The hygroscopic growth and CCN activity of complex biomass pyrolysis OC aerosol was experimentally measured with and without controlled conditions of humidity and chemical aging by atmospherically relevant tracer species, NH3 and O3. The role of these aging conditions in the enhancement of hygroscopicity of organic aerosols was investigated. From measurements of hygroscopic growth at subsaturated RH and CCN activity at supersaturated RH, I measured the hygroscopicity parameters, κGF and κCCN, respectively. I compared the κGF and κCCN of each aerosol population and analyzed the discrepancies to infer the presence of surfactants in these aerosol particles. My results suggest that approximating the surface tension of droplets to that of pure water, which is the basis of κ-Köhler theory, underestimates the CCN activity of biomass pyrolysis particles. An evidence of surfactant presence in OC particles is the enhanced CCN activation of particles in the 70 to 100 nm mobility diameter range.
Increase in κCCN of NH3-aged OC particles, while κGF remains unaffected, suggests the presence of insoluble or sparingly soluble organic acidic groups in enough proportions to influence the overall hygroscopicity of the particles. My results suggest that in atmospheric conditions of humidity and gas-phase NH3 levels, neutralization of acidic groups in organic particles by gas-phase NH3 is a prominent pathway to an increased CCN activity of these particles. Whether or not this increase in hygroscopicity has significant atmospheric implications depends on several other factors such as mixing of aerosol particles with other hygroscopic or hydrophobic particles, updraft velocity of the parcel carrying these particles, availability of condensable water vapor and number of CCN competing for the water (Petters et al. 2006;
Roberts et al. 2003). Reutter et al. (2009) modeled deep clouds formed above BB fires (pyro-convective clouds) using a cloud parcel model, and showed that the cloud droplet number concentration, NCD, is sensitive to changes in κ of aerosol particles, when κ is lower than 0.2. For instance, an 81% increase in κ (as measured in this study) of particles having initial κ = 0.057 can cause a 20% increase in NCD.
I confirm the findings of Slade et al. (2015) that O3-aging has no effect on the measured hygroscopicity of OC aerosol. However, my findings suggest the formation of organic films on particles after O3 oxidation and condensation of organic gases in the aerosol. An evidence of this finding is the retarded growth of droplets after they activate in the cloud chamber. Even though
cloud chamber studies do not simulate limitations on the amount of condensable water available for droplets to grow, these limitations exist in the atmosphere (Roberts et al. 2003). As shown by Feingold and Chuang (2002) and Ruehl et al. (2007), in such conditions of competition, CCN coated with such growth-retarding organic films could grow slower compared to other uncoated CCN, leading to broadened size distributions and possibly prolonged lifetimes of droplets in the atmosphere.
REFERENCES
Abbatt, J. P. D., A. K. Y. Lee, and J. A. Thornton. (2012). “Quantifying Trace Gas Uptake to Tropospheric Aerosol:
Recent Advances and Remaining Challenges.” Chemical Society Reviews 41 (19). The Royal Society of Chemistry: 6555–81. doi:10.1039/C2CS35052A.
Albrecht, B. A. (1989). “Aerosols, Cloud Microphysics, and Fractional Cloudiness.” Science 245 (4923): 1227–30.
http://www.scopus.com/inward/record.url?eid=2-s2.0-0024812929&partnerID=tZOtx3y1.
Andreae, M. O., and D. Rosenfeld. (2008). “Aerosol-Cloud-Precipitation Interactions. Part 1. The Nature and Sources of Cloud-Active Aerosols.” Earth-Science Reviews 89: 13–41. doi:10.1016/j.earscirev.2008.03.001.
Asa-Awuku, A., A. Nenes, S. Gao, R. C. Flagan, and J. H. Seinfeld. (2010). “Water-Soluble SOA from Alkene Ozonolysis: Composition and Droplet Activation Kinetics Inferences from Analysis of CCN Activity.”
Atmospheric Chemistry and Physics 10 (4): 1585–97. doi:10.5194/acp-10-1585-2010.
Bela, M. M., K. M. Longo, S. R. Freitas, D. S. Moreira, V. Beck, S. C. Wofsy, C. Gerbig, K. Wiedemann, M. O.
Andreae, and P. Artaxo. (2015). “Ozone Production and Transport over the Amazon Basin during the Dry-to-Wet and Dry-to-Wet-to-Dry Transition Seasons.” Atmospheric Chemistry and Physics Discussions 14 (10): 14005–
70. doi:10.5194/acpd-14-14005-2014.
Blanchard, D. C., and A. H. Woodcock. (1957). “Bubble Formation and Modification in the Sea and Its Meteorological Significance.” Tellus 9 (2): 145–58.
Bond, T. C., D. G. Streets, K. F. Yarber, S. M. Nelson, J. Woo, and Z. Klimont. (2004). “A Technology-Based Global Inventory of Black and Organic Carbon Emissions from Combustion.” Journal of Geophysical Research 109 (D14): D14203. doi:10.1029/2003JD003697.
Brem, B. T., F. C. Mena Gonzalez, S. R. Meyers, T. C. Bond, and M. J. Rood. (2012). “Laboratory-Measured Optical Properties of Inorganic and Organic Aerosols at Relative Humidities up to 95%.” Aerosol Science and Technology 46 (2). Taylor & Francis Group: 178–90. doi:10.1080/02786826.2011.617794.
Camponogara, G., M. A. F. Silva-Dias, and G. G. Carrió. (2014). “Relationship between Amazon Biomass Burning Aerosols and Rainfall over the La Plata Basin.” Atmospheric Chemistry and Physics 14 (9): 4397–4407.
doi:10.5194/acp-14-4397-2014.
Chand, D., R. Wood, S. J. Ghan, M. Wang, M. Ovchinnikov, P. J. Rasch, S. Miller, B. Schichtel, and T. Moore.
(2012). “Aerosol Optical Depth Increase in Partly Cloudy Conditions.” Journal of Geophysical Research:
Atmospheres 117 (17): 1–8. doi:10.1029/2012JD017894.
Chen, Y., and T. C. Bond. (2010). “Light Absorption by Organic Carbon from Wood Combustion.” Atmospheric Chemistry and Physics 10 (4). Copernicus GmbH: 1773–87. doi:10.5194/acp-10-1773-2010.
Dinar, E., T. Anttila, and Y. Rudich. (2008). “CCN Activity and Hygroscopic Growth of Organic Aerosols Following Reactive Uptake of Ammonia.” Environmental Science and Technology 42 (3): 793–99.
Dusek, U., D. S. Covert, A. Wiedensohler, C. Neusüss, D. Weise, and W. Cantrell. (2003). “Cloud Condensation Nuclei Spectra Derived from Size Distributions and Hygroscopic Properties of the Aerosol in Coastal South-West Portugal during ACE-2.” Tellus, Series B: Chemical and Physical Meteorology 55 (1): 35–53.
doi:10.1034/j.1600-0889.2003.00041.x.
Dusek, U., G. P. Frank, A. Massling, K. Zeromskiene, Y. Iinuma, O. Schmid, G. Helas, T. Hennig, A.
Wiedensohler, and M. O. Andreae. (2011). “Water Uptake by Biomass Burning Aerosol at Sub- and Supersaturated Conditions: Closure Studies and Implications for the Role of Organics.” Atmospheric Chemistry and Physics 11 (18): 9519–32. doi:10.5194/acp-11-9519-2011.
Engelhart, G. J., A. Asa-Awuku, A. Nenes, and S. N. Pandis. (2008). “CCN Activity and Droplet Growth Kinetics of Fresh and Aged Monoterpene Secondary Organic Aerosol.” Atmospheric Chemistry and Physics 8 (14):
3937–49.
Evans, R. J., and T. A. Milne. (1987). “Molecular Characterization of the Pyrolysis of Biomass. 1. Fundamentals.”
Energy & Fuels 1 (2): 123–37.
Feingold, G., and P. Y. Chuang. (2002). “Analysis of the Influence of Film-Forming Compounds on Droplet Growth: Implications for Cloud Microphysical Processes and Climate.” Journal of the Atmospheric Sciences 59 (12): 2006–18. doi:10.1175/1520-0469(2002)059<2006:AOTIOF>2.0.CO;2.
Fiore, A. (2003). “Variability in Surface Ozone Background over the United States: Implications for Air Quality Policy.” Journal of Geophysical Research 108 (D24). doi:10.1029/2003JD003855.
Flagan, R. C. (2011). “Electrical Mobility Methods for Submicrometer Particle Characterization.” In Aerosol Measurement: Principles, Techniques and Applications, edited by P. Kulkarni, P. A. Baron, and K. Willeke, Third, 339–64. John Wiley & Sons, Inc. doi:10.1002/9781118001684.ch15.
Fuchs, N. A. (1963). “On the Stationary Charge Distribution on Aerosol Particles in a Bipolar Ionic Atmosphere.”
Geofisica Pura E Applicata 56 (1): 185–93. doi:10.1007/BF01993343.
Gysel, M., G. McFiggans, and H. Coe. (2009). “Inversion of Tandem Differential Mobility Analyser (TDMA) Measurements.” Journal of Aerosol Science 40: 134–51. doi:10.1016/j.jaerosci.2008.07.013.
IEA. (2013). “(International Energy Agency) World Energy Outlook.” Paris: International Energy Agency. Paris.
doi:92-64-20131-9.
Jacob, D. (1999). Introduction to Atmospheric Chemistry. Princeton University Press.
John, W. (2011). “Size Distribution Characteristics of Aerosols.” In Aerosol Measurement: Principles, Techniques and Applications, edited by P. Kulkarni, P. A. Baron, and K. Willeke, Third, 41–54. John Wiley & Sons, Inc.
doi:10.1002/9781118001684.ch4.
John, W., S. M. Wall, J. L. Ondo, and W. Winklmayr. (1990). “Modes in the Size Distributions of Atmospheric Inorganic Aerosol.” Atmospheric Environment. Part A. General Topics 24 (9): 2349–59. doi:10.1016/0960-1686(90)90327-J.
Junge, C. E. (1963). Air Chemistry and Radioactivity. New York : Academic Press,.
Kanakidou, M., J. H. Seinfeld, S. N. Pandis, I. Barnes, F. J. Dentener, M. C. Facchini, R. Van Dingenen, et al.
(2005). “Organic Aerosol and Global Climate Modelling: A Review.” Atmospheric Chemistry and Physics 5 (4): 1053–1123. doi:10.5194/acp-5-1053-2005.
Köhler, H. (1936). “The Nucleus in and the Growth of Hygroscopic Droplets.” Transactions of the Faraday Society 32 (0). The Royal Society of Chemistry: 1152–61. doi:10.1039/TF9363201152.
Lambe, A. T., A. T. Ahern, J. P. Wright, D. R. Croasdale, P. Davidovits, and T. B. Onasch. (2015). “Oxidative Aging and Cloud Condensation Nuclei Activation of Laboratory Combustion Soot.” Journal of Aerosol Science 79 (January). Elsevier Ltd: 31–39. doi:10.1016/j.jaerosci.2014.10.001.
Lance, S., A. Nenes, J. Medina, and J. N. Smith. (2006). “Mapping the Operation of the DMT Continuous Flow CCN Counter.” Aerosol Science and Technology 40 (4): 242–54. doi:10.1080/02786820500543290.
Lathem, T. L., and A. Nenes. (2011). “Water Vapor Depletion in the DMT Continuous-Flow CCN Chamber: Effects on Supersaturation and Droplet Growth.” Aerosol Science and Technology 45 (5): 604–15.
doi:10.1080/02786826.2010.551146.
Lewin, E. E., R. G. De Pena, and J. P. Shimshock. (1986). “Atmospheric Gas and Particle Measurement at a Rural Northeastern U.S. Site.” Atmospheric Environment - Part A General Topics 20 (1): 59–70.
Li, Z., A. L. Williams, and M. J. Rood. (1998). “Influence of Soluble Surfactant Properties on the Activation of Aerosol Particles Containing Inorganic Solute.” Journal of the Atmospheric Sciences 55 (10). American Meteorological Society: 1859–66. doi:10.1175/1520-0469(1998)055<1859:IOSSPO>2.0.CO;2.
Madonna, L. A., C. M. Sciulli, L. N. Canjar, and G. M. Pound. (1961). “Low Temperature Cloud Chamber Studies on Water Vapour.” Proceedings of the Physical Society 78 (6): 1218–22. doi:10.1088/0370-1328/78/6/317.
McCormick, R. A., and J. H. Ludwig. (1967). “Climate Modification by Atmospheric Aerosols.” Science 156 (3780): 1358–59. http://www.scopus.com/inward/record.url?eid=2-s2.0-0014196775&partnerID=tZOtx3y1.
Myhre, G., D. Shindell, F.-M. Bréon, W. Collins, J. Fuglestvedt, J. Huang, D. Koch, et al. (2013). “2013:
Anthropogenic and Natural Radiative Forcing.” Climate Change 2013: The Physical Science Basis.
Contribution of Working Group I to the Fifth Assessment Report of the Intergovernmental Panel on Climate Change, 659–740. doi:10.1017/ CBO9781107415324.018.
Petters, M. D., C. M. Carrico, S. M. Kreidenweis, A. J. Prenni, P. J. DeMott, J. L. Collett, and H. Moosmüller.
(2009). “Cloud Condensation Nucleation Activity of Biomass Burning Aerosol.” Journal of Geophysical Research: Atmospheres 114 (22).
Petters, M. D., and S. M. Kreidenweis. (2007). “A Single Parameter Representation of Hygroscopic Growth and Cloud Condensation Nucleus Activity.” Atmospheric Chemistry and Physics 7 (8): 1961–71.
http://www.scopus.com/inward/record.url?eid=2-s2.0-34247382562&partnerID=tZOtx3y1.
Petters, M. D., A. J. Prenni, S. M. Kreidenweis, P. J. DeMott, A. Matsunaga, Y. B. Lim, and P. J. Ziemann. (2006).
“Chemical Aging and the Hydrophobic-to-Hydrophilic Conversion of Carbonaceous Aerosol.” Geophysical Research Letters 33 (24): 1–5. doi:10.1029/2006GL027249.
Rader, D. J., and P. H. McMurry. (1986). “Application of the Tandem Differential Mobility Analyzer to Studies of Droplet Growth or Evaporation.” Journal of Aerosol Science 17 (5): 771–87.
doi:10.1016/0021-8502(86)90031-5.
Reutter, P., J. Trentmann, H. Su, M. Simmel, D. Rose, H. Wernli, M. O. Andreae, and U. Pöschl. (2009). “Aerosol- and Updraft-Limited Regimes of Cloud Droplet Formation: Influence of Particle Number, Size and
Hygroscopicity on the Activation of Cloud Condensation Nuclei (CCN).” Atmospheric Chemistry and Physics Discussions 9 (2): 8635–65. doi:10.5194/acpd-9-8635-2009.
Roberts, G. C., and A. Nenes. (2005). “A Continuous-Flow Streamwise Thermal-Gradient CCN Chamber for Atmospheric Measurements.” Aerosol Science and Technology 39 (3): 206–21.
doi:10.1080/027868290913988.
Roberts, G. C., A. Nenes, J. H. Seinfeld, and M. O. Andreae. (2003). “Impact of Biomass Burning on Cloud Properties in the Amazon Basin.” Journal of Geophysical Research 108 (D2). doi:10.1029/2001JD000985.
Rood, M. J., M. A. Shaw, T. V. Larson, and D. S. Covert. (1989). “Ubiquitous Nature of Ambient Metastable Aerosol.” Nature 337 (6207): 537–39. http://dx.doi.org/10.1038/337537a0.
Rudich, Y., N. M. Donahue, and T. F. Mentel. (2007). “Aging of Organic Aerosol: Bridging the Gap between Laboratory and Field Studies.” Annual Review of Physical Chemistry.
Ruehl, C. R., P. Y. Chuang, and A. Nenes. (2007). “How Quickly Do Cloud Droplets Form on Atmospheric Particles?” Atmospheric Chemistry and Physics Discussions 7 (5): 14233–64. doi:10.5194/acpd-7-14233-2007.
Slade, J. H., and D. A. Knopf. (2013). “Heterogeneous OH Oxidation of Biomass Burning Organic Aerosol Surrogate Compounds: Assessment of Volatilisation Products and the Role of OH Concentration on the Reactive Uptake Kinetics.” Physical Chemistry Chemical Physics 15 (16). The Royal Society of Chemistry:
5898–5915. doi:10.1039/C3CP44695F.
Slade, J. H., R. Thalman, J. Wang, and D. A. Knopf. (2015). “Chemical Aging of Single and Multicomponent Biomass Burning Aerosol Surrogate-Particles by OH: Implications for Cloud Condensation Nucleus Activity.”
Atmospheric Chemistry and Physics Discussions 15 (5): 6771–6819. doi:10.5194/acpd-15-6771-2015.
Stier, P., J. Feichter, S. Kloster, E. Vignati, and J. Wilson. (2006). “Emission-Induced Nonlinearities in the Global Aerosol System: Results from the ECHAM5-HAM Aerosol-Climate Model.” Journal of Climate 19 (16):
3845–62. doi:10.1175/JCLI3772.1.
Tang, I. N. (1979). “Deliquescence Properties and Particle Size Change of Hygroscopic Aerosols.” Brookhaven National Lab., Upton, NY (USA).
Tegen, I. (2003). “Modeling the Mineral Dust Aerosol Cycle in the Climate System.” Quaternary Science Reviews 22 (18-19): 1821–34. doi:10.1016/S0277-3791(03)00163-X.
Trebs, I., S. Metzger, F. X. Meixner, G. Helas, A. Hoffer, Y. Rudich, A. H. Falkovich, et al. (2005). “The NH4+-NO3 --Cr-SO4 2--H2O Aerosol System and Its Gas Phase Precursors at a Pasture Site in the Amazon Basin:
How Relevant Are Mineral Cations and Soluble Organic Acids?” Journal of Geophysical Research:
Atmospheres 110 (7): 1–18. doi:10.1029/2004JD005478.
Twohy, C. H., J. A. Coakley, and W. R. Tahnk. (2009). “Effect of Changes in Relative Humidity on Aerosol Scattering near Clouds.” Journal of Geophysical Research: Atmospheres 114 (5): 1–12.
doi:10.1029/2008JD010991.
Twomey, S. (1974). “Pollution and the Planetary Albedo.” Atmospheric Environment (1967) 8 (12): 1251–56.
doi:10.1016/0004-6981(74)90004-3.
Watson, J. G. (2002). “Spatial Differences in Outdoor PM10 Mass and Aerosol Composition in Mexico City.”
Journal of the Air and Waste Management Association 52 (4). Taylor and Francis Inc.: 423–34.
Whitby, K. T. (1978). “The Physical Characteristics of Sulfur Aerosols.” Atmospheric Environment (1967) 12 (1-3):
135–59. doi:10.1016/0004-6981(78)90196-8.
Wilson, C. T. R. (1897). “Condensation of Water Vapour in the Presence of Dust-Free Air and Other Gases.”
Philosophical Transactions of the Royal Society of London A: Mathematical, Physical and Engineering
Winter, K. E. (2002). “Control of Relative Humidity in an Automated Nephelometer System for Ambient Aerosol Measurements.” Master’s Thesis, University of Illinois at Urbana-Champaign.
Wu, Z. J., A. Nowak, L. Poulain, H. Herrmann, and A. Wiedensohler. (2011). “Hygroscopic Behavior of Atmospherically Relevant Water-Soluble Carboxylic Salts and Their Influence on the Water Uptake of Ammonium Sulfate.” Atmospheric Chemistry and Physics 11 (24): 12617–26. doi:10.5194/acp-11-12617-2011.