Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 6 12 2006 10.5194/acp-6-4101-2006 http://www.atmos-chem-phys.net/6/4101/2006/ http://www.atmos-chem-phys.net/6/4101/2006/acp-6-4101-2006.html http://www.atmos-chem-phys.net/6/4101/2006/acp-6-4101-2006.pdf 4101 4115 2006-09-13 Organics in the Northeastern Pacific and their impacts on aerosol hygroscopicity in the subsaturated and supersaturated regimes K. C. Kaku katie@atmos.washington.edu D. A. Hegg D. S. Covert J. L. Santarpia H. Jonsson G. Buzorius D. R. Collins Department of Atmospheric Sciences, Seattle, WA, USA Edgewood Chemical Biological Center, Aberdeen Proving Grounds, MD, USA CIRPAS, Department of Research, NPS, Marina, CA, USA Texas A&M University, Department of Atmospheric Sciences, College Station, TX, USA Aerosol samples were collected by aircraft during the summer of 2004 in the Northeastern Pacific and compared to measurements of aerosol hygroscopicity. Chemical speciation analyses of the samples revealed that a significant portion of the marine aerosols was organic, and on average 8% of the total aerosol mass was insoluble organic material, tentatively attributed to natural marine emissions. Two chemical models were explored in an attempt to achieve closure between the marine aerosol chemical and physical properties through reproduction of the observed aerosol growth, both in the subsaturated and supersaturated regimes. Results suggest that at subsaturated relative humidities, the nonideal behavior of water activity with respect to aerosol chemistry has an important effect on aerosol growth. At supersaturations, the underprediction of critical supersaturations by all models suggests the hypothesis that formation of a complete monolayer by the insoluble organics may inhibit the activation of aerosols to form cloud droplets. Abbatt, J. P D., Broekhuizen, K., and Kumar, P P.: Cloud condensation nucleus activity of internally mixed ammonium sulfate/organic acid aerosol particles, Atmos. Environ., 39, 4767–4778, 2005. Barger, W R. and Garrett, W D.: Surface active organic material in air over the Mediterranean and over the eastern equatorial Pacific, J. Geophys. Res., 81, 3151–3157, 1976. Bates, T S., Quinn, P K., Coffman, D J., and Johnson, J E.: Dominance of organic aerosol in the marine boundary layer over the Gulf of Maine during NEAQS 2002 and their role in aerosol light scattering, J. Geophys. Res., 110, D18202, doi:10.1029/2005/JD005797, 2005. Bigg, E K.: Discrepancy between observation and prediction of concentrations of cloud condensation nuclei, Atmos. Res., 20, 80–86, 1986. Bilde, M. and Svenningsson, B.: CCN activation of slightly soluble organics: the importance of small amounts of inorganic salt and particle phase, Tellus, 56, 128–134, 2004. Chuang, P Y.: Measurement of the timescale of hygroscopic growth for atmospheric aerosols, J. Geophys. Res., 108, AAC 5–1 – AAC 5–13, 2003. Chuang, P Y., Charlson, R J., and Seinfeld, J H.: Kinetic limitations on droplet formation in clouds, Nature, 390, 594–596, 1997. Cini, R. and Loglio, G.: Adsorption and pollutant transport by marine aerosol, Mar. Pollut. Bull., 34, 501–504, 1997. Coale, K., Colbert, D., Kingsley, E., and Zamzow, H.: Monterey Bay National Marine Sanctuary site characterization: Chemical oceanography, web address: http://bonita.mbnms.nos.noaa.gov/sitechar/clim1.html, 1996. Crahan, K., Hegg, D A., and Covert, D S.: An exploration of aqueous oxalic acid production in the coastal marine atmosphere, Atmos. Environ., 38, 3757–3764, 2004a. Crahan, K., Hegg, D A., Covert, D S., Jonsson, H., Reid, J., and Khelif, K.: Speciation of organics aerosols in the tropical mid-Pacific and their relationship to light scattering, J. Atmos. Sci., 61, 2544–2558, 2004b. Duarte, C M. and Cebrian, J.: The fate of marine autotrophic production, Limnol. Oceanogr., 41, 1758–1766, 1996. Eliason, T L., Gilman, J B., and Vaida, V.: Oxidation of organic films relevant to atmospheric aerosols, Atmos. Environ., 38, 1367–1378, 2003. Ellison, G B., Tuck, A F., and Vaida, V.: Atmospheric processing of organic aerosols, J. Geophys. Res., 104, 11 633–11 641, 1999. Ervens, B., George, C., Williams, J E., Buxton, G V., Salmon, G A., Bydder, M., Wilkinson, F., Denter, F., Miranel, P., Wolke, R., and Hermann, J.: CAPRAM2.4 (MODAC mechanism): An extended and condensed tropospheric aqueous phase mechanism and its application, J. Geophys. Res., 108, 4426, doi:10.1029/2002JD002 202, 2003. Facchini, M C., Decesari, S., Mircea, M., Fuzzi, S., and Loglio, G.: Surface tension of atmospheric wet aerosol and cloud/fog droplets in relation to their organic content and chemical composition, Atmos. Environ., 24, 4853–4857, 2000. Gao, S., Hegg, D A., Covert, D S., and Jonsson, H.: Aerosol chemistry, and light-scattering and hygroscopicity budgets during ACE-Asia, J. Geophys. Res., 46, 55–88, 2003. Gassó, S., Hegg, D A., Covert, D S., Collins, D., Noone, K J., Ostron, E., Schmid, B., Russell, P B., Livingston, J M., Durkee, P A., and Jonsson, H.: Influence of humidity on the aerosol scattering coefficient and its effect on the upwelling radiance during ACE-2, Tellus, 52B, 546–567, 2000. Griffin, R J., Dadbub, D., and Seinfeld, J H.: Secondary organic aerosols. 1: Atmospheric chemical mechanism for production of molecular constituents, J. Geophys. Res., 107, 4215, doi:10.1026/2001JD000541, 2002. Haywood, J., Ramaswamy, V., and Soden, B.: Tropospheric aerosol climate forcing in clear sky satellite observation over the oceans, Science, 283, 1299–1303, 1999. Hegg, D A., Livingston, J., Hobbs, P., Novakov, T., and Russell, P.: Chemical apportionment of aerosol column optical depth off the mid-Atlantic coast of the United States, J. Geophys. Res., 102, 25 293–25 303, 1997. Hegg, D A., Covert, D S., Jonsson, H., and Covert, P A.: Determination of the transmission efficiency of an aircraft aerosol inlet, Aerosol Sci. Technol., 39, 966–971, 2005. Houghton, J., Ding, Y., Griggs, D J., Noguer, M., van~der Linden, P J., Dai, X., Maskell, K., and Johnson, C A. (Eds.): IPCC 2001: Climate Change 2001, Cambridge University Press, Cambridge, England, 2001. Kanakidou, M., Seinfeld, J., Pandis, S., Barnes, I., Dentener, F., Facchini, M., Dingenen, R V., Ervens, B., Nenes, A., Nielsen, C., Swietlicki, E., Putaud, J., Balkanski, Y., Fuzzi, S., Horth, J., Moortgat, G., Winterhalter, R., Myhre, F., Tsigaridis, K., Vignati, E., Stephanou, E., and Wilson, J.: Organic aerosol and global climate modeling: a review, Atmos. Chem. Phys., 5, 1053–1123, 2005. Kasten, F.: Visibility forecast in the phase of pre-condensation, Tellus, 21, 631–635, 1969. Kawamura, K. and Sakaguchi, F.: Molecular distribution of water soluble dicarboxylic acids in marine aerosols over the Pacific Ocean including the tropics, J. Geophys. Res., 104, 3501–3509, 1999. Kindle, J.: Near real-time depiction of the California current system, web address: http://www7320.nrlssc.navy.mil/ccsnrt/ArchiveGen_5dMODIS.php?year=2004&month=6&Wday=30&var=seawifs, 2005. Lewis, E R. and Schwartz, S E. (Eds.): Sea Salt Aerosol Production: Mechanisms, methods, measurements, and models, American Geophysical Union, Washington, D.C., 2004. Maria, S F., Russell, L M., Giles, M K., and Myneni, S. C B.: Organic aerosol growth mechanisms and their climate-forcing implications, Nature, 306, 1921–1924, 2004. Ma$ß$ling, A., Weidensohler, A., Busch, B., Neusüß, C., Quinn, P., Bates, T., and Covert, D.: Hygroscopic properties of different aerosol types over the Atlantic and Indian Oceans, Atmos. Chem. Phys., 3, 1377–1397, 2003. Ming, Y. and Russell, L M.: Predicted hygroscopic growth of sea salt aerosols, J. Geophys. Res., 106, 28 259–28 274, 2001. Ming, Y. and Russell, L M.: Thermodynamic Equilibrium of Organic-Electrolyte mixtures in aerosol particles, AICHE Journal, 48, 1331–1348, 2002. Murphy, D M., Anderson, J R., Quinn, P K., McInnes, L M., Brechtel, F J., Kreidenweis, S M., Middlebrook, A M., Posfai, M., Thomson, D S., and Buseck, P R.: Influence of sea-salt on aerosol radiative properties in the Southern Ocean marine boundary layer, Nature, 392, 62–65, 1998. Nuss, W.: Monterey Bay National Marine Sanctuary site characterization: Climate & Meteorology, web address: http://bonita.mbnms.nos.noaa.gov/sitechar/chem.html, 1996. O'Doud, C., Smith, M H., Consterdine, I E., and Lowe, J A.: Marine aerosol, sea-salt and the marine sulfur cycle: a short review, Atmos. Environ., 31, 73–80, 1997. O'Doud, C., Facchini, M., Cavalli, F., Ceburnis, D., Mircea, M., Decesary, S., Fuzzi, S., Yoon, Y., and Putaud, J.: Biogenically driven organic contribution to marine aerosol, Nature, 431, 676–680, 2004. Oppo, C S., Bellandi, S., Innocenti, N D., Stortini, A M., Loglio, G., Schiavuta, E., and Cici, R.: Surfactant components of marine organic matter as agents for biogeochemical fractionation and pollution transport via marine aerosols, Mar. Chem., 63, 235–253, 1999. Pun, B K., Seigeur, S., Grajean, D., and Saxena, P.: Gas-phase formation of water soluble organic compounds in the atmosphere: A retrosynthetic analysis, J. Atmos. Chem., 35, 199–223, 2000. Putaud, J P., Van Dingenen, R., Mangoni, M., Virkkula, A., Raes, F., Maring, H., Prospero, J M., Swietlicki, E., Berg, O H., Hillamo, R., and Makelo, T.: Chemical mass closure and assessment of the origin of the submicron aerosol in the marine boundary layer and the free troposphere at Tenerife during ACE-2, Tellus, 52, 141–198, 2000. Quinn, P K. and Bates, T S.: Regional aerosol properties: Comparisons of boundary layer measurements from ACE-1, ACE-2, Aerosols99, INDOEX, ACE Asia, TARFOX, and NEAQS, J. Geophys. Res., 110, D14202, doi:10.1029/2004JD004755, 2005. Quinn, P K., Coffman, D J., Kapustin, V N., Bates, T S., and Covert, D S.: Aerosol optical properties in the marine boundary layer during the First Aerosol Characterization Experiment (ACE-1) and the underlying chemical and physical aerosol properties, J. Geophys. Res., 103, 16 547–16 563, 1998. Santarpia, J L., Li, R J., and Collins, D R.: Direct measurement of the hydration state of ambient aerosol populations, J. Geophys. Res., 109, D18209, doi:10.1029/2004JD004653, 2004. Seidl, W.: Model for a surface film of fatty acids on rainwater and aerosol particles, Atmos. Environ., 34, 4917–1932, 2000. Shantz, N C., Leaitch, W R., and Caffrey, P F.: Effects of organics of low solubility on the growth rate of cloud droplets, J. Geophys. Res., 108, 4168, doi:10.1029/2002JD002540, 2003. Svenningsson, B., Rissler, J., Swietlicki, E., Mircea, M., Bilde, M., Facchini, M., Decesari, S., Fuzzi, S., Shou, J., M$\o$nster, J., and Rosen$\o$rn, T.: Hygroscopic growth and critical supersaturations for mixed aerosol particles of inorganics and organic compounds of atmospheric relevance, Atmos. Chem. Phys., 6, 1937–1952, 2005. Tervahattu, H., Juhanoja, J., and Kupianinen, K.: Identification of an organic coating on marine aerosol particles by TOF-SIMS, J. Geophys. Res.-Atmos., 107, 4319, 2002. Turpin, B J., Saxena, P., and Andrews, E.: Measuring and simulating particulate organics in the atmosphere: problems and prospects, Atmos. Environ., 34, 2983–3013, 2000. Warnick, P.: In-cloud chemistry opens pathway to the formation of oxalic acid in the marine atmosphere, Atmos. Environ., 37, 2423–2427, 2003. Winkler, P. and Kaminski, U.: Formation and the physiochemical properties of the tropospheric aerosol, Phys. Chem. Chem. Phys., 96, 368–377, 1992.