Atmospheric Chemistry and Physics www.atmos-chem-phys.net 1680-7316 1680-7324 8 14 2008 10.5194/acp-8-3735-2008 http://www.atmos-chem-phys.net/8/3735/2008/ http://www.atmos-chem-phys.net/8/3735/2008/acp-8-3735-2008.html http://www.atmos-chem-phys.net/8/3735/2008/acp-8-3735-2008.pdf 3735 3748 2008-07-15 CCN activation experiments with adipic acid: effect of particle phase and adipic acid coatings on soluble and insoluble particles S. S. Hings W. C. Wrobel E. S. Cross D. R. Worsnop P. Davidovits T. B. Onasch Department of Chemistry, Boston College, Chestnut Hill, MA 02467, USA Aerodyne Research Inc., Billerica, MA 01821, USA Slightly soluble atmospherically relevant organic compounds may influence particle CCN activity and therefore cloud formation. Adipic acid is a frequently employed surrogate for such slightly soluble organic materials. The 11 published experimental studies on the CCN activity of adipic acid particles are not consistent with each other nor do they, in most cases, agree with the Köhler theory. The CCN activity of adipic acid aerosol particles was studied over a significantly wider range of conditions than in any previous single study. The work spans the conditions of the previous studies and also provides alternate methods for producing "wet" (deliquesced solution droplets) and dry adipic acid particles without the need to produce them by atomization of aqueous solutions. The experiments suggest that the scatter in the previously published CCN measurements is most likely due to the difficulty of producing uncontaminated adipic acid particles by atomization of solutions and possibly also due to uncertainties in the calibration of the instruments. The CCN activation of the small (<i>d</i>_<i>m</i><150 nm) initially dry particles is subject to a deliquescence barrier, while for the larger particles the activation follows the Köhler curve. Wet adipic acid particles follow the Köhler curve over the full range of particle diameters studied. In addition, the effect of adipic acid coatings on the CCN activity of both soluble and insoluble particles has also been studied. When a water-soluble core is coated by adipic acid, the CCN-hindering effect of particle phase is eliminated. An adipic acid coating on hydrophobic soot yields a CCN active particle. If the soot particle is relatively small (<i>d</i>_core≤102 nm), the CCN activity of the coated particles approaches the deliquescence line of adipic acid, suggesting that the total size of the particle determines CCN activation and the soot core acts as a scaffold. Bilde, M. and Svenningsson, B.: CCN Activation of Slightly Soluble Organics: The Importance of Small Amounts of Inorganic Salt and Particle Phase, Tellus, 56 B, 128–134, 2004. Broekhuizen, K., Kumar, P. P., and Abbatt, J. P. D.: Partially soluble organics as cloud condensation nuclei: Role of trace soluble and surface active species, Geophys. Res. Lett., 31, L01107, doi:01110.01029/02003GL018203, 2004. Cruz, C. N. and Pandis, S. N.: A Study of the Ability of Pure Secondary Organic Aerosol to act as Cloud Condensation Nuclei, Atmos. Environ., 31, 2205–2214, 1997. Corrigan, C. E. and Novakov, T.: Cloud Condensation Nucleus Activity of Organic Compounds: A Laboratory Study, Atmos. Environ., 33, 2661–2668, 1999. DeCarlo, P. D., Slowik, J. G., Worsnop, D. R., Davidovits, P., and Jimenez, J. L.: Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 1: Theory, Aerosol Sci. Technol., 38, 1185–1205, doi:10.1080/027868290903907, 2004. 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., Worsnop, D. R., and Jimenez, J. L.: Field-Deployable, High-Resolution, Time-of-Flight Aerosol Mass Spectrometer, Anal. Chem., 78 8281–8289, 2006. Dinar, E., Anttila, T., and Rudich, Y.: CCN Activity and Hygroscopic Growth of Organic Aerosols Following Reactive Uptake of Ammonia, Environ. Sci. Technol., 42, 3, 793–799, 2008. 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. DMT: Cloud Condensation Nuclei Counter Operator Manual DOC-0086 Revision A12, Droplet Measurement Technologies Inc., 2004. Dusek, U., Frank, G. P., Hildebrandt, L., Curtius, J., Schneider, J., Walter, S., Chand, D., Drewnick, F., Hings, S., Jung, D., Borrmann, S., and Andreae, M. O.: Size matters more than chemistry for cloud nucleating ability of aerosol particles, Science, 312, 1375–1378, 2006. 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 Carbon Content and Chemical Composition, Atmos. Environ., 34, 4853–4857, 2000. Giebl, H., Berner, A., Reischl, G., Puxbaum, H., Kasper-Giebl, A., and Hitzenberger, R.: CCN Activation of Oxalic and Malonic Acid Test Aerosols with the University of Vienna Cloud Condensation Nuclei Counter, Aerosol Sci., 33, 1623–1634, 2002. Henning, S., Rosenoern, T., D'Anna, B., Gola, A. A., Svenningsson, B., and Bilde, M.: Cloud Droplet Activation and Surface Tension of Mixtures of Slighlty Soluble Organics and Inorganic Salt, Atmos. Chem. Phys., 5, 575–582, 2005. Hori, M., Ohta, S., Murao, N., and Yamagata, S.: Activation Capability of Water Soluble Organic Substances as CCN, Aerosol Sci., 34, 419–448, 2003. Huff Hartz, K. E., Tischuk, J. E., Chang, M. N., Chang, C. K., Donahue, M. N., and Pandis, S. N.: Cloud Condensation Nuclei Activation of Limited Solubility Organic Aerosol, Atmos. Environ., 40, 605–617, 2006. IPCC: Climate Change 2007: The Physical Science Basis, in: Contribution of Working Group I to the Fourth Assessment Report of the Intergovernmental Panel on Climate Change, edited by: Solomon, S., Qin, D., Manning, M., Chen, Z., Marquis, M., Averyt, K. B., Tignor, M., and Miller, H. L., Cambridge University Press, Cambridge, UK and New York, NY, USA, 996 pp., 2007. Kaufman, Y. J. and Koren, I.: Smoke and Pollution Aerosol Effect on Cloud Cover, Science, 313, 655–658, 2006. Kreidenweis, S. M., Petters, M. D., and DeMott, P. J.: Deliquescence-Controlled Activation of Organic Aerosols, Geophys. Res. Lett. , 33, L068801, doi:10.1029/2005GL024863, 2006. Kumar, P. P., Broekhuizen, K., and Abbatt, J. P. D.: Organic Acids as Cloud Condensation Nuclei: Laboratory Studies of Highly Soluble and Insoluble Species, Atmos. Chem. Phys., 3, 509–520, 2003. Laaksonen, A., Korhonen, P., Kulmala, M., and Charlson, R. J.: Modification of the Köhler Equation to Include Soluble Trace Gases and Slightly Soluble Substances, J. Atmos. Sci., 55, 853–862, 1998. Lance, S., Medina, J., Smith, J. N., and Nenes, A.: Mapping the Operation of the DMT Continuous Flow CCN Counter, Aerosol Sci. Technol., 40, 242–254, 2006. Lohmann, U. and Feichter, J.: Global Indirect Aerosol Effect: a Review, Aerosol Chem. Phys. 5, 715–737, 2005. McFiggans, G., Artaxo, P., Baltensperger, U., Coe, H., Facchini, M. C., Feingold, G., Fuzzi, S., Gysel, M., Laaksonen, A., Lohmann, U., Mentel, T. F., Murphy, D. M., O'Dowd, C. D., Snider, J. R., and Weingartner, E.: The effect of physical and chemical aerosol properties on warm cloud droplet activation, Atmos. Chem. Phys., 6, 2593–-2649, 2006. Petters, M. D. and Kreidenweis, S. M.: A Single Parameter Representation of Hygroscopic Growth and Cloud Condensation Nucleus Activity, Atmos. Chem. Phys., 7, 1961–1971, 2007. Prenni, A. J., DeMott, P. J., Kreidenweis, S. M., Sherman, D. E., Russell, L. M., and Ming, Y.: The Effects of Low Molecular Weight Dicarboxylic Acids on Cloud Formation, J. Phys. Chem A, 105, 11 240–11 248, 2001. Pruppacher, H. R. and Klett, J. D.: Microphysics of Clouds and Precipitation, second ed., 714 pp., D. Reidel Publishing Company, Dordrecht, Holland, 1997. Raymond, T. M. and Pandis, S. N.: Formation of Cloud Droplets by Multicomponent Organic Particles, J. Geophys. Res., 4469, 108, doi:10.1029/2003JD003503, 2002. Rissman, T. A., Varutbangkul, V., Surratt, J. D., Topping, D. O., McFiggans, G., Flagan, R. C., and Seinfeld, J. H.: Cloud Condensation Nucleus (CCN) Behavior of Organic Aerosol Particles Generated by Atomization of Water and Methanol Solutions, Atmos. Chem. Phys., 7, 2949–2971, 2007. Roberts, G. C. and Nenes, A.: A Continuous-Flow Streamwise Thermal-Gradient CCN Chamber for Atmospheric Measurements, Aerosol Sci. Technol., 39, 206–221, 2005. Rose, D., Frank, G. P., Dusek, U., Gunthe, S. S., Andreae, M. O., and Pöschl, U.: Calibration and Measurement Uncertainties of a Continuous-Flow Cloud Condensation Nuclei Counter (DMT-CCNC): CCN Activation of Ammonium Sulfate and Sodium Chloride Aerosol Particles in Theory and Experiment, Atmos. Chem. Phys. Discuss., 7, 8193–8260, 2007. Saxena, P. and Hildemann, L. M.: Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds, J. Atmos. Chem., 24, 57–109, doi:110.1007/BF00053823, 1996. Schwartz, S. E., Charlson, R. J., and Rhode, H.: Quantifying Climate Change – Too Rosy a Picture?, Nature Reports Climate Change, 2, 23–24, 2007. Shulman, M. L., Jacobson, M. C., Carlson, R. J., Synovec, R. E., and Young, T. E.: Dissolution Behavior and Surface Tension Effects of Organic Compounds in Nucleating Cloud Droplets, Geophys. Res. Lett., 23, 277–280, 1996. Slowik, J. G., Stainken, K., Davidovits, P., Williams, L. R., Jayne, J. T., Kolb, C. E., Worsnop, D. R., Rudich, Y., DeCarlo, P. F., and Jimenez, J. L.: Particle Morphology and Density Characterization by Combined Mobility and Aerodynamic Diameter Measurements. Part 2: Application to Combustion-Generated Soot Aerosols as a Function of Fuel Equivalence Ratio, Aerosol Sci. Technol., 38, 1206–1222, 2004.