebe, H. A., Bottenheim, J. W., Shepson, P. B., and Biesenthal, T. A.: Emission ratios and photochemical production efficiencies of nitrogen oxides, ketones, and aldehydes in the Lower Fraser Valley during the Summer Pacific 1993 oxidant study, Atmos. Environ., 31, 2037–2048, 1997.

Lindinger, W., Hansel, A., and Jordan, A.: Proton-transfer reaction mass spectrometry (PTR-MS): on-line monitoring of volatile organic compounds at pptv levels, Chem. Soc. Rev., 27, 347–354, 1998.

McLafferty, F. W.: Interpretation of Mass Spectra, University Science Books, Mill Valley, CA, 1980.

Owega, S., Khan, B. U. Z., D'Souza, R., Evans, G. J., Fila, M., and Jervis, R. E. : Receptor Modelling of Toronto PM2. 5 Characterised by Aerosol Laser Ablation Mass Spectrometry, Environ. Sci. Technol., 38, 5712–5720, 2004.

Paatero, P.: Least squares formulation of robust non-negative factor analysis, Chemom. Intell. Lab. Syst., 37, 23–35, 1997.

Paatero, P.: Interactive Comment on "Simultaneous factor analysis of organic particle and gas mass spectra: AMS and PTR-MS measurements at an urban site" by J. G. Slowik et al., Atmos. Chem. Phys. Discuss., 9, C114-C123, 2009.

Paatero, P. and Tapper, U.: Positive Matrix Factorization: A non-negative factor model with optimal utilization of error estimates of data values, Environmetrics, 5, 111–126, 1994.

Polissar, A. V., Hopke, P. K., and Poirot, R. L.: Atmospheric aerosol over Vermont: chemical composition and sources, Environ. Sci. Technol., 35, 4604–4621, 2001.

Pope, C. A. and Dockery, D. W.: Health effects of fine particulate air pollution: lines that connect, J. Air Waste Man. Assoc., 56, 709–742, 2006.

Possanzini, M., Palo, V. D., and Cecinato, A.: Sources and photodecomposition of formaldehyde and acetaldehyde in Rome ambient air, Atmos. Environ., 36, 3195–3201, 2002.

Quinn, P. K., Bates, T. S., Coffman, D., Onasch, T. B., Worsnop, D. R., Baynard, T., de Gouw, J. A., Goldan, P. D., Kuster, W. C., Williams, E., Roberts, J. M., Lerner, B., Stohl, A., Pettersson, A., and Lovejoy, E. R.: Impacts of sources and aging on submicrometer aerosol properties in the marine boundary layer across the Gulf of Maine, J. Geophys. Res., 111, D23S36, doi:10.1029/2006JD007582, 2006.

Ramadan, Z., Song, X.-H., and Hopke, P. K.: Identification of sources of Phoenix aerosol by positive matrix factorization, J. Air Waste Manag. Assoc., 50, 1308–1320, 2000.

Ramanathan, V., Crutzen, P. J., Kiehl, J. T., and Rosenfeld, D.: Aerosols, climate, and the hydrologic cycle, Science, 294, 2119–2124, 2001.

Roberts, J. M., Fehsenfeld, F. C., Liu, S. C., Bollinger, M. J., Hahn, C., Albritton, D. L., and Sievers, R. E. : Measurements of aromatic hydrocarbon ratios and NOx concentrations in the rural troposphere: Estimates of air mass photochemical age and NOx removal rate, Atmos. Environ., 18, 2421–2432, 1984.

Robinson, A. L., Donahue, N. M., Shrivastava, M. K., Weitkamp, E. A., Sage, A. M., Grieshop, A. P., Lane, T. E., Pierce, J. R., and Pandis, S. N.: Rethinking Organic Aerosol: Semivolatile Emissions and Photochemical Aging, Science, 315, 1259–1262, 2007.

Rolph, G. D., Real-time Environmental Applications and Display sYstem (READY) Website (http://www.arl.noaa.gov/ready/hysplit4.html), NOAA Air Resources Laboratory, Silver Spring, MD, 2003.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of Emissions from Air Pollution Sources, 1 C$_1$ through C$_29$ Organic Compounds from Meat Charbroiling, Environ. Sci. Technol., 33, 1566–1577, 1999.

Schindler, D. W.: Effects of acid-rain on fresh-water ecosystems, Science, 239, 149–157, 1988.

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, 2009.

Ulbrich, I. M., Lechner, M., and Jimenez, J. L.: AMS Spectral Database, online available: http://cires.colorado.edu/jimenez-group/AMSsd/, 2009b.

Vlasenko, A., Slowik, J. G., Bottenheim, J. W., Brickell, P. C., Chang, R. Y.-W., Macdonald, A. M., Shantz, N. C., Sjostedt, S. J., Wiebe, H. A., Leaitch, W. R., and Abbatt, J. P. D.: Measurements of VOCs by proton transfer reaction mass spectrometry at a rural Ontario site: Sources and correlation to aerosol composition, J. Geophys. Res., 114, D21305, doi:10.1029/2009JD12025, 2009.

Watson, J. G.: Visibility: Science and Regulation, J. Air Waste Manag., 52, 628–713, 2002.

Weimer, S., Alfarra, M. R., Schreiber, D., Mohr, M., Prevot, A. S. H., and Baltensperger, U. : Organic aerosol mass spectral signatures from wood-burning emissions: Influence of burning conditions and wood type, J. Geophys. Res., 113, D10304, doi:10.1029/2007JD009309, 2008.

Zervas, E., Montagne, X., and Lahaye, J.: C-C organic acid emissions from an SI engine: influence of fuel and air/fuel equivalence ratio, Environ. Sci. Technol., 35, 2746–2751, 2001.

Zhang, Q., Alfarra, M. R., Worsnop, D. R., Allan, J. D., Coe, H., Canagaratna, M. R., and Jimenez, J. L.: Deconvolution and Quantification of Hydrocarbon-like and Oxygenated Organic Aerosols Based on Aerosol Mass Spectrometry, Environ. Sci. Technol., 39, 4938–4952, 2005.

Zhang, Q., Jimenez, J. L., Canagaratna, M. R., Allan, J. D., Coe, H., Ulbrich, I., Alfarra, M. R., Takami, A., Middlebrook, A. M., Sun, Y. L., Dzepina, K., Dunlea, E., Docherty, K., DeCarlo, P. F., Salcedo, D., Onasch, T. B., Jayne, J. T., Miyoshi, T., Shimono, A., Hatakeyama, S., Takegawa, N., Kondo, Y., Schneider, J., Drewnick, F., Borrmann, S., Weimer, S., Demerjian, K. L., Williams, P., Bower, K., Bahreini, R., Cottrell, L., Griffin, R. J., Rautiainen, J., Sun, J. Y., Zhang, Y. M., and Worsnop, D. R.: Ubiquity and dominance of oxygenated species in organic aerosols in anthropogenically-influenced Northern Hemisphere midlatitudes, Geophys. Res. Let., 34, L13801, doi:10.1029/2007GL029979, 2007.

Zhao, W. X. and Hopke, P. K.: Source identification for fine aerosols in Mammoth Cave National Park, Atmos. Res., 80, 309–322, 2006.