ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-9-2459-2009 Real-time secondary aerosol formation during a fog event in London Dall'Osto M. 1 3 Harrison R. M. 1 Coe H. 2 Williams P. 2 National Centre for Atmospheric Science Division of Environmental Health and Risk Management School of Geography, Earth and Environmental Sciences University of Birmingham, Edgbaston, Birmingham B15 2TT, UK National Centre for Atmospheric Science School of Earth, Atmospheric and Environmental Sciences The University of Manchester, Simon Building Oxford Road, Manchester M13 9PL, UK now at: Centre for Climate and Air Pollution Studies, Environmental Change Institute, National University of Ireland, Galway, Ireland 03 04 2009 9 7 2459 2469 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/9/2459/2009/acp-9-2459-2009.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/2459/2009/acp-9-2459-2009.pdf

A fog event was monitored with state-of-the art real-time aerosol mass spectrometers in an urban background location in London (England) during the REPARTEE-I experiment. Specific particle types rich in hydroxymethanesulphonate (HMS) were found only during the fog event. Formation of inorganic and organic secondary aerosol was observed as soon as fog was detected and two different mechanisms are suggested to be responsible for the production of two different types of aerosol. Nitrate aerosol is produced in the liquid phase within the droplet. Contrary to previous studies, the formation of HULIS was observed on interstitial particles rather than evaporated fog droplets, suggesting heterogeneous formation mechanisms depending on parameters other than the water content and not fully understood. Not only are secondary aerosol constituents produced during the fog event, but the primary aerosol is observed to be processed by the fog event, dramatically changing its chemical properties.

 References Abdalmogith, S. S. and Harrison, R. M.: An analysis of spatial and temporal properties of daily sulphate, nitrate and chloride concentrations at UK Urban and rural sites, J. Environ. Monit., 8, 691–699, 2006. Alfarra, M. R., Paulsen, D., Gysel, M., Garforth, A. A., Dommen, J., Prevot, 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, 2006. Allan, J. D., Jimenez, J. L., Coe, H., Bower, K. N., Williams, P. I., and Worsnop, D. R.: Quantitative sampling using an aerodyne aerosol mass spectrometer. Part 1: Techniques of data interpretation and error analysis, J. Geophys, Res. Atmos., 108(D3), 4090, doi:10.1029/2002JD002358, 2003. 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: extraction of chemically resolved mass spectra from aerodyne aerosol mass spectrometer data, J. Aerosol Sci,, 35, 909–922, 2004. Altieri, K. E., Carlton, A. G., Lim, H. J., Turpin, B. J., and Seitzinger, S. P.: Evidence for oligomer formation in clouds: Reactions of isoprene oxidation products, Environ. Sci. Technol., 40, 4956–4960, 2006. Andreae, M. O. and Gelencser, A.: Black carbon or brown carbon? The nature of light-absorbing carbonaceous aerosols, Atmos. Chem. Phys., 6, 3131–3148, 2006. Blando, J. D. and Turpin, B. J.: Secondary organic aerosol formation in cloud and fog droplets: a literature evaluation of plausibility, Atmos. Environ., 34, 1623-1632, 2000. 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., 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(2), 185–222, 2007. Cappiello, A., De Simon, E, Fiorucci, C., Mangani, F., Palma, P., Trufelli, H., Decesari, S., Facchini, M. C., and Fuzzi, S.: Molecular characterization of the water-soluble organic compounds in fogwater by ESIMS/MS, Environ. Sci. Technol., 37, 1229–1240, 2003. Carlton, A. G., Turpin, B. J., Altieri, K. E., Seitzinger, S., Reff, A., Lim, H. J., and Ervens, B.: Atmospheric oxalic acid and SOA production from glyoxal: Results of aqueous photooxidation experiments, Atmos. Environ., 41, 7588–7602, 2007. Carlton, A. G., Turpin, B. J., Lim, H. J., Altieri, K. E., and Seitzinger, S.: Link between isoprene and secondary organic aerosol (SOA): Pyruvic acid oxidation yields low volatility organic acids in clouds, Geophys. Res. Lett., 33, L06822, doi:10.1029/2005GL025374, 2006. Dall'Osto, M. and Harrison, R. M.: Chemical characterisation of single airborne particles in Athens (Greece) by ATOFMS, Atmos. Environ., 40, 7614–7631, 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 Drewnick, F., Hings, S. S., DeCarlo, P., Jayne, J. T., Gonin, M., Fuhrer, K., Weimer, S., Jimenez, J. L., Demerjian, K. L., Borrmann, S., 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. Ervens, B., Feingold, G., Frost, G. J., and Kreidenweis, S. M.: A modeling study of aqueous production of dicarboxylic acids: 1. Chemical pathways and speciated organic mass production, J. Geophys. Res.-Atmospheres, 109(D15), 2004. Facchini, M. C., Fuzzi, S., Zappoli, S., Andracchio, A., Gelencser, A., Kiss, G., Krivacsy, Z., Meszaros, E., Hansson, H. C., Alsberg, T., and Zebuhr, Y.: Partitioning of the organic aerosol component between fog droplets and interstitial air, J. Geophys. Res.-Atmospheres, 104(D21), 26821–26832, 1999. Feng, J. S. and Moller, D.: Characterization of water-soluble macromolecular substances in cloud water, J. Atmos. Chem., 48, 217–233, 2004. Fuzzi, S., Facchini, M. C., Decesari, S., Matta, E., and Mircea, M.: Soluble organic compounds in fog and cloud droplets: what have we learned over the past few years?, Atmos. Res., 64, 89–98, 2002. 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. Gelencser, A. and Varga, Z.: Evaluation of the atmospheric significance of multiphase reactions in atmospheric secondary organic aerosol formation, Atmos. Chem. Phys., 5, 2823–2831, 2005. Graber, E. R. and Rudich, Y.: Atmospheric HULIS: How humic-like are they? A comprehensive and critical review, Atmos. Chem. Phys., 6, 729–753, 2006. Gross, D. S., Galli, M. E., Kalberer, M., Prevot, A. S. H., Dommen, J., Alfarra, M. R., Duplissy, J., Gaeggeler, K., Gascho, A., Metzger, A., and Baltensperger, U.: Real-time measurement of oligomeric species in secondary organic aerosol with the aerosol time-of-flight mass spectrometer, Anal. Chem., 78, 2130–2137, 2006. 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. Henningan, C. J., Sullivan, A. P., Fountoukis, C. I., Nenes, A., Hecobian, A., Vargas, O., Case Hanks, A. T., Huey, L. G., Lefer, B. L., Russell, A. G. and Weber, R. J.: On the volatility and production mechanisms of newly formed nitrate and water soluble organic aerosol in Mexico City, Atmos. Chem. Phys. Discuss., 8, 4611-4829, 2008 . Herckes, P., Chang, H., Lee, T., and Collett, J. L.: Air pollution processing by radiation fogs, Water Air and Soil Pollut., 181(1–4), 65–75, 2007a. Herckes, P., Leenheer, J. A. and Collett, J. L.: Comprehensive characterization of atmospheric organic matter in Fresno, California fog water, Environ. Sci. Technol., 41, 393–399, 2007b. Herckes, P., Lee, T., Trenary, L., Kang, G. G., Chang, H., and Collett, J. L.: Organic matter in Central California radiation fogs, Environ. Sci. Technol., 36, 4777–4782, 2002. Herrmann, H., Ervens, B., Jacobi, H. W., Wolke, R.,. Nowacki, P, and Zellner, R.: CAPRAM2.3: A chemical aqueous phase radical mechanism for tropospheric chemistry, J. Atmos. Chem., 36(3), 231–284, 2000. Herrmann, H.: Kinetics of aqueous phase reactions relevant for atmospheric chemistry, Chem. Rev., 103(12), 4691–4716, 2003. Jimenez, J. L., Jayne, J. T., Shi, Q., Kolb, C. E., Worsnop, D. R., Yourshaw, I., Seinfeld, J. H., Flagan, R. C., Zhang, X., Smith, K. A., Morris, J. W., and Davidovits, P.: Ambient aerosol sampling using the Aerodyne aerosol mass spectrometer, J. Geophys. Res., 108(D7), 8425, 2003. Kiss, G., Tombacz, E., Varga, B., Alsberg, T., and Persson, L.: Estimation of the average molecular weight of humic-like substances isolated from fine atmospheric aerosol, Atmos. Environ., 37, 3783–3794, 2003. Kiss, G., Varga, B., Gelencser, A., Krivacsy, Z., Molnar, A., Alsberg, T., Persson, L., Hansson, H. C., and Facchini, M. C.: Characterisation of polar organic compounds in fog water, Atmos. Environ., 35, 2193–2200, 2001. Kok, G. L., Gitlin, S. N., and Lazrus, A. L.: Kinetics Of The Formation And Decomposition Of Hydroxymethanesulfonate, J., Geophys. Res.-Atmos., 91(D2), 2801–2804, 1986. Krivacsy, Z., Gelencser, A., Kiss, G., Meszaros, E., Molnar, A., Hoffer, A., Meszaros, T., Sarvari, Z. Temesi, D., Varga, B., Baltensperger, U., Nyeki, S., and Weingartner E.: Study on the chemical character of water soluble organic compounds in fine atmospheric aerosol at the Jungfraujoch, J. Atmos. Chem., 39, 235–259, 2001. Lagrange, J., Wenger, G., and Lagrange, P.: Kinetic study of HMSA formation and decomposition: Tropospheric relevance, J. Chim. Phys. Phys.-Chim. Biol., 96(4), 610–633, 1999. Laj, P., Fuzzi, S., Facchini, M. C., Orsi, G., Berner, A., Kruisz, C., Wobrock, W., Hallberg, A., Bower, K. N., Gallagher, M. W., Beswick, K. M., Colvile, R. N., Choularton, T. W., Nason, P., and Jones, B.: Experimental evidence for in-cloud production of aerosol sulphate, Atmos. Environ., 31, 2503–2514, 1997. Lillis, D., Cruz, C. N., Collett, J., Richards, L. W., and Pandis, S. N.: Production and removal of aerosol in a polluted fog layer: model evaluation and fog effect on PM, Atmos. Environ., 33, 4797–4816, 1999. Lim, H. J., Carlton, A. G., and Turpin, B. J.: Isoprene forms secondary organic aerosol through cloud processing: Model simulations, Environ. Sci. Technol., 39, 4441–4446, 2005. Loeffler, K. W., Koehler, C. A., Paul, N. M., and De Haan, D. O.: Oligomer formation in evaporating aqueous glyoxal and methyl glyoxal solutions, Environ. Sci. Technol., 40, 6318–6323, 2006. Moffet, R. C., de Foy, B., Molina, L. T., Molina, M. J., and Prather, K. A.: Measurement of ambient aerosols in northern Mexico City by single particle mass spectrometry, Atmos. Chem. Phys., 8(16), 4499–4516, 2008. 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 . Noble, C. A. and Prather, K. A.: Real-time single particle mass spectrometry: A historical review of a quarter century of the chemical analysis of aerosols, Mass Spectrom. Rev., 19, 248–274, 2000. Prenni, A. J., Petters, M. D., Kreidenweis, S. M., DeMott, P. J., and Ziemann, P. J.: Cloud droplet activation of secondary organic aerosol, J. Geophys. Res.-Atmos., 112(D10), 2007. % % %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. Qin, X. Y. and Prather, K. A.: Impact of biomass emissions on particle chemistry during the California Regional Particulate Air Quality Study, Intl. J. Mass Spectrom., 258, 142–150, 2006. Rebotier, T. P. and Prather, K. A.: Aerosol time-of-flight mass spectrometry data analysis: A benchmark of clustering algorithms, Anal. Chim. Acta, 585, 38–54, 2007. Reinard, M. S., Adou, K., Martini, J. M., and Johnston, M. V.: Source characterization and identification by real-time single particle mass spectrometry, Atmos. Environ., 41, 9397–9409, 2007. Shilling, J. E., King, S. M., Mochida, M., and Martin, S. T.: Mass spectral evidence that small changes in composition caused by oxidative aging processes alter aerosol CCN properties, J. Phys. Chem. A, 111, 3358–3368, 2007. 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. 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, 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. Toner, S. M., Shields, L. G., Sodeman, D. A., and Prather, K. A.: Using mass spectral source signatures to apportion exhaust particles from gasoline and diesel powered vehicles in a freeway study using UF-ATOFMS, Atmos. Environ., 42, 568, 2008. Warneck, P.: In-cloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere, Atmos. Environ., 37, 2423–2427, 2003. Whiteaker, J. R. and Prather, K. A.: Hydroxymethanesulfonate as a tracer for fog processing of individual aerosol particles, Atmos. Environ., 37, 1033–1043, 2003. Williams, P. I., McFiggans, G., and Gallagher, M. W.: Latitudinal aerosol size distribution variation in the Eastern Atlantic Ocean measured aboard the FS-Polarstern, Atmos. Chem. Phys., 7, 2563–2573, 2007. Yao, X.H., Fang, M., and Chan, C. K.: Size distributions and formation of dicarboxylic acids in atmospheric particles, Atmos. Environ., 36, 2099–2107, 2002. Yao, X. H., Lau, A. P. S., Fang, M., Chan, C. K., and Hu, M.: Size distributions and formation of ionic species in atmospheric particulate pollutants in Beijing, China: 2 – dicarboxylic acids, Atmos. Environ., 37, 3001–3007, 2003. % %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, X., Smith, K. A., Worsnop, D. R., Jimenez, J. L., Jayne, J. T., and Kolb, C. E.: A numerical characterization of particle beam collimation by an aerodynamic lens-nozzle system. Part I: An individual lens or nozzle, Aerosol Sci. Technol., 36, 617–631 2002. Zhang, X., Smith, K. A., Worsnop, D. R., Jimenez, J. L., Jayne, J. T., Kolb, C. E., Morris, J., and Davidovits, P.: Numerical characterization of particle beam collimation: Part II: Integrated aerodynamic lens-nozzle system, Aerosol Sci. Technol., 38, 619–638, 2004. 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.