References

ACP

Atmospheric Chemistry and Physics

ACP

1680-7324

Copernicus GmbH

Göttingen, Germany

10.5194/acp-9-7053-2009

Cloud condensation nuclei measurements in the marine boundary layer of the Eastern Mediterranean: CCN closure and droplet growth kinetics

Bougiatioti

¹ Fountoukis

³ ⁴ Kalivitis

¹ Pandis

S. N.

⁴ ⁵ Nenes

² ³ Mihalopoulos

Environmental Chemical Processes Laboratory, Department of Chemistry, University of Crete, Voutes, 71003, Heraklion, Greece

Earth and Atmospheric Sciences, Georgia Institute of Technology, Atlanta, GA, USA

Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, USA

Institute of Chemical Engineering and High Temperature Chemical Processes (ICE-HT), Foundation for Research and Technology Hellas (FORTH), Patras, 26504, Greece

Department of Chemical Engineering, Carnegie Mellon University, Pittsburgh, PA 15213, USA

24 09 2009

9 18 7053 7066

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/9/7053/2009/acp-9-7053-2009.html

The full text article is available as a PDF file from http://www.atmos-chem-phys.net/9/7053/2009/acp-9-7053-2009.pdf

Measurements of cloud condensation nuclei (CCN) concentrations (cm−3) between 0.2 and 1.0% supersaturation, aerosol size distribution and chemical composition were performed at a remote marine site in the eastern Mediterranean, from September to October 2007 during the FAME07 campaign. Most of the particles activate at ~0.6% supersaturation, characteristic of the aged nature of the aerosol sampled. Application of Köhler theory, using measurements of bulk composition, size distribution, and assuming that organics are insoluble resulted in agreement between predicted and measured CCN concentrations within 7±11% for all supersaturations, with a tendency for CCN underprediction (16±6%; r2=0.88) at the lowest supersaturations (0.21%). Including the effects of the water-soluble organic fraction (which represent around 70% of the total organic content) reduces the average underprediction bias at the low supersaturations, resulting in a total closure error of 0.6±6%. Using threshold droplet growth analysis, the growth kinetics of ambient CCN is consistent with NaCl calibration experiments; hence the presence of aged organics does not suppress the rate of water uptake in this environment. The knowledge of the soluble salt fraction is sufficient for the description of the CCN activity in this area.

References 1

Albrecht, B. A.: Aerosols, cloud microphysics, and fractional cloudiness, Science, 245, 1227–1230, 1989.

Asa-Awuku, A., Engelhart, G. J., Lee, B. H., Pandis, S. N., and Nenes, A.: Relating CCN activity, volatility, and droplet growth kinetics of β-caryophyllene secondary organic aerosol, Atmos. Chem. Phys., 9, 795–812, 2009.

Asa-Awuku, A., Sullivan, A. P., Hennigan, C. J., Weber, R. J., and Nenes, A.: Investigation of molar volume and surfactant characteristics of water-soluble organic compounds in biomass burning aerosol, Atmos. Chem. Phys., 8, 799–812, 2008.

Asa-Awuku, A., Nenes, A., Gao, S., Flagan, R. C., and Seinfeld, J. H.: Alkene ozonolysis SOA: inferences of composition and droplet growth kinetics from Köhler theory analysis, Atmos. Chem. Phys. Discuss., 7, 8983–9011, 2007.

Barahona, D. and Nenes, A.: Parameterization of cloud droplet formation in large-scale models: Including effects of entrainment, J. Geophys. Res.-Atmos., 112(D16), D16206, doi:10.1029/2007JD008473, 2007.

Bardouki, H., Liakakou, H., Economou, C., Sciare, J., Smolik, J., Zdimal, V., Eleftheriadis, K., Lazaridis, M., Dye, C., and Mihalopoulos, N.: Chemical composition of size-resolved atmospheric aerosols in the eastern Mediterranean during summer and winter, Atmos. Environ., 37, 195–208, 2003.

Brechtel, F. J. and Kreidenweis, S. M.: Predicting particle critical supersaturation from hygroscopic growth measurements in the humidified TDMA, Part~1: Theory and sensitivity studies, J. Aerosol Sci., 57, 1854–1871, 2000.

Broekhuizen, K., Chang, R.Y.-W., Leaitch, W. R., Li, S.-M., and Abbatt, J. P. D.: Closure between measured and modeled cloud condensation nuclei (CCN) using size-resolved aerosol compositions in downtown Toronto, Atmos. Chem. Phys., 6, 2513–2524, 2006.

Cantrell, W. G., Shaw, G., Cass, G., Chowdhury, Z., Hughes, L., Prather, K., Guazzotti, S., and Coffee, K.: Closure between aerosol particles and cloud condensation nuclei at Kaashidhoo climate observatory, J. Geophys. Res., 106(D22), 28711–28718, 2001.

Chang, R. Y.-W., Liu, P. S. K., Leaitch, W. R., and Abbatt, J. P. D.: Comparison between measured and predicted CCN concentrations at Egbert, Ontario: Focus on the organic aerosol fraction at a semi-rural site, Atmos. Environ., 41, 8172–8182, 2007.

Charlson, R., Seinfeld, J., Nenes, A., Kulmala, M., Laaksonen, A., and Facchini, M.: Reshaping the theory of cloud formation, Science, 292, 2025–2026, 2001.

Covert, D., Gras, J., Wiedensholer, A., and Stratmann, F.: Comparison of directly measured CCN with CCN modeled from the number-size distribution in the marine boundary layer during ACE~1 at Cape Grim, Tasmania, J. Geophys. Res., 108(D21), 16597–16608, 1998.

Clegg, S. L. and Brimblecombe, P.: Equilibrium partial pressures of strong acids over concentrated saline solutions – I HNO3, Atmos. Environ., 22, 91–100, 1988.

CRC, Handbook of Chemistry and Physics, 74th Edition, CRC Press Inc., 1993.

Cross, E. S., Slowik, J. G., Davidovits, P., Allan, J. D., Worsnop, D. R., Jayne, J. T., Lewis, D. K., Canagaratna, M., and Onasch, T. B.: Laboratory and ambient particle density determinations using light scattering in conjunction with aerosol mass spectrometry, Aerosol Sci. Tech., 41, 343–359, 2007.

Decesari, S., Facchini, M. C., Mircea, M., Cavalli, F., and Fuzzi, S.: Solubility properties of surfactants in atmospheric aerosol and cloud/fog water samples, J. Geophys. Res., 108(D21), 4685, doi:10.1029/ 2003JD003566, 2003.

Dinar, E., Taraniuk, I., Graber, E. R., Katsman, S., Moise, T., Anttila, T., Mentel, T. F., and Rudich, Y.: Cloud Condensation Nuclei properties of model and atmospheric HULIS, Atmos. Chem. Phys., 6, 2465–2482, 2006.

Dusek, U., Covert, D., Wiedensholer, A., Neususs, C., Weise, D., and Cantrell, W.: Cloud condensation nuclei spectra derived from size distributions and hygroscopic properties of the aerosol in coastal southwest Portugal during ACE-2, Tellus, 55B, 35–53, 2003.

Engelhart, G. J., Asa-Awuku, A., Nenes, A., and Pandis, S. N.: CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol, Atmos. Chem. Phys., 8, 3937–3949, 2008.

Ervens, B., Cubison, M., Andrews, E., Feingold, G., Ogren, J. A., Jimenez, J. L., DeCarlo, P., and Nenes, A.: Prediction of cloud condensation nucleus number concentration using measurements of aerosol size distributions and composition and light scattering enhancement due to humidity, J. Geophys. Res., 112, D10S32, doi:10.1029/2006JD007426, 2007.

Facchini, M., Mircea, M., Fuzzi, S., and Charlson, R.: Cloud albedo enhancement by surface-active organic solutes in growing droplets, Nature, 401, 257–259, 1999.

Finlayson-Pitts, B. J. and Piits Jr., J. N.: Chemistry of the Upper and Lower Atmosphere: Theory, Experiments and Applications, Academic Press, San Diego, California, USA, 2000.

Fountoukis, C. and Nenes, A.: Continued development of a cloud droplet formation parameterization for global climate models, J. Geophys. Res., 110, D11212, doi:10.1029/2004JD005591, 2005.

Furutani, H., Dall'osto, M., Roberts, G. C., and Prather, K. A.: Assessment of the relative importance of atmospheric aging on CCN activity derived from field observations, Atmos. Environ., 42, 3130–3142, 2008.

Gunthe, S. S., King, S. M., Rose, D., Chen, Q., Roldin, P., Farmer, D. K., Jimenez, J. L., Artaxo, P., Andreae, M. O., Martin, S. T., and Pöschl, U.: Cloud condensation nuclei in pristine tropical rainforest air of Amazonia: size-resolved measurements and modeling of atmospheric aerosol composition and CCN activity, Atmos. Chem. Phys. Discuss., 9, 3811–3870, 2009.

Hallquist, M., Wenger, J. C., Baltensperger, U., Rudich, Y., Simpson, D., Claeys, M., Dommen, J., Donahue, N. M., George, C., Goldstein, A. H., Hamilton, J. F., Herrmann, H., Hoffmann, T., Iinuma, Y., Jang, M., Jenkin, M. E., Jimenez, J. L., Kiendler-Scharr, A., Maenhaut, W., McFiggans, G., Mentel, T. F., Monod, A., Prévót, A. S. H., Seinfeld, J. H., Surratt, J. D., Szmigielski, R., and Wildt, J.: The formation, properties and impact of secondary organic aerosol: current and emerging issues, Atmos. Chem. Phys., 9, 5155–5235, 2009.

Intergovernmental Panel on Climate Change: Climate Change 2007: Synthesis Report, 2007.

Jaffrezo, J.-L., Aymoz, G., Delaval, C., and Cozic, J.: Seasonal variations of the water soluble organic carbon mass fraction of aerosol in two valleys of the French Alps, Atmos. Chem. Phys., 5, 2809–2821, 2005.

Ji, Q., Shaw, G., and Cantrell, W.: A new instrument for measuring cloud condensation nuclei: Cloud condensation nucleus "remover", J. Geophys. Res., 103, 28013–28019, 1998.

Köhler, H.: Zur condensation des wasserdampfe in der atmosphere, Geofys. Publ., 2, 3–15, 1921.

Köhler, H.: The nucleus in the growth of hygroscopic droplets, T. Faraday Soc., 32, 1152, 1936.

Kostenidou, E., Pathak, R. K., and Pandis, S.: An algorithm for the calculation of secondary organic aerosol density combining AMS and SMPS data, Aerosol Sci. Tech., 41(11), 1002–1010, 2007.

Koulouri, E., Saarikoski, S., Theodosi, C., Markaki, Z., \mboxGerasopoulos, E., Kouvarakis, G., Mäkelä, T., Hillamo, R., and Mihalopoulos, N.: Chemical composition and sources of fine and coarse particles in the Eastern Mediterranean, Atmos. Environ., 42, 6542–6550, 2008.

Krämer, L., Pöschl, U., and Niessner, R.: Microstructural rearrangement of sodium chloride condensation aerosol particles on interaction with water vapor, J. Aerosol Sci., 31, 673–685, 2000.

Lance, S., Medina, J., Smith, J., and Nenes, A.: Mapping the operation of the DMT continuous flow CCN counter, Aerosol Sci. Tech., 40, 242–254, 2006.

Lance, S., Nenes, A., Mazzoleni, C., Dubey, M. K., Gates, H., Varutbangkul, V., Rissman, T. A., Murphy, S. M., Sorooshian, A., Flagan, T. A., Seinfeld, J. H., Feingold, G., and Jinsson, H.: Cloud condensation nuclei activity, closure, and droplet growth kinetics of Houston aerosol during the Gulf of Mexico Atmospheric Composition and Climate Study (GoMACCS), J. Geophys. Res., 114, D00F15, doi:10.1029/2008JD011699, 2009.

Lelieveld, J., Berresheim, H., Borrmann, S., Crutzen, P. J., Dentener, F. J., Fischer, H., Feichter, J., Flatau, P. J., Heland, J., Holzinger, R., Korrmann, R., Lawrence, M. G., Levin, Z., Markowicz, K. M., Mihalopoulos, N., Minikin, A., Ramanathan, V., De Reus, M., Roelofs, G. J., Scheeren, H. A., Sciare, J., Schlager, H., Schultz, M., Siegmund, P., Steil, B., Stephanou, E. G., Stier, P., Traub, M., Warneke, C., Williams, J., and Ziereis, H.: Global Air Pollution Crossroads over the Mediterranean, Science, 298, 794–799, 2002.

Liu, P., Leaitch, W., Banic, C., Li, S., Ngo, D., and Megaw, W.: Aerosol observations at Chebogue Point during the 1993 North Atlantic Regional Experiment: Relationships among cloud condnensation nuclei, size distribution and chemistry, J. Geophys. Res., 101, 28971–28990, 1996.

Maenhaut, W., Hillamo, R., Mäkelä, T., Jafferzo, J.-L., Bergin, M. H., and Davidson, C. I.: A new cascade impactor for aerosol sampling with subsequent PIXE analysis, Nucl. Instr. Meth. B, 109/110, 482–487, 1996.

McMurry, P. H., Wang, X., Park, K., and Ehara, K.: The relationship between mass and mobility for atmospheric particles: A new technique for measuring particle density, Aerosol Sci. Tech., 36, 227–238, 2002.

Medina, J., Nenes, A., Sotiropoulou, R.-E. P., Cottrell, L. D., Ziemba, L. D., Beckman, P. J., and Griffin, R. J.: Cloud condensation nuclei closure during the International Consortium for Atmospheric Research on Transport and Transformation~2004 campaign: Effects of size-resolved composition, J. Geophys. Res., 112, D10S31, doi:10.1029/2006JD007588, 2007.

Mihalopoulos, N., Stephanou, E., Kanakidou, M., Pilitsidis, S., and Bousquet, P.: Tropospheric aerosol ionic composition above the Eastern Mediterranean area, Tellus, 49B, 314–326, 1997.

Mikhailov, E., Vlasenko, S., Niessner, R., and Pöschl, U.: Interaction of aerosol particles composed of protein and saltswith water vapor: hygroscopic growth and microstructural rearrangement, Atmos. Chem. Phys., 4, 323–350, 2004.

Mircea, M., Facchini, M. C., Decesari, S., Cavalli, F., Emblico, L., Fuzzi, S., Vestin, A., Rissler, J., Swietlicki, E., Frank, G., Andreae, M. O., Maenhaut, W., Rudich, Y., and Artaxo, P.: Importance of the organic aerosol fraction for modeling aerosol hygroscopic growth and activation: a case study in the Amazon Basin, Atmos. Chem. Phys. Discuss., 5, 5253–5298, 2005.

Moore, R. H., Ingall, E. D., Sorooshian, A., and Nenes, A.: Molar mass surface tension, and droplet growth kinetics on marine organics from measurements of CCN activity, Geophys. Res. Lett., 35, L07801, doi:10.1029/2008GL033350, 2008.

Murphy, S. M., Agrawal, H., Sorooshian, A., Padro, L. T., Gates, H., Hersey, S., Welch, W. A., Jung, H., Miller, J. W., Cocker~III, D. R., Nenes, A., Jonsson, H. H., Flagan, R. C., and Seinfeld, J. H.: Comprehensive Simultaneous Shipboard and Airborne Characterization of Exhaust from a Modern Container Ship at Sea, Environ. Sci. Technol., 43, 13, 4626–4640, 2009.

Nenes, A., Ghan, S., Abdul-Razzak, H., Chuang, P., and Seinfeld, J. H.: Kinetic limitations on cloud droplet formation and impact on cloud albedo, Tellus, 53B, 133–149, 2001.

Nenes, A., Charlson, R. J., Facchini, M. C., Kulmala, M., Laaksonen, A., and Seinfeld, J. H.: Can chemical effects on cloud droplet number rival the first indirect effect?, Geophys. Res. Lett., 29(17), 1848, doi:10.1029/2002GL015295, 2002.

Padró, L. T., Asa-Awuku, A., Morrison, R., and Nenes, A.: Inferring thermodynamic properties from CCN activation experiments: single-component and binary aerosols, Atmos. Chem. Phys., 7, 5263–5274, 2007.

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.

Pitzer, K. S.: Thermodynamics of electrolytes, I, Theoretical Basis and general equations, J. Phys. Chem., 77, 268–277, 1973.

Pitzer, K. S. and Mayorga, G.: Thermodynamics of electrolytes, II, Activity and osmotic coefficients for strong electrolytes with one or both ions univalent, J. Phys. Chem., 77, 2300–2308, 1973.

Reade, L., Jennings, S. G., and McSweeney, G.: Cloud condensation nuclei measurements at Mace Head, Ireland, over a period 1994–2002, Atmos. Res., 82, 610–621, 2006.

Rissman, T. A., VanReken, T. M., Wang, J., Gasparini, R., Collins, D. R., Jonsson, H. H., Brechtel, F. J., Flagan, R. C., and Seinfeld, J. H.: Characterization of ambient aerosol from measurements of cloud condensation nuclei during the 2003 atmospheric radiation measurement aerosol intensive observational period at the Southern Great Plains site in Oklahoma, J. Geophys. Res., 111, D05S11/1–D05S11/20, 2006.

Roberts, G. C., Nenes, A., Seinfeld, J. H., and Andreae, M. O.: Impact of biomass burning on cloud properties in the Amazon Basin, J. Geophys. Res, 108(D2), 4062, doi:10.1029/2001JD000985, 2003.

Roberts, G. and Nenes, A.: A continuous-flow streamwise thermal-gradient CCN chamber for atmospheric measurements, Aerosol Sci. Tech., 39, 206–221, 2005.

Roberts, G. C., Mauger, G., Hadley, O., and Ramanathan, V.: North American and Asian aerosols over the Eastern Pacific Ocean and their role in regulating cloud condensation nuclei, J. Geophys. Res., 111, D13205, doi:10.1029/2005JD006661, 2006.

Rose, D., Nowak, A., Achtert, P., Wiedensohler, A., Hu, M., Shao, M., Zhang, Y., Andreae, M. O., and Pöschl, U.: Cloud condensation nuclei in polluted air and biomass burning smoke near the mega-city Guangzhou, China - Part~1: Size-resolved measurements and implications for the modeling of aerosol particle hygroscopicity and CCN activity, Atmos. Chem. Phys. Discuss., 8, 17343–17392, 2008.

Rose, D., Gunthe, S. S., Mikhailov, E., Frank, G. P., Dusek, U., 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., 8, 1153–1179, 2008.

Ruehl, C. R., Chuang, P. Y., and Nenes, A.: How quickly do cloud droplets form on atmospheric particles?, Atmos. Chem. Phys., 8, 1043–1055, 2008.

Salma, I., Ocskay, R., Varga, I., and Maenhaut, W.: Surface tension of atmospheric humic-like substances in connection with relaxation, dilution and solution pH, J. Geophys. Res., 111, D23205, doi:10.1029/2005JD007015, 2006.

Seinfeld, J., and Pandis, S.: Atmospheric Chemistry and Physics: From Air Pollution to Climate Change, John Wiley, Hoboken, N J., 1998.

Sciare, J., Oikonomou, K., Cachier, H., Mihalopoulos, N., Andreae, M. O., Maenhaut, W., and Sarda-Estève, R.: Aerosol mass closure and reconstruction of the light scattering coefficient over the Eastern Mediterranean Sea during the MINOS campaign, Atmos. Chem. Phys., 5, 2253–2265, 2005.

Shantz, N. C., Leaitch, W. R., Phinney, L., Mozurkewich, M., and Toom-Sauntry, D.: The effect of organic compounds on the growth rate of cloud droplets in marine and forest settings, Atmos. Chem. Phys., 8, 5869–5887, 2008.

Shulman, M., Jacobson, M., Charlson, R., Synovec, R., and Young, T.: Dissolution behavior and surface tension effects of organic compounds in nucleating cloud droplets, Geophys. Res. Lett., 23, 277–280, 1996.

Snider, J., Guibert, S., Brenguier, J., and Putaud, J.: Aerosol activation in marine stratocumulus clouds: 2, Köhler and parcel theory closures studies, J. Geophys. Res., 108(D15), 8629, doi:10.1029/2002JD002692, 2003.

Sorooshian, A., Murphy, S. M., Hersey, S., Gates, H., Padro, L. T., Nenes, A., Brechtel, F. J., Jonsson, H., Flagan, R. C., and Seinfeld, J. H.: Comprehensive airborne characterization of aerosol from a major bovine source, Atmos. Chem. Phys., 8, 5489–5520, 2008.

Sotiropoulou, R. E. P, Nenes, A., Adams, P. J., and Seinfeld, J. H.: Cloud condensation nuclei prediction error from application of Kohler theory: Importance for the aerosol indirect effect, J. Geoph. Res., 112, D12202, doi:10.1029/2006JD007834, 2007.

Sotiropoulou, R. E. P, Medina, J., and Nenes, A.: CCN predictions: is theory sufficient for assessments of the indirect effect?, Geophs. Res. Lett., 33, L05816, doi:10.1029/2005GL025148, 2006.

Stein, S. W., Turpin, B. J., Cai, X., Huang, P.-F., and McMurry, P. H.: Measurements of relative humidity-dependent bounce and density for atmospheric particles using the DMA-impactor technique, Atmos. Environ., 28, 1739–1746, 1994.

Stroud, C. A., Nenes, A., Jimenez, J. L., DeCarlo, P. F., Huffman, J. A., Bruintjes, R., Nemitz, E., Delia, A. E., Toohey, D. W., Guenther, A. B., and Nandi, S.: Cloud activating properties of aerosol observed during CELTIC, J. Atmos. Sci., 64, 441–459, 2006.

Turšiè, J., Podkrajšek, B., Grgi\'c, I., Ctyroky, P., Berner, A., Dusek, U., and Hitzenberger, R.: Chemical composition and hygroscopic properties of size-segregated aerosol particles collected at the Adriatic coast of Slovenia, Chemosphere, 63, 1193–1202, 2006.

Twomey, S.: The influence of pollution on the shortwave albedo of clouds, J. Atmos. Sci., 34, 1149–1152, 1977.

VanReken, T. M., Rissman, T. A., Roberts, G. C., Varutbangkul, V., Jonsson, H. H., Flagan, R. C., and Seinfeld, J. H.: Toward aerosol/cloud condensation nuclei (CCN) closure during CRYSTAL-FACE, J. Geophys. Res., 108(D20), 4633, doi:10.1029/2003JD003582, 2003.

Vrekoussis, M., Liakakou, E., Koçak, M., Kubilay, N., Oikonomou, K., Sciare, J., and Mihalopoulos, N.: Seasonal variability of optical properties of aerosols in the Eastern Mediterranean, Atmos. Environ., 39, 37, 7083–7094, 2005.

Ziese, M., Wex, H., Nilsson, E., Salma, I., Ocskay, R., Hennig, T., Massling, A., and Stratmann, F.: Hygroscopic growth and activation of HULIS particles: experimental data and a new iterative parameterization scheme for complex aerosol particles, Atmos. Chem. Phys., 8, 1855–1866, 2008.