ACP Atmospheric Chemistry and Physics ACP 1680-7324 Copernicus GmbH Göttingen, Germany 10.5194/acp-11-5099-2011 Influences on the fraction of hydrophobic and hydrophilic black carbon in the atmosphere McMeeking G. R. 1 Good N. 1 Petters M. D. 2 McFiggans G. 1 Coe H. 1 Centre for Atmospheric Science, University of Manchester, Manchester, UK Department of Marine Earth and Atmospheric Sciences, Raleigh, NC, USA 31 05 2011 11 10 5099 5112 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/11/5099/2011/acp-11-5099-2011.html The full text article is available as a PDF file from http://www.atmos-chem-phys.net/11/5099/2011/acp-11-5099-2011.pdf

Black carbon (BC) is a short term climate forcer that directly warms the atmosphere, slows convection, and hinders quantification of the effect of greenhouse gases on climate change. The atmospheric lifetime of BC particles with respect to nucleation scavenging in clouds is controlled by their ability to serve as cloud condensation nuclei (CCN). To serve as CCN under typical conditions, hydrophobic BC particles must acquire hygroscopic coatings. However, the quantitative relationship between coatings and hygroscopic properties for ambient BC particles is not known nor is the time scale for hydrophobic-to-hydrophilic conversion. Here we introduce a method for measuring the hygroscopicity of externally and internally mixed BC particles by coupling a single particle soot photometer with a humidified tandem differential mobility analyzer. We test this technique using uncoated and coated laboratory generated model BC compounds and apply it to characterize the hygroscopicity distribution of ambient BC particles. From these data we derive that the observed number fraction of BC that is CCN active at 0.2 % supersaturation is generally low in an urban area near sources and that it varies with the trajectory of the airmass. We anticipate that our method can be combined with measures of air parcel physical and photochemical age to provide the first quantitative estimates for characterizing hydrophobic-to-hydrophilic conversion rates in the atmosphere.

 References Alexander, D. T. L., Crozier, P. A., and Anderson, J. R.: Brown carbon spheres in East Asian outflow and their optical properties, Science, 321, 833–836, http://dx.doi.org/10.1126/science.1155296doi:10.1126/science.1155296, 2008. Baumgardner, D., Kok, G., and Raga, G.: Warming of the Arctic lower stratosphere by light absorbing particles, Geophys. Res. Lett., 31, L06117, http://dx.doi.org/10.1029/2003GL018883doi:10.1029/2003GL018883, 2004. Baumgardner, D., Kok, G. L., and Raga, G. B.: On the diurnal variability of particle properties related to light absorbing carbon in Mexico City, Atmos. Chem. Phys., 7, 2517–2526, http://dx.doi.org/10.5194/acp-7-2517-2007doi:10.5194/acp-7-2517-2007, 2007. Chung, S. H. and Seinfeld, J. H.: Global distribution and climate forcing of carbonaceous aerosols, J. Geophys. Res., 107, D4407, http://dx.doi.org/10.1029/2001JD001397doi:10.1029/2001JD001397, 2002. Cooke, W. F. and Wilson, J. J. N.: A global black carbon aerosol model, J. Geophys. Res., 101, 19395–19409, 1996. Cubison, M. J., Coe, H., and Gysel, M.: A modified hygroscopic tandem DMA and a data retrieval method based on optimal estimation, J. Aerosol Sci., 36, 846–865, 2005. Draxler, R. R. and Rolph, G. D.: HYSPLIT (HYbrid Single-Particle Lagrangian Integrated Trajectory) Model access via NOAA ARL READY Website, available at: http://ready.arl.noaa.gov/HYSPLIT.php, NOAA Air Resources Laboratory, Silver Spring, MD, 2010. Dusek, U., Reischl, G. P., and Hitzenberger, R.: CCN activation of pure and coated carbon black particles, Environ. Sci. Technol., 40, 1223–1230, 2006. Fletcher, N. H.: Size effects in heterogeneous nucleation, J. Chem. Phys., 29, 572–576, 1958. Gao, R. S., J. P. Schwarz, K. K., Kelly, D. W., Fahey, L. A., Watts, T. L., Thompson, J. R., Spackman, J. G., Slowik, E. S., Cross, J.-H., Han, P., Davidovits, T. B., Onasch, and Worsnop, D. R.: A novel method for estimating light-scattering properties of soot aerosols using a modified single-particle soot photometer, Aerosol Sci. Technol., 41, 125–135, http://dx.doi.org/10.1080/02786820601118398doi:10.1080/02786820601118398, 2007. Good, N., Topping, D. O., Duplissy, J., Gysel, M., Meyer, N. K., Metzger, A., Turner, S. F., Baltensperger, U., Ristovski, Z., Weingartner, E., Coe, H., and McFiggans, G.: Widening the gap between measurement and modelling of secondary organic aerosol properties?, Atmos. Chem. Phys., 10, 2577–2593, http://dx.doi.org/10.5194/acp-10-2577-2010doi:10.5194/acp-10-2577-2010, 2010. Gysel, M., Nyeki, S., Weingartner, E., Baltensperger, U., Giebl, H., Hitzenberger, H., Petzold, A., and Wilson, C. W.: Properties of jet engine combustion particles during the PartEmis experiment: Hygroscopicity at subsaturated conditions, Geophys. Res. Lett., 30, 1566, http://dx.doi.org/10.1029/2003GL016896doi:10.1029/2003GL016896, 2003. Gysel, M., McFiggans, G. B., and Coe, H.: Inversion of tandem differential mobility analyser (TDMA) measurements, J. Aerosol Sci., 40, 134–151, 2009. Henning, S., Wex, H., Wennrich, C., Hennig, T., Kiselev, A., Snider, J. R., Rose, D., Dusek, U., Frank, G. P., Pöschl, U., Kristensson, A., Bilde, M., Tillmann, R., Kiendler-Scharr, A., Mentel, Th. F., Walter, S., Schneider, J., and Stratmann, F.: Soluble mass, hygroscopic growth, and droplet activation of coated soot particles during LACIS Experiment in November (LExNo), J. Geophys. Res., 115, D11206, http://dx.doi.org/10.1029/2009JD012626doi:10.1029/2009JD012626, 2010. Henson, B. F.: An adsorption model of insoluble particle activation: Application to black carbon, J. Geophys. Res., 112, D24S16, http://dx.doi.org/10.1029/2007JD008549doi:10.1029/2007JD008549, 2007. Herich, H., Kammermann, L., Gysel, M., Weingartner, E., Baltensperger, U., Lohmann, U., Cziczo, D. J.: In situ determination of atmospheric aerosol composition as a function of hygroscopic growth, J. Geophys. Res., 113, D16213, http://dx.doi.org/10.1029/2008JD009954doi:10.1029/2008JD009954, 2008. Junge, C., : Das Wachstum der Kondensationskerne mit der relativen Feuchtigkeit, Annalen der Meteorologie, 3, 129–135, 1950. 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. Khalizov, A. F, Zhang, R., Zhang, D., Xue, H., Pagels, J., and McMurry, P. H.: Formation of highly hygroscopic soot aerosols upon internal mixing with sulfuric acid vapor, J. Geophys. Res., 114, D05208, http://dx.doi.org/10.1029/2008JD010595doi:10.1029/2008JD010595, 2009. Koch, D.: Transport and direct radiative forcing of carbonaceous and sulfate aerosols in the GISS GCM, J. Geophys. Res., 106, 20311–20332, 2001. Koch, D., Schulz, M., Kinne, S., McNaughton, C., Spackman, J. R., Balkanski, Y., Bauer, S., Berntsen, T., Bond, T. C., Boucher, O., Chin, M., Clarke, A., De Luca, N., Dentener, F., Diehl, T., Dubovik, O., Easter, R., Fahey, D. W., Feichter, J., Fillmore, D., Freitag, S., Ghan, S., Ginoux, P., Gong, S., Horowitz, L., Iversen, T., Kirkevåg, A., Klimont, Z., Kondo, Y., Krol, M., Liu, X., Miller, R., Montanaro, V., Moteki, N., Myhre, G., Penner, J. E., Perlwitz, J., Pitari, G., Reddy, S., Sahu, L., Sakamoto, H., Schuster, G., Schwarz, J. P., Seland, Ø., Stier, P., Takegawa, N., Takemura, T., Textor, C., van Aardenne, J. A., and Zhao, Y.: Evaluation of black carbon estimations in global aerosol models, Atmos. Chem. Phys., 9, 9001–9026, http://dx.doi.org/10.5194/acp-9-9001-2009doi:10.5194/acp-9-9001-2009, 2009. Koehler, K. A., DeMott, P. J., Kreidenweis, S. M., Popovicheva, O., Petters, M. D., Carrico, C. M., Kireeva, E., Khokhlova, T., and Shonija, N.: Cloud condensation nuclei and ice nucleation activity of hydrophobic and hydrophilic soot particles, Phys. Chem. Chem. Phys., 11, 7906–7920, http://dx.doi.org/10.1039/b905334bdoi:10.1039/b905334b, 2009. Lammel, G. and Novakov, T.: Water nucleation properties of carbon-black and diesel soot particles, Atmos .Environ., 29, 813–823, 1995. Lewis, K. A., Arnott, W. P., Moosmüller, H., Chakrabarty, R. K., Carrico, C. M., Kreidenweis, S. M., Day, D. E., Malm, W. C., Laskin, A., Jimenez, J. L., Ulbrich, I. M., Huffman, J. A., Onasch, T. B., Trimborn, A., Liu, L., and Mishchenko, M. I.: Reduction in biomass burning aerosol light absorption upon humidification: roles of inorganically-induced hygroscopicity, particle collapse, and photoacoustic heat and mass transfer, Atmos. Chem. Phys., 9, 8949–8966, http://dx.doi.org/10.5194/acp-9-8949-2009doi:10.5194/acp-9-8949-2009, 2009. Liu, D., Flynn, M., Gysel M., Targino, A., Crawford, I., Bower, K., Choularton, T., Juranyi, Z., Steinbacher, M., Huglin, C., Curtius, J., Kampus, M., Petzold, A., Weingartner, E., Baltensperger, U., and Coe, H.: Single particle characterization of black carbon aerosols at a tropospheric alpine site in Switzerland, Atmos. Chem. Phys., 10, 7389–7407, http://dx.doi.org/10.5194/acp-10-7389-2010doi:10.5194/acp-10-7389-2010, 2010. Mahata, P. C. and Alofs, D. J.: Insoluble condensation nuclei: The effect of contact angle, surface roughness and adsorption, J. Atmos. Sci., 32, 116–122, 1975. McMeeking, G. R., Hamburger, T., Liu, D., Flynn, M., Morgan, W. T., Northway, M., Highwood, E. J., Krejci, R., Allan, J. D., Minikin, A., and Coe, H.: Black carbon measurements in the boundary layer over western and northern Europe, Atmos. Chem. Phys., 10, 9393–9414, http://dx.doi.org/10.5194/acp-10-9393-2010doi:10.5194/acp-10-9393-2010, 2010. Moffet, R. C. and Prather, K. A.: In-situ measurements of the mixing state and optical properties of soot with implications for radiative forcing estimates, P. Natl. Acad. Sci. USA, 106(29), 11872–11877, 2009. Morgan, W. T., Allan, J. D., Bower, K. N., Esselborn, M., Harris, B., Henzing, J. S., Highwood, E. J., Kiendler-Scharr, A., McMeeking, G. R., Mensah, A. A., Northway, M. J., Osborne, S., Williams, P. I., Krejci, R., and Coe, H.: Enhancement of the aerosol direct radiative effect by semi-volatile aerosol components: airborne measurements in North-Western Europe, Atmos. Chem. Phys., 10, 815-1-8171, http://dx.doi.org/10.5194/acp-10-8151-2010doi:10.5194/acp-10-8151-2010, 2010. Moteki, N. and Kondo, Y.: Dependence of laser-induced incandescence on physical properties of black carbon aerosols: Measurements and theoretical interpretation, Aerosol Sci. Tech., 44, 663–675, http://dx.doi.org/10.1080/02786826.2010.484450doi:10.1080/02786826.2010.484450, 2010. Moteki, N., Kondo, Y., Miyazaki, Y., Takegawa, N., Komazaki, Y., Kurata, G., Shirai, T., Blake, D. R., Miyakawa, T., and Koike, M.: Evolution of mixing state of black carbon particles: Aircraft measurements over the western Pacific in March 2004, Geophys. Res. Lett., 34, L11803, http://dx.doi.org/10.1029/2006GL028943doi:10.1029/2006GL028943, 2007. Moteki, N., Kondo, Y., and Nakamura, S.: Method to measure refractive indices of small nonspherical particles: Application to black carbon particles, J. Aerosol Sci., 41, 513–521, http://dx.doi.org/10.1016/j.jaerosci.2010.02.013doi:10.1016/j.jaerosci.2010.02.013, 2010. Pagels, J., Khalizov, A. F., McMurry, P. H., and Zhang, R. Y.: Processing of soot by controlled sulphuric acid and water condensation-Mass and mobility relationships, Aerosol Sci. Technol., 43(7), 629–640, 2009. 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, http://dx.doi.org/10.5194/acp-7-1961-2007doi:10.5194/acp-7-1961-2007, 2007. Petters, M. D. and Kreidenweis, S. M.: A single parameter representation of hygroscopic growth and cloud condensation nucleus activity - Part 2: Including solubility, Atmos. Chem. Phys., 8, 6273–6279, http://dx.doi.org/10.5194/acp-8-6273-2008doi:10.5194/acp-8-6273-2008, 2008. Petters, M. D., Prenni, A. J., Kreidenweis, S. M., DeMott, P. J., Matsunaga, A., Lim, Y. B., and Ziemann, P. J.: Chemical aging and the hydrophobic-to-hydrophilic conversion of carbonaceous aerosol, Geophys. Res. Lett., 33, L24806, http://dx.doi.org/10.1029/2006GL027249doi:10.1029/2006GL027249, 2006. Popovicheva, O. B., Persiantseva, N. M., Tishkova, V., Shonija, N. K., and Zubareva, N. A.: Quantification of water uptake by soot particles, Environ. Res. Lett., 3, 025009, http://dx.doi.org/10.1088/1748-9326/3/2/025009doi:10.1088/1748-9326/3/2/025009, 2008a. Popovicheva, O., Persiantseva, N. M., Shonija, N. K., DeMott, P. J., Koehler, K. A., Petters, M. D., Kreidenweis, S. M., Tishkova, V., Demirdjian, B., and Suzanne, J.: Water interaction with hydrophobic and hydrophilic soot particles, Phys. Chem. Chem. Phys., 10(17), 2332–2344, 2008b. Pratt, K. A., and Prather, K. A.: Aircraft measurements of vertical profiles of aerosol mixing states, J. Geophys. Res., 115, D11305, http://dx.doi.org/10.1029/2009JD013150doi:10.1029/2009JD013150, 2010. Pruppacher, H. R.,and Klett, J. R.: Microphysics of Clouds and Precipitation, 1997. Rader, D. J. and McMurry, P. H.: Application of the Tandem Differential Mobility Analyzer to studies of droplet growth or evaporation, J. Aerosol Sci., 17, 771–787, 1986. Ramanathan, V. and Carmichael, G.: Global and regional climate changes due to black carbon, Nat. Geosci., 1, 221-2-27, http://dx.doi.org/10.1038/ngeo156doi:10.1038/ngeo156, 2008. Riemer, N., West, M., Zaveri, R. A., and Easter, R. C.: Estimating black carbon aging time scales with a particle-resolved aerosol model, J. Aerosol Sci., 41, 143–158, http://dx.doi.org/10.1016/j.jaerosci.2009.08.009doi:10.1016/j.jaerosci.2009.08.009, 2010. Rodhe, H., Persson, C., and Akesson, O.: An investigation into regional transport of soot and sulfate aerosols, Atmos. Environ., 6, 675–693, 1972. 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, 1996. Schwarz, J. P., Gao, R. S., Fahey, D. W., Thomson, D. S., Watts, L. A., Wilson, J. C., Reeves, J. M., Darbeheshti, M., Baumgardner, D. G., Kok, G. L., Chung, S. H., Schulz, M., Hendricks, J., Lauer, A., Karcher, B., Slowik, J. G., Rosenlof, K. H., Thompson, T. L., Langford, A. O., Loewenstein, M., and Aikin, K. C.: Single-particle measurements of midlatitude black carbon and light-scattering aerosols from the boundary layer to the lower stratosphere, J. Geophys. Res., 111, D16207, http://dx.doi.org/10.1029/2006JD007076doi:10.1029/2006JD007076, 2006. Schwarz, J. P., Gao, R. S., Spackman, J. R., Watts, L. A., Thomson, D. S., Fahey, D. W., Ryerson, T. B., Peischl, J., Holloway, J. S., Trainer, M., Frost, G. J., Baynard, T., Lack, D. A., de Gouw, J. A., Warneke, C., and Del Negro, L. A.: Measurement of the mixing state, mass, and optical size of individual black carbon particles in urban and biomass burning emissions, Geophys. Res. Lett., 35, L13810, http://dx.doi.org/10.1029/2008GL033968doi:10.1029/2008GL033968, 2008. Schwarz, J. P., Spackman, J. R., Gao, R. S., Perring, A. E., Cross, E., Onasch, T. B., Ahern, A., Wrobel, W., Davidovits, P., Olfert, J., Dubey, M. K., Mazzoleni, C., and Fahey, D. W.: The detection efficiency of the Single Particle Soot Photometer, Aerosol Sci. Technol., 44, 612–628, http://dx.doi.org/10.1080/02786826.2010.481298doi:10.1080/02786826.2010.481298, 2010. Shiraiwa, M., Kondo, Y., Moteki, N., Taegawa, N., Miyazaki, Y., and Blake, D. R.: Evolution of mixing state of black carbon in polluted air from Tokyo, Geophys. Res. Lett., 34, L16803, http://dx.doi.org/10.1029/2007GL029819doi:10.1029/2007GL029819, 2007. Simoneit, B. R. T.: Biomass burning – A review of organic tracers for smoke from incomplete combustion, Appl. Geochem., 17, 129–162, 2002. Slowik, J. G., Cross, E. S., Han, J.-H., Davidovits, P., Onasch, T. B., Jayne, J. T., Williams, L. R., Canagaratna, M. R., D. R., Chakrabarty, R. K., Moosmuller, H., Arnott, W. P., Schwarz, J. P., Gao, R. S., Fahey, D. W., Kok, G. L., and Petzold, A.: An inter-comparison of instruments measuring black carbon content of soot particles, Aerosol Sci. Technol., 41, 295–314,Worsnop, http://dx.doi.org/10.1080/02786820701197078doi:10.1080/02786820701197078, 2007. Snider, J. R., Guibert, S., Brenguier, J. L., and Putaud, J. P.: Aerosol activation in marine stratocumulus clouds: 2. Kohler and parcel theory closure studies, J. Geophys. Res., 108, 8629, http://dx.doi.org/10.1029/2002JD002692doi:10.1029/2002JD002692, 2003. Snider, J. R., Wex, H., Rose, D., Kristensson, A., Stratmann, F., Hennig, T., Henning, S., Kiselev, A., Bilde, M., Burkhart, M., Dusek, U., Frank, G. P., Kiendler-Scharr, A., Mentel, T. F., Petters, M. D., and Pöschl, U.: Intercomparison of cloud condensation nuclei and hygroscopic fraction measurements: Coated soot particles investigated during the LACIS Experiment in November (LExNo), J. Geophys. Res., 115, D11205, http://dx.doi.org/10.1029/2009JD012618doi:10.1029/2009JD012618, 2010. Sorjamaa, R. and Laaksonen, A.: The effect of H2O adsorption on cloud drop activation of insoluble particles: a theoretical framework, Atmos. Chem. Phys., 7, 6175–6180, http://dx.doi.org/10.5194/acp-7-6175-2007doi:10.5194/acp-7-6175-2007, 2007. Stephens, M., Turner, N., and Sandberg, J.: Particle identification by laser-induced incandescence in a solid-state laser cavity, Appl. Optics, 42, 3726–3736, http://dx.doi.org/10.1364/AO.42.003726doi:10.1364/AO.42.003726, 2003. Subramanian, R., Kok, G. L., Baumgardner, D., Clarke, A., Shinozuka, Y., Campos, T. L., Heizer, C. G., Stephens, B. B., de Foy, B., Voss, P. B., and Zaveri, R. A.: Black carbon over Mexico: the effect of atmospheric transport on mixing state, mass absorption cross-section, and BC/CO ratios, Atmos. Chem. Phys., 10, 219–237, http://dx.doi.org/10.5194/acp-10-219-2010doi:10.5194/acp-10-219-2010, 2010. Weingartner, E., Burtscher, H., and Baltensperger, U.: Hygroscopic properties of carbon and diesel soot particles, Atmos. Environ., 31, 2311–2327, 1997. Wyslouzil, B. E., Carleton, K. I., Sonnenfroh, D. M., Rawlins, W. T., and Arnold, S.: Observation of hydration of single modified carbon aerosols, Geophys. Res. Lett., 21, 2107–2110, 1994. Zelenyuk, A., Imre, D., Han, J.-H., Oatis, S.: Simultaneous measurements of individual ambient particle size, composition, effective density, and hygroscopicity, Anal. Chem., 80, 1401–1407, 2008. 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 spectrometery, Environ. Sci. Technol., 39, 4938–4952, 2005. Zhang, R. Y., Khalizov, A. F., Pagels, J., Zhang, D., Xue, H., and McMurry, P. H.: Variability in morphology, hygroscopicity, and optical properties of soot aerosols during atmospheric processing, P. Natl. Acad. Sci. USA, 105, 10291–10296, http://dx.doi.org/10.1073/pnas.0804860105doi:10.1073/pnas.0804860105, 2008.