Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra
10.5194/acp-7-1503-2007
Crossref journal-article
Copernicus GmbH
Atmospheric Chemistry and Physics (3145)
Abstract

Abstract. Submicron ambient aerosol was characterized in summer 2005 at an urban background site in Zurich, Switzerland, during a three-week measurement campaign. Highly time-resolved samples of non-refractory aerosol components were analyzed with an Aerodyne aerosol mass spectrometer (AMS). Positive matrix factorization (PMF) was used for the first time for aerosol mass spectra to identify the main components of the total organic aerosol and their sources. The PMF retrieved factors were compared to measured reference mass spectra and were correlated with tracer species of the aerosol and gas phase measurements from collocated instruments. Six factors were found to explain virtually all variance in the data and could be assigned either to sources or to aerosol components such as oxygenated organic aerosol (OOA). Our analysis suggests that at the measurement site only a small (<10%) fraction of organic PM1 originates from freshly emitted fossil fuel combustion. Other primary sources identified to be of similar or even higher importance are charbroiling (10–15%) and wood burning (~10%). The fraction of all identified primary sources is considered as primary organic aerosol (POA). This interpretation is supported by calculated ratios of the modelled POA and measured primary pollutants such as elemental carbon (EC), NOx, and CO, which are in good agreement to literature values. A high fraction (60–69%) of the measured organic aerosol mass is OOA which is interpreted mostly as secondary organic aerosol (SOA). This oxygenated organic aerosol can be separated into a highly aged fraction, OOA I, (40–50%) with low volatility and a mass spectrum similar to fulvic acid, and a more volatile and probably less processed fraction, OOA II (on average 20%). This is the first publication of a multiple component analysis technique to AMS organic spectral data and also the first report of the OOA II component.

Bibliography

Lanz, V. A., Alfarra, M. R., Baltensperger, U., Buchmann, B., Hueglin, C., & Prévôt, A. S. H. (2007). Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra. Atmospheric Chemistry and Physics, 7(6), 1503–1522.

Authors 6
  1. V. A. Lanz (first)
  2. M. R. Alfarra (additional)
  3. U. Baltensperger (additional)
  4. B. Buchmann (additional)
  5. C. Hueglin (additional)
  6. A. S. H. Prévôt (additional)
References 59 Referenced 647
  1. Alfarra, M. R.: Insights into Atmospheric Organic Aerosols Using an Aerosol Mass Spectrometer, Ph.D. thesis, University of Manchester Institute of Science and Technology (UMIS), Manchester, 2004.
  2. Alfarra, M. R., Coe, H., Allan, J. D., Bower, K. N., Boudries, H., Canagaratna, M. R., Jimenez, J. L., Jayne, J. T., Garforth, A., Li, S.-M., and Worsnop, D. R.: Characterization of urban and regional organic aerosols in the lower Fraser Valley using two Aerodyne Aerosol Mass Spectrometers, Atmos. Environ., 38, 5745–5758, 2004. (10.1016/j.atmosenv.2004.01.054)
  3. Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prév\\^ot, A. S. H., Worsnop, D. R., Baltensperger, U., and Coe, H.: A mass spectrometric study of secondary organic aerosols formed from the photooxidation of anthropogenic and biogenic precursors in a reaction chamber, Atmos. Chem. Phys., 6, 5279–5293, 2006a. (10.5194/acp-6-5279-2006)
  4. 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.-Atmos., 108(D3), 4090, https://doi.org/10.1029/2002JD002358, 2003. (10.1029/2002JD002358)
  5. 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. (10.1016/j.jaerosci.2004.02.007)
  6. Bahreini, R., Keywood, M., Ng, N. L., Varutbangkul, V., Gao, S., Flagan, R. C., Seinfeld, J. H., Worsnop, D. R., and Jimenez, J. L.: Measurements of secondary organic aerosol from oxidation of cycloalkanes, terpenes, and m-xylene using the Aerodyne Aerosol Mass Spectrometer, Environ. Sci. Technol., 39, 5674–5688, 2005. (10.1021/es048061a)
  7. Begum, B. A., Kim, E., Biswas, S. K., and Hopke, P. K.: Investigation of sources of atmospheric aerosol at urban and semi-urban areas in Bangladesh, Atmos. Environ., 38, 3025–3038, 2004. (10.1016/j.atmosenv.2004.02.042)
  8. 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, Suppl. 2, 482–499, 2006. (10.1016/j.atmosenv.2005.12.074)
  9. Cabada, J. C., Pandis, S. N., and Robinson, A. L.: Sources of atmospheric carbonaceous particulate matter in Pittsburgh, Pennsylvania, J. Air Waste Manag. Assoc., 52(6), 732–741, 2002. (10.1080/10473289.2002.10470811)
  10. Cabada, J. C., Pandis, S. N., Subramanian, R., Robinson, A. L., Polidori, A., and Turpin, B.: Estimating the secondary organic aerosol contribution to PM2.5 using the EC tracer method, Aerosol Sci. Technol., 38, Suppl. 1, 140–155, 2004. (10.1080/02786820390229084)
  11. Canagaratna, M. R., Jayne, J. T., Ghertner, D. A., Herndon, S., Shi, Q., Jimenez, J. L., Silva, P. J., Williams, P., Lanni, T., Drewnick, F., Demerjian, K. L., Kolb, C. E., and Worsnop, D. R.: Chase studies of particulate emissions from in-use New York city vehicles, Aerosol Sci. Technol., 38, 555–573, https://doi.org/10.1080/02786820490465504, 2004. (10.1080/02786820490465504)
  12. Chung, Y. S., Kim, S. H., Moon, J. H., Kim, Y. J., Lim, J. M., and Lee, J. H.: Source identification and long-term monitoring of airborne particulate matter PM2.5/PM10) in an urban region of Korea, J. Radioanal. Nucl. Chem., 267, 35–48, 2005. (10.1007/s10967-006-0006-z)
  13. 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.-Atmos., 110, D16305, https://doi.org/10.1029/2004JD005623, 2005. (10.1029/2004JD005623)
  14. EKL: Status-Bericht der Eidg. Kommission für Lufthygiene. Stickstoffhaltige Luftschadstoffe in der Schweiz, Schriftenreihe Umwelt Nr. 384, Herausgegeben vom Bundesamt für Umwelt, Wald und Landschaft BUWAL, Bern, 2005.
  15. Empa: Technischer Bericht zum Nationalen Beobachtungsnetz für Luftfremdstoffe (NABEL), available at: http://www.empa.ch/nabel, Dübendorf, Switzerland, 2005.
  16. Fuzzi, S., Andreae, M. O., Huebert, B. J., Kulmala, M., Bond, T. C., Boy, M., Doherty, S. J., Guenther, A., Kanakidou, M., Kawamura, K., Kerminen, V.-M., Lohmann, U., Russell, L. M., and Pöschl, U.: Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change, Atmos. Chem. Phys., 6, 2017–2038, 2006. (10.5194/acp-6-2017-2006)
  17. Hedberg, E., Gidhagen, L., and Johansson, C.: Source contributions to PM10 and arsenic concentrations in Central Chile using positive matrix factorization, Atmos. Environ., 39, 549–561, 2005. (10.1016/j.atmosenv.2004.11.001)
  18. Hien, P. D., Bac, V. T., and Thinh, N. T. H.: PMF receptor modelling of fine and coarse PM10 in air masses governing monsoon conditions in Hanoi, Northern Vietnam, Atmos. Environ., 38, 189–201, 2004. (10.1016/j.atmosenv.2003.09.064)
  19. Hopke, P. K: Recent developments in receptor modeling, J. Chemom., 17, 255–265, 2003. (10.1002/cem.796)
  20. Huang, S., Rahn, K. A., and Arimoto, R.: Testing and optimizing two factor-analysis techniques on aerosol at Narragansett, Rhode Island, Atmos. Environ., 33, 2169–2185, 1999. (10.1016/S1352-2310(98)00324-0)
  21. Horvath, H.: Atmospheric light-absorption – A review, Atmos. Environ. Part A-General Topics, 27, 293–317, 1993. (10.1016/0960-1686(93)90104-7)
  22. Jaffrezo, J.-L., Aymoz, G., and Cozic, J.: Size distribution of EC and OC in the aerosol of Alpine valleys during summer and winter, Atmos. Chem. Phys., 5, 2915–2925, 2005. (10.5194/acp-5-2915-2005)
  23. Jayne, J. T., Leard, D. C., Zhang, X. F., Davidovits, P., Smith, K. A., Kolb, C. E., and Worsnop, D. R.: Development of an aerosol mass spectrometer for size and composition analysis of submicron particles, Aerosol Sci. Technol., 33, 49–70, 2000. (10.1080/027868200410840)
  24. Jenkin, M. E., Saunders, S. M., Wagner, V., and Pilling, M. J.: Protocol for the development of the Master Chemical Mechanism, MCM v3 (Part B): tropospheric degradation of aromatic volatile organic compounds, Atmos. Chem. Phys., 3, 181–193, 2003. (10.5194/acp-3-181-2003)
  25. Jimenez, J.-L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X. F., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne Aerosol Mass Spectrometer, 108(D7), 8425, https://doi.org/10.1029/2001JD001213, 2003. (10.1029/2001JD001213)
  26. Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S. H., Fisseha, R., Weingartner, E., Frankevich, V., Zenobi, R., and Baltensperger, U.: Identification of polymers as major components of atmospheric organic aerosols, Science, 303, 1659–1662, 2004. (10.1126/science.1092185)
  27. 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. (10.5194/acp-5-1053-2005)
  28. Katrib, Y., Martin, S. T., Hung, H. M., Rudich, Y., Zhang, H. Z., Slowik, J. G., Davidovits, P., Jayne, J. T., and Worsnop, D. R.: Products and mechanisms of ozone reactions with oleic acid for aerosol particles having core-shell morphologies, J. Phys. Chem., A 108, 6686–6695, 2004. (10.1021/jp049759d)
  29. Kim, E., Hopke, P. K., and Edgerton, E. S.: Source identification of Atlanta aerosol by positive matrix factorization, J Air Waste Manage. Assoc., 53, 731–739, 2003. (10.1080/10473289.2003.10466209)
  30. Kim, E. and Hopke, P. K.: Identification of fine particle sources in mid-Atlantic US area, Water Air Soil Pollut., 168, 391–421, 2005. (10.1007/s11270-005-1894-1)
  31. Kirchstetter, T., Harley, R., Kreisberg, N., Stolzenburg, M., and Hering, S.: On-road measurement of fine particle and nitrogen oxide emissions from light- and heavy-duty motor vehicles, Atmos. Environ., 33(18), 2955–2968, 1999. (10.1016/S1352-2310(99)00089-8)
  32. Lee, E., Chun, C. K., and Paatero, P.: Application of Positive Matrix Factorization in Source Apportionment of Particulate Pollutants, Atmos. Environ., 33, 3201–3212, 1999. (10.1016/S1352-2310(99)00113-2)
  33. Li, Z., Hopke, P. K., Husain, L., Qureshi, S., Dutkiewicz, V. A., Schwab, J. J., Drewnick, F., and Demerjian, K. L.: Sources of fine particle composition in New York city, edited by: Li, Z., Hopke, P. K., and Husain, L., Atmos. Environ., 38, 6521–6529, 2004. (10.1016/j.atmosenv.2004.08.040)
  34. Liu, W., Hopke, P. K., and VanCuren, R. A.: Origins of fine aerosol mass in the western United States using positive matrix factorization, J. Geophys. Res.-Atmos., 108(D23), 4716, https://doi.org/10.1029/2003JD003678, 2003. (10.1029/2003JD003678)
  35. Lohmann, U. and Feichter, J.: Global indirect aerosol effects: a review, Atmos. Chem. Phys., 5, 715–737, 2005. (10.5194/acp-5-715-2005)
  36. Nel, A.: Air pollution-related illness: effects of particles, Science, 308, 804–806, 2005. (10.1126/science.1108752)
  37. NIST: National Institute of Standards and Technology, NIST Chemistry WebBook, available at: http://webbook.nist.gov/chemistry, July 2006.
  38. Paatero, P.: Least squares formulation of robust non-negative factor analysis, Chemom. Intell. Lab. Syst., 37, 23–35, 1997. (10.1016/S0169-7439(96)00044-5)
  39. Paatero, P.: User's guide for positive matrix factorization programs PMF2.EXE and PMF3.EXE, University of Helsinki, Finland, 2000.
  40. Paatero, P: User's guide for positive matrix factorization programs PMF2 and PMF3, part 1: tutorial, University of Helsinki, Finland, 2007.
  41. 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. (10.1002/env.3170050203)
  42. Pekney, N. J., Davidson, C. I., Robinson, A., Zhou, L., Hopke, P., Eatough, D., and Rogge, W. F.: Major source categories for PM2.5 in Pittsburgh using PMF and UNMIX, Aerosol Sci. Technol., 40, 910–924, 2006. (10.1080/02786820500380271)
  43. Quinn, P. K., Bates, T. S., Coffman, D., Onasch, T. B., Worsnop, D., 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, https://doi.org/10.1029/2006JD007582, 2006. (10.1029/2006JD007582)
  44. Ramadan, Z., Song, X. H., and Hopke, P. K.: Identification of sources of Phoenix aerosol by positive matrix factorization, J. Air Waste Manage. Assoc., 50, 1308–1320, 2000. (10.1080/10473289.2000.10464173)
  45. Schauer, J. J., Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simoneit, B. R. T.: Source apportionment of airborne particulate matter using organic compounds as tracers, Atmos. Environ., 30, 3837–3855, 1996. (10.1016/1352-2310(96)00085-4)
  46. Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 1. C1 through C29 organic compounds from meat charbroiling, Environ. Sci. Technol., 33, 1566–1577, 1999. (10.1021/es980076j)
  47. Schneider, J., Weimer, S., Drewnick, F., Borrmann, S., Helas, G., Gwaze, P., Schmid, O., Andreae, M. O., and Kirchner, U.: Mass spectrometric analysis and aerodynamic properties of various types of combustion-related aerosol particles, Int. J. Mass. Spec., 258, 37–49, 2006. (10.1016/j.ijms.2006.07.008)
  48. Simoneit, B. R. T., Rogge, W. F., Mazurek, M. A., Standley, L. J., Hildemann, L. M., and Cass, G. R.: Lignin pyrolysis products, lignans, and resin acids as specific tracers from biomass combustion, Environ. Sci. Technol., 27, 2533–2540, 1993. (10.1021/es00048a034)
  49. Song, X. H., Polissar, A. V., and Hopke, P. K.: Sources of fine particle composition in the northeastern US, Atmos. Environ., 35, 5277–5286, 2001. (10.1016/S1352-2310(01)00338-7)
  50. Steinbacher, M., Zellweger, C., and Schwarzenbach, B.: Nitrogen oxides measurements at rural sites in Switzerland: bias of conventional measurement techniques, J. Geophys. Res., accepted, 2007. (10.1029/2006JD007971)
  51. Szidat, S., Jenk, T. M., Synal, H.-A., Kalberer, M., Wacker, L., Hajdas, I., Kasper-Giebl, A., and Baltensperger, U.: Contributions of fossil fuel, biomass-burning, and biogenic emissions to carbonaceous aerosols in Zurich as traced by 14C, J. Geophys. Res., 111, D07206, https://doi.org/10.1029/2005JD006590, 2006. (10.1029/2005JD006590)
  52. Takegawa, N., Miyakawa, T., Kondo, Y., Jimenez, J. L., Zhang, Q., Worsnop, D. R., and Fukuda, M.: Seasonal and diurnal variations of submicron organic aerosol in Tokyo observed using the Aerodyne aerosol mass spectrometer, J. Geophys. Res., 111, D11206, https://doi.org/10.1029/2005JD006515, 2006. (10.1029/2005JD006515)
  53. Turpin, B. J. and Huntzicker, J. J.: Identification of secondary organic aerosol episodes and quantification of primary and secondary organic aerosol concentrations during SCAQS, Atmos. Environ., 29, 3527–3544, 1995. (10.1016/1352-2310(94)00276-Q)
  54. Volkamer, R., Jimenez, J. L., San Martini, F., Dzepina, K., Zhang, Q., Salcedo, D., Molina, L. T., Worsnop, D. R., and Molina, M. J.: Secondary organic aerosol formation from anthropogenic air pollution: rapid and higher than expected, Geophys. Res. Lett., 33, L17811, https://doi.org/10.1029/2006GL026899, 2006. (10.1029/2006GL026899)
  55. Yu, S., Dennis, R. L., Bhave, P. V., and Eder, B. K.: Primary and secondary organic aerosols over the United States: estimates on the basis of observed organic carbon (OC) and elemental carbon (EC), and air quality modeled primary OC/EC ratios, Atmos. Environ., 38(31), 5257–5268, 2004. (10.1016/j.atmosenv.2004.02.064)
  56. Yuan, Z. B., Lau, A. K. H., Zhang, H. Y., Yu, J. Z., Louie, P. K. K., and Fung, J. C. H.: Identification and spatiotemporal variations of dominant PM10 sources over Hong Kong, Atmos. Environ., 40, 1803–1815, 2006. (10.1016/j.atmosenv.2005.11.030)
  57. 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, 2005a. (10.1021/es048568l)
  58. Zhang, Q., Worsnop, D. R., Canagaratna, M. R., and Jimenez, J. L.: Hydrocarbon-like and oxygenated organic aerosols in Pittsburgh: insights into sources and processes of organic aerosols, Atmos. Chem. Phys., 5, 3289–3311, 2005b. (10.5194/acp-5-3289-2005)
  59. Zhao, W. X. and Hopke, P. K.: Source identification for fine aerosols in Mammoth Cave National Park, Atmos. Res., 80, 309–322, 2006. (10.1016/j.atmosres.2005.10.002)
Dates
Type When
Created 15 years, 4 months ago (April 29, 2010, 9:52 a.m.)
Deposited 6 months, 2 weeks ago (Feb. 16, 2025, 2:32 a.m.)
Indexed 1 week, 6 days ago (Aug. 19, 2025, 6:18 a.m.)
Issued 18 years, 5 months ago (March 20, 2007)
Published 18 years, 5 months ago (March 20, 2007)
Published Online 18 years, 5 months ago (March 20, 2007)
Funders 0

None

@article{Lanz_2007, title={Source apportionment of submicron organic aerosols at an urban site by factor analytical modelling of aerosol mass spectra}, volume={7}, ISSN={1680-7324}, url={http://dx.doi.org/10.5194/acp-7-1503-2007}, DOI={10.5194/acp-7-1503-2007}, number={6}, journal={Atmospheric Chemistry and Physics}, publisher={Copernicus GmbH}, author={Lanz, V. A. and Alfarra, M. R. and Baltensperger, U. and Buchmann, B. and Hueglin, C. and Prévôt, A. S. H.}, year={2007}, month=mar, pages={1503–1522} }