References

ACPD

Atmospheric Chemistry and Physics Discussions

ACPD

1680-7375

Copernicus GmbH

Göttingen, Germany

10.5194/acpd-11-5043-2011

Urban organic aerosols measured by single particle mass spectrometry in the megacity of London

Dall'Osto

¹ ² Harrison

R. M.

National Centre for Atmospheric Science, Division of Environmental Health & Risk Management, School of Geography, Earth & Environmental Sciences University of Birmingham Edgbaston, Birmingham B15 2TT, UK

now at: Institute of Environmental Assessment and Water Research (IDǼA) Consejo Superior de Investigaciones Científicas (CSIC) C/LLuis Solé i Sabarís S/N 08028 Barcelona, Spain

10 02 2011

11 2 5043 5078

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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During the month of October 2006, as part of the REPARTEE-I experiment (Regent's Park and Tower Environmental Experiment) an Aerosol Time-Of-Flight Mass Spectrometer (ATOFMS) was deployed at an urban background location in the city of London, UK. Fifteen particle types were classified, some of which were accompanied by Aerosol Mass Spectrometer (AMS) quantitative aerosol mass loading measurements (Dall'Osto et al., 2009a, b). In this manuscript the origins and properties of four particle types associated with locally generated aerosols, independent of the air mass type advected into London, are examined. One particle type, originating from lubricating oil (referred to as Ca-EC), was associated with morning rush hour traffic emissions. A second particle type, composed of both inorganic and organic species (called Na-EC-OC), was found enhanced in particle number concentration during evening time periods, and is likely to originate from a source operating at this time of day, or more probably from condensation of semi-volatile species, and contains both primary and secondary components. A third class, internally mixed with organic carbon and sulphate (called OC), was found to spike both in the morning and evenings. The fourth class (SOA-PAH) exhibited maximum frequency during the warmest part of the day, and a number of factors point towards secondary production from traffic-related volatile aromatic compounds. Single particle mass spectra of this particle type showed an oxidized polycyclic aromatic compound signature. Finally, a comparison of ATOFMS particle class data is made with factors obtained by Positive Matrix Factorization from AMS data.. Both the Ca-EC and OC particle types correlate with the AMS HOA primary organic fraction (R2 = 0.65 and 0.50 respectively), and Na-EC-OC, but not SOA-PAH, which correlates weakly with the AMS OOA secondary organic aerosol factor (R2 = 0.35). A detailed analysis was conducted to identify ATOFMS particle type(s) representative of the AMS COA cooking aerosol factor, but no convincing associations were found.

References 1

Allan, J. D., Williams, P. I., Morgan, W. T., Martin, C. L., Flynn, M. J., Lee, J., Nemitz, E., Phillips, G. J., Gallagher, M. W., and Coe, H.: Contributions from transport, solid fuel burning and cooking to primary organic aerosols in two UK cities, Atmos. Chem. Phys., 10, 647–668, http://dx.doi.org/10.5194/acp-10-647-2010doi:10.5194/acp-10-647-2010, 2010. %

%Allan, J. D., Williams, P. I., Morgan, W. T., Martin, C. L., Flynn, M. J., %Lee, J., Nemitz, E., Phillips, G. J., Gallagher, M. W., and Coe, H.: %Contributions from transport, solid fuel burning and cooking to primary %organic aerosols in UK cities: Supplementary material – Selection of %solution sets. Atmos. Chem. Phys., 10, 647-668, Supplement; 2010b.

Bunce, N. J., Liu, L., Zhu, J., and Lane, D. A.: Reaction of naphthalene and its derivatives with hydroxyl radicals in the gas phase, Environ. Sci. Technol., 31, 2252–2259, 1997.

Canagaratna, M. R., Jayne, J. T., Jimenez, J. L., Allan, J. D., Alfarra, M. R., Zhang, Q., Onasc, T. B., Drewnick, F., Coe, H., Middlebrook, A., 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 Spectrom. Rev., 26, 185–222, 2007.

Chan, A. W. H., Kautzman, K. E., Chhabra, P. S., Surratt, J. D., Chan, M. N., Crounse, J. D., Kürten, A., Wennberg, P. O., Flagan, R. C., and Seinfeld, J. H.: Secondary organic aerosol formation from photooxidation of naphthalene and alkylnaphthalenes: implications for oxidation of intermediate volatility organic compounds (IVOCs), Atmos. Chem. Phys., 9, 3049–3060, http://dx.doi.org/10.5194/acp-9-3049-2009doi:10.5194/acp-9-3049-2009, 2009.

Cuyckens, F. and Claeys, M.: Mass spectrometry in the structural analysis of flavonoids, J. Mass Spectrom., 39, 1–15, 2004.

Dall'Osto, M. and Harrison R. M.: Chemical Characterisation of single airborne particles in Athens (Greece) by ATOFMS, Atmos. Environ., 40, 7614–7631, 2006.

Dall'Osto, M., Harrison, R. M., Beddows, D. C. S., Freney, E. J., Heal, M. R., and Donovan, R. J.: Single-particle detection efficiencies of aerosol time-of-flight mass spectrometry during the North Atlantic marine boundary layer experiment, Environ. Sci.Technol., 40(16), 5029–5035, 2006.

Dall'Osto, M., Harrison, R. M., Coe, H., Williams, P. I., and Allan, J. D.: Real time chemical characterization of local and regional nitrate aerosols, Atmos. Chem. Phys., 9, 3709–3720, http://dx.doi.org/10.5194/acp-9-3709-2009doi:10.5194/acp-9-3709-2009, 2009a.

Dall'Osto, M., Harrison, R. M., Coe, H., and Williams, P.: Real-time secondary aerosol formation during a fog event in London, Atmos. Chem. Phys., 9, 2459–2469, http://dx.doi.org/10.5194/acp-9-2459-2009doi:10.5194/acp-9-2459-2009, 2009b.

Donahue, N. M., Robinson, A. L., and Pandis, S. N.: Atmospheric organic particulate matter: From smoke to secondary organic aerosol, Atmos. Environ., 43(1), 94–106, 2009.

Drewnick, F., Hings, S. S., DeCarlo, P., 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.

Drewnick, F., Dall'Osto, M., and Harrison, R.: Characterization of aerosol particles from grass mowing by joint deployment of ToF-AMS and ATOFMS instruments, Atmos. Environ., 42(13), 3006–3017, 2008.

Gard, E., Mayer, J. E., Morrical, B. D., Dienes, T., Fergenson, D. P., and Prather K. A.: Real-time analysis of individual atmospheric aerosol particles: Design and performance of a portable ATOFMS, Anal. Chem., 69, 4083–4091, 1997.

Goldstein, A. H. and Galbally, I. E.: Known and unexplored organic constituents in the earth's atmosphere, Environ. Sci.Technol., 41, 1514–1521, 2007.

Gross, D. S., Galli, M. E., Silva, P. J., Wood, S. H., Liu, D. Y., and Prather, K. A.: Single particle characterization of automobile and diesel truck emissions in the Caldecott Tunnel, Aerosol Sci. Technol., 32, 152–163, 2000.

Kalberer, M., Paulsen, D., Sax, M., Steinbacher, M., Dommen, J., Prevot, A. S., 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.

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, http://dx.doi.org/10.5194/acp-5-1053-2005doi:10.5194/acp-5-1053-2005, 2005.

Kroll, J. H. and Seinfeld, J. H.: Chemistry of secondary organic aerosol: Formation and evolution of low-volatility organics in the atmosphere, Atmos. Environ., 42, 3593–3624, 2008.

Langford, B., Nemitz, E., House, E., Phillips, G. J., Famulari, D., Davison, B., Hopkins, J. R., Lewis, A. C., and Hewitt, C. N.: Fluxes and concentrations of volatile organic compounds above central London, UK, Atmos. Chem. Phys., 10, 627–645, http://dx.doi.org/10.5194/acp-10-627-2010doi:10.5194/acp-10-627-2010, 2010.

Maul, R., Schebb, N. H., and Kulling, S. E.: Application of LC and GC hyphenated with mass spectrometry as tool for characterization of unknown derivatives of isoflavonoids, Anal. Bioanal. Chem., 391, 239–250, 2008.

McLafferty, F. W.: Interpretation of Mass Spectra, third ed., 303~pp., 1983.

Mihele, C. M., Wiebe, H. A., and Lane, D. A.: Particle formation and gas/particle partition measurements of the products of the naphthalene-OH radical reaction in a smog chamber, Polycycl. Aromat. Comp., 22, 729–736, 2002.

Murphy, D. M.: The design of single particle laser mass spectrometers, Mass Spectrom. Rev., 26, 150–165, 2007.

Ning, Z., Geller, M. D., Moore, K. F., Sheesley, R., Schauer, J. J., and Sioutas, C.: Daily variation in chemical characteristics of urban ultrafine aerosols and inference of their sources, Environ. Sci.Technol., 41, 6000–6006, 2007.

Pandis, S. N., Wexler, A. S., and Seinfeld, J. H.: Secondary organic aerosol formation and transport.2. Predicting the ambient secondary organic aerosol-size distribution, Atmos. Environ., Part A-General Topics, 27, 2403–2416, 1993.

Petzold, A. and Schonlinner, M.: Multi-angle absorption photometry - a new method for the measurement of aerosol light absorption and atmospheric black carbon, J. Aerosol Sci., 35, 421–441, 2004.

Qin, X. Y., Bhave, P. V., and Prather, K. A.: Comparison of two methods for obtaining quantitative mass concentrations from aerosol time-of-flight mass spectrometry measurements, Anal. Chem., 78(17), 6169–6178, 2006.

Reinard, M. S. and Johnston, M. V.: Ion formation mechanism in laser desorption ionization of individual nanoparticles, J. Am. Soc. Mass Spectrom., 19, 389–399, 2008.

Robinson, A. L., Subramanian, R., Donahue, N. M., Bernardo-Bricker, A., and Rogge, W. F.: Source apportionment of molecular markers and organic aerosol, 3. Food cooking emissions, Environ. Sci. Technol., 40, 7820–7827, http://dx.doi.org/10.1021/Es060781pdoi:10.1021/Es060781p, 2006.

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 aerosols: Semivolatile emissions and photochemical aging, Science, 315, 1259–1262, 2007.

Rogge, W. F., Hildemann, L. M., Mazurek, M. A., Cass, G. R., and Simoneit, B. R. T.: Sources of fine organic aerosol.2. Noncatalyst and catalyst-equipped automobiles and heavy-duty diesel trucks, Environ. Sci.Technol., 27, 636–651, 1993.

Sasaki, J., Aschmann, S. M., Kwok, E. S. C., Atkinson, R., and Arey, J.: Products of the gas-phase OH and NO3 radical-initiated reactions of naphthalene, Environ Sci Technol., 31, 3173–3179, 1997.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 2. C- 1 through C-30 organic compounds from medium duty diesel trucks, Environ. Sci. Technol., 33, 1578–1587, 1999.

Schauer, J. J., Kleeman, M. J., Cass, G. R., and Simoneit, B. R. T.: Measurement of emissions from air pollution sources. 3. C-1-C- 29 organic compounds from fireplace combustion of wood, Environ. Sci. Technol., 35, 1716–1728, 2001.

Silva, P. J. and Prather K. A.: Interpretation of mass spectra from organic compounds in aerosol time-of-flight mass spectrometry, Anal. Chem., 72, 3553–3562, 2000.

Silva, P. J., Liu, D.-Y., Noble, C. A., and Prather, K. A.: Size and chemical characterization of individual particles resulting from biomass burning of local Southern California species, Environ. Sci. Technol., 33(18), 3068–3076, 1999.

Song, X. H., Hopke, P. K., Fergenson, D. P., and Prather, K. A.: Classification of single particles analyzed by ATOFMS using an artificial neural network, ART-2A, Anal. Chem., 71(4), 860–865, 1999.

Spencer, M. T., Shields, L. G., Sodeman, D. A., Toner, S. M., and Prather, K. A.: Comparison of oil and fuel particle chemical signatures with particle emissions from heavy and light duty vehicles, Atmos. Environ., 40, 5224–5235, 2006.

Sullivan, R. C. and Prather, K. A. Recent advances in our understanding of atmospheric chemistry and climate made possible by on-line aerosol analysis instrumentation, Anal. Chem., 77(12), 3861–3885, 2005.

Toner, S.: Source characterization and source apportionment of anthropogenic aerosols, PhD Thesis, UCSD, California, USA, 2008.

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.

Verma, V., Ning, Z., Cho, A. K., Schauer, J. J., Shafer, M. M., and Sioutas C.: Redox activity of urban quasi-ultrafine particles from primary and secondary sources, Atmos. Environ., 43, 6360–6368, 2009.

Walgraeve, C., Demeestere, K., Dewulf, J., Zimmermann, R., and Van Langenhove, H.: Oxygenated polycyclic aromatic hydrocarbons in atmospheric particulate matter: Molecular characterization and occurrence, Atmos. Environ., 44, 1831–1846, 2010.

Wang, L., Atkinson, R., and Arey, J.: Dicarbonyl products of the OH radical-initiated reactions of naphthalene and the C-1- and C-2-alkylnaphthalenes, Environ. Sci. Technol., 41, 2803–2810, 2007.

Webb, P. J., Hamilton, J. F., Lewis, A. C., and Wirtz, K.: Formation of oxygenated-polycyclic aromatic compounds in aerosol from the photo-oxidation of o-tolualdehyde, Polycyclic Aromatic Compounds, 26, 237–252, 2006.

Whiteaker, J. R. and Prather, K. A.: Hydroxymethanesulfonate as a tracer for fog processing of individual aerosol particles, Atmos. Environ., 37, 1033–1043, 2003.