Aerosol hygroscopicity at high (99 to 100%) relative humidities

Abstract. The hygroscopicity of an aerosol strongly influences its effects on climate and, for smaller particles, atmospheric lifetime. While many aerosol hygroscopicity measurements have been made at lower relative humidities (RH) and under cloud formation conditions (RH>100%), relatively few have been made at high RH (99 to 100%), where the Kelvin (curvature) effect is comparable to the Raoult (solute) effect. We measured the size of droplets at high RH that had formed on particles composed of one of seven compounds with dry diameters between 0.1 and 0.5 μm. We report the hygroscopicity of these compounds using a parameterization of the Kelvin term, in addition to a standard parameterization (κ) of the Raoult term. For inorganic compounds, hygroscopicity could reliably be predicted using water activity data (measured in macroscopic solutions) and assuming a surface tension of pure water. In contrast, most organics exhibited a slight to mild increase in hygroscopicity with droplet diameter. This trend was strongest for sodium dodecyl sulfate (SDS), the most surface-active compound studied. The results suggest that, for single-component aerosols at high RH, partitioning of solute to the particle-air interface reduces particle hygroscopicity by reducing the bulk solute concentration. This partitioning effect is more important than the increase in hygroscopicity due to surface tension reduction. Furthermore, we found no evidence that micellization limits SDS activity in micron-sized solution droplets, as observed in macroscopic solutions. We conclude that while the high-RH hygroscopicity of inorganic compounds can be reliably predicted using readily available data, surface-activity parameters obtained from macroscopic solutions with organic solutes may be inappropriate for calculations involving micron-sized droplets.

[1]  C. Ruehl,et al.  Distinct CCN activation kinetics above the marine boundary layer along the California coast , 2009 .

[2]  M. Petters,et al.  Towards closing the gap between hygroscopic growth and activation for secondary organic aerosol: Part 1 – Evidence from measurements , 2009 .

[3]  A. Wexler,et al.  Thermodynamic Model of the System H , 2009 .

[4]  D. Topping,et al.  The Kelvin versus the Raoult Term in the Kohler Equation , 2008 .

[5]  M. Petters,et al.  A single parameter representation of hygroscopic growth and cloud condensation nucleus activity – Part 2: Including solubility , 2008 .

[6]  Laura Mitchem,et al.  Comparative thermodynamic studies of aqueous glutaric acid, ammonium sulfate and sodium chloride aerosol at high humidity. , 2008, The journal of physical chemistry. A.

[7]  Y. Rudich,et al.  Enrichment of surface‐active compounds in coalescing cloud drops , 2008 .

[8]  Tomi Raatikainen,et al.  Ternary solution of sodium chloride, succinic acid and water; surface tension and its influence on cloud droplet activation , 2008 .

[9]  Spyros N. Pandis,et al.  CCN activity and droplet growth kinetics of fresh and aged monoterpene secondary organic aerosol , 2008 .

[10]  D. Worsnop,et al.  CCN activation experiments with adipic acid: effect of particle phase and adipic acid coatings on soluble and insoluble particles , 2008 .

[11]  S. Kreidenweis,et al.  Measurements of the hygroscopic and deliquescence properties of organic compounds of different solubilities in water and their relationship with cloud condensation nuclei activities. , 2008, Environmental science & technology.

[12]  M. Rusdi,et al.  Examination of Surface Adsorption of Soluble Surfactants by Surface Potential Measurement at the Air/Solution Interface , 2008 .

[13]  R. H. Moore,et al.  Molar mass, surface tension, and droplet growth kinetics of marine organics from measurements of CCN activity , 2008 .

[14]  E. Lewis.  An examination of Köhler theory resulting in an accurate expression for the equilibrium radius ratio of a hygroscopic aerosol particle valid up to and including relative humidity 100 , 2008 .

[15]  Martin Gysel,et al.  Cloud forming potential of secondary organic aerosol under near atmospheric conditions , 2008 .

[16]  C. Ruehl,et al.  How quickly do cloud droplets form on atmospheric particles , 2007 .

[17]  Frank Stratmann,et al.  Hygroscopic growth and activation of HULIS particles: Experimental data and a new iterative parameterization scheme for complex aerosol particles , 2007 .

[18]  H. Hansson,et al.  Modelling the cloud condensation nucleus activity of organic acids , 2007 .

[19]  J. Heintzenberg,et al.  LACIS-measurements and parameterization of sea-salt particle hygroscopic growth and activation , 2007 .

[20]  Yinon Rudich,et al.  Hygroscopic growth of atmospheric and model humic-like substances , 2007 .

[21]  A. Nenes,et al.  Atmospheric Chemistry and Physics Discussions Interactive comment on “ Investigation of molar volume and surfactant characteristics of water-soluble organic compounds in biomass burning aerosol ” , 2007 .

[22]  Martin Gysel,et al.  Hygroscopic growth and water uptake kinetics of two-phase aerosol particles consisting of ammonium sulfate, adipic and humic acid mixtures , 2007 .

[23]  Alfred Wiedensohler,et al.  Hygroscopic growth and measured and modeled critical super‐saturations of an atmospheric HULIS sample , 2007 .

[24]  S. Sjogrena,et al.  Hygroscopic growth and water uptake kinetics of two-phase aerosol particles consisting of ammonium sulfate, adipic and humic acid mixtures , 2007 .

[25]  Riikka Sorjamaa,et al.  The influence of surfactant properties on critical supersaturations of cloud condensation nuclei , 2006 .

[26]  Maria Cristina Facchini,et al.  Surface tensions of multi-component mixed inorganic/organic aqueous systems of atmospheric significance: measurements, model predictions and importance for cloud activation predictions , 2006 .

[27]  M. Petters,et al.  A single parameter representation of hygroscopic growth and cloud condensation nucleus activity , 2006 .

[28]  Yinon Rudich,et al.  Cloud Condensation Nuclei properties of model and atmospheric HULIS , 2006 .

[29]  N. Matubayasi,et al.  Thermodynamic quantities of surface formation of aqueous electrolyte solutions. VI. Comparison with typical nonelectrolytes, sucrose and glucose. , 2006, Journal of colloid and interface science.

[30]  Harri Kokkola,et al.  Cloud formation of particles containing humic‐like substances , 2006 .

[31]  Alla Zelenyuk,et al.  From Agglomerates of Spheres to Irregularly Shaped Particles: Determination of Dynamic Shape Factors from Measurements of Mobility and Vacuum Aerodynamic Diameters , 2006 .

[32]  M. Facchini,et al.  Importance of the organic aerosol fraction for modeling aerosol hygroscopic growth and activation: a case study in the Amazon Basin , 2005 .

[33]  F. Stratmann,et al.  Measured and modeled equilibrium sizes of NaCl and (NH4)2SO4 particles at relative humidities up to 99.1 , 2005 .

[34]  Sonia M. Kreidenweis,et al.  Influence of water‐soluble organic carbon on cloud drop number concentration , 2005 .

[35]  Axel Lauer,et al.  © Author(s) 2006. This work is licensed under a Creative Commons License. Atmospheric Chemistry and Physics Analysis and quantification of the diversities of aerosol life cycles , 2022 .

[36]  A. Tabazadeh.  Organic aggregate formation in aerosols and its impact on the physicochemical properties of atmospheric particles , 2005 .

[37]  J. Abbatt,et al.  Cloud condensation nucleus activity of internally mixed ammonium sulfate/organic acid aerosol particles , 2005 .

[38]  Hans-Christen Hansson,et al.  Surface Tension Effects of Humic-Like Substances in the Aqueous Extract of Tropospheric Fine Aerosol , 2005 .

[39]  A. Nenes,et al.  A Continuous-Flow Streamwise Thermal-Gradient CCN Chamber for Atmospheric Measurements , 2005 .

[40]  U. Lohmann,et al.  Importance of submicron surface-active organic aerosols for pristine Arctic clouds , 2005 .

[41]  B. Svenningsson,et al.  Cloud droplet activation and surface tension of mixtures of slightly soluble organics and inorganic salt , 2004 .

[42]  A. Laaksonen,et al.  Atmospheric Chemistry and Physics The role of surfactants in Köhler theory reconsidered , 2004 .

[43]  M. Rusdi,et al.  Difference in Surface Properties between Insoluble Monolayer and Adsorbed Film from Kinetics of Water Evaporation and BAM Image. , 2004, The journal of physical chemistry. B.

[44]  J. Seinfeld,et al.  Chemical Amplification (or Dampening) of the Twomey Effect: Conditions Derived from Droplet Activation Theory , 2004 .

[45]  S. Ghan,et al.  Parameterization of the influence of organic surfactants on aerosol activation , 2004 .

[46]  K. Broekhuizen,et al.  Partially soluble organics as cloud condensation nuclei: Role of trace soluble and surface active species , 2004 .

[47]  A. Laaksonen,et al.  The role of surfactants in K ¨ ohler theory reconsidered , 2004 .

[48]  W. Kunz,et al.  Vapor Pressures and Osmotic Coefficients of Aqueous Solutions of SDS, C6TAB, and C8TAB at 25 °C , 2003 .

[49]  A. Kasper-Giebl,et al.  Surface tension of Rax cloud water and its relation to the concentration of organic material , 2002 .

[50]  L. Russell,et al.  Mapping organic coatings on atmospheric particles , 2002 .

[51]  Kaarle Kupiainen,et al.  New evidence of an organic layer on marine aerosols , 2002 .

[52]  Sonia M. Kreidenweis,et al.  The effects of low molecular weight dicarboxylic acids on cloud formation , 2001 .

[53]  M. Facchini,et al.  Comments on “Influence of Soluble Surfactant Properties on the Activation of Aerosol Particles Containing Inorganic Solute” , 2001 .

[54]  Peter Brimblecombe,et al.  Thermodynamic modelling of aqueous aerosols containing electrolytes and dissolved organic compounds , 2001 .

[55]  E. Franses,et al.  Adsorption and surface tension of ionic surfactants at the air–water interface: review and evaluation of equilibrium models , 2001 .

[56]  Microstructural rearrangement of sodium chloride condensation aerosol particles on interaction with water vapor , 2000 .

[57]  M. Facchini,et al.  Cloud albedo enhancement by surface-active organic solutes in growing droplets , 1999, Nature.

[58]  Adrian F. Tuck,et al.  Atmospheric processing of organic aerosols , 1999 .

[59]  Measurements of interfacial properties with the axisymmetric bubble-shape analysis technique: effects of vibrations , 1998 .

[60]  M. Rood,et al.  Influence of Soluble Surfactant Properties on the Activation of Aerosol Particles Containing Inorganic Solute , 1998 .

[61]  A. Wexler,et al.  Thermodynamic Model of the System H+−NH4+−Na+−SO42-−NO3-−Cl-−H2O at 298.15 K , 1998 .

[62]  P. Saxena,et al.  Water-soluble organics in atmospheric particles: A critical review of the literature and application of thermodynamics to identify candidate compounds , 1996 .

[63]  J. Hudson,et al.  Volatility and size of cloud condensation nuclei , 1996 .

[64]  R. Synovec,et al.  Dissolution behavior and surface tension effects of organic compounds in nucleating cloud droplets , 1996 .

[65]  Elias I. Franses,et al.  Adsorption dynamics of surfactants at the air/water interface: a critical review of mathematical models, data, and mechanisms , 1995 .

[66]  R. Synovec,et al.  Laser-based dynamic surface tension detection for liquid chromatography by probing a repeating drop radius , 1995 .

[67]  E. Franses,et al.  Adsorption dynamics of single and binary surfactants at the air/water interface , 1992 .

[68]  W. Bachalo,et al.  Phase/Doppler Spray Analyzer For Simultaneous Measurements Of Drop Size And Velocity Distributions , 1984 .

[69]  W. Seidl,et al.  Surface-active substances on rainwater and atmospheric particles , 1983 .

[70]  Charles J. Weschler,et al.  Organic films on atmospheric aerosol particles, fog droplets, cloud droplets, raindrops, and snowflakes , 1983 .

[71]  J. W. Fitzgerald,et al.  The Size and Scattering Coefficient of Urban Aerosol Particles at Washington, DC as a Function of Relative Humidity. , 1982 .

[72]  W. Bachalo.  Method for measuring the size and velocity of spheres by dual-beam light-scatter interferometry. , 1980, Applied optics.

[73]  Rudolf B. Husar,et al.  Thermal Analyses of the Los Angeles Smog Aerosol. , 1975 .

[74]  R. Robinson,et al.  Interactions in Aqueous Nonelectrolyte Solutions. I. Solute-Solvent Equilibria , 1966 .

[75]  W. Kieffer.  The physico-chemical constants of binary systems in concentrated solutions. Volumes 1 and 2: Two organic compounds (Timmermans, Jean) , 1960 .

[76]  J. Timmermans.  The physico-chemical constants of binary systems in concentrated solutions , 1959 .

[77]  B. Szyszkowski.  Experimentelle Studien über kapillare Eigenschaften der wässerigen Lösungen von Fettsäuren , 1908 .

[78]  A. Eaton.  Cloud Formation. , 1893, Science.