Phase, morphology, and hygroscopicity of mixed oleic acid/sodium chloride/water aerosol particles before and after ozonolysis.

Aerosol optical tweezers are used to probe the phase, morphology, and hygroscopicity of single aerosol particles consisting of an inorganic component, sodium chloride, and a water insoluble organic component, oleic acid. Coagulation of oleic acid aerosol with an optically trapped aqueous sodium chloride droplet leads to formation of a phase-separated particle with two partially engulfed liquid phases. The dependence of the phase and morphology of the trapped particle with variation in relative humidity (RH) is investigated by cavity enhanced Raman spectroscopy over the RH range <5% to >95%. The efflorescence and deliquescence behavior of the inorganic component is shown to be unaffected by the presence of the organic phase. Whereas efflorescence occurs promptly (<1 s), the deliquescence process requires both dissolution of the inorganic component and the adoption of an equilibrium morphology for the resulting two phase particle, occurring on a time-scale of <20 s. Comparative measurements of the hygroscopicity of mixed aqueous sodium chloride/oleic acid droplets with undoped aqueous sodium chloride droplets show that the oleic acid does not impact on the equilibration partitioning of water between the inorganic component and the gas phase or the time response of evaporation/condensation. The oxidative aging of the particles through reaction with ozone is shown to increase the hygroscopicity of the organic component.

[1]  P. Vandenabeele,et al.  Reference database of Raman spectra of biological molecules , 2007 .

[2]  K. Hunter,et al.  Relationship between the lipid compositions of marine aerosols, the sea surface microlayer, and subsurface water , 1979 .

[3]  J. Nájera,et al.  Infrared spectroscopic study of the effect of oleic acid on the deliquescence behaviour of ammonium sulfate aerosol particles. , 2009, Physical chemistry chemical physics : PCCP.

[4]  Jonathan P. Reid,et al.  Spectroscopic studies of the size and composition of single aerosol droplets , 2007 .

[5]  C. Chan,et al.  Single particle Raman spectroscopy for investigating atmospheric heterogeneous reactions of organic aerosols , 2007 .

[6]  C. Chan,et al.  The effects of organic species on the hygroscopic behaviors of inorganic aerosols. , 2002, Environmental science & technology.

[7]  W. R. Leaitch,et al.  The hygroscopicity parameter (κ) of ambient organic aerosol at a field site subject to biogenic and anthropogenic influences: relationship to degree of aerosol oxidation , 2010 .

[8]  C. G. D. Kruif,et al.  Thermodynamic properties of the normal alkanoic acids III. Enthalpies of vaporization and vapour pressures of 13 normal alkanoic acids , 1982 .

[9]  Jonathan P. Reid,et al.  Optical manipulation and characterisation of aerosol particles using a single-beam gradient force optical trap. , 2008, Chemical Society reviews.

[10]  Jariya Buajarern,et al.  Characterizing multiphase organic/inorganic/aqueous aerosol droplets. , 2007, The journal of physical chemistry. A.

[11]  Scot T. Martin,et al.  Phase Transitions of Aqueous Atmospheric Particles. , 2000, Chemical reviews.

[12]  Laura Mitchem,et al.  In situ comparative measurements of the properties of aerosol droplets of different chemical composition. , 2008, Faraday discussions.

[13]  Deresh Ramjugernath,et al.  Estimation of pure component properties: Part 1. Estimation of the normal boiling point of non-electrolyte organic compounds via group contributions and group interactions , 2004 .

[14]  Jonathan P. Reid,et al.  Observation of bistability of trapping position in aerosol optical tweezers , 2010 .

[15]  Deresh Ramjugernath,et al.  Estimation of pure component properties: Part 3. Estimation of the vapor pressure of non-electrolyte organic compounds via group contributions and group interactions , 2008 .

[16]  M. Kalberer,et al.  Product study of oleic acid ozonolysis as function of humidity , 2009 .

[17]  Daphne L. Che,et al.  Variations in organic aerosol optical and hygroscopic properties upon heterogeneous OH oxidation , 2011 .

[18]  A. Robinson,et al.  Laboratory measurements of the oxidation kinetics of organic aerosol mixtures using a relative rate constants approach , 2007 .

[19]  A. Demond,et al.  Estimation of interfacial tension between organic liquids and water , 1993 .

[20]  Thomas Peter,et al.  Mixing of the Organic Aerosol Fractions: Liquids as the Thermodynamically Stable Phases , 2004 .

[21]  T. Petäjä,et al.  Relationship between aerosol oxidation level and hygroscopic properties of laboratory generated secondary organic aerosol (SOA) particles , 2010 .

[22]  J. Abbatt,et al.  Heterogeneous oxidation of atmospheric aerosol particles by gas-phase radicals. , 2010, Nature chemistry.

[23]  T. Peter,et al.  Efflorescence of ammonium sulfate and coated ammonium sulfate particles: evidence for surface nucleation. , 2010, Journal of Physical Chemistry A.

[24]  I. Tang,et al.  Aerosol growth studies—II. Preparation and growth measurements of monodisperse salt aerosols , 1977 .

[25]  A. Ravishankara,et al.  Evidence for liquid-like and nonideal behavior of a mixture of organic aerosol components , 2008, Proceedings of the National Academy of Sciences.

[26]  J. Hearn,et al.  Measuring rates of reaction in supercooled organic particles with implications for atmospheric aerosol. , 2005, Physical chemistry chemical physics : PCCP.

[27]  Jariya Buajarern,et al.  A strategy for characterizing the mixing state of immiscible aerosol components and the formation of multiphase aerosol particles through coagulation. , 2006, The journal of physical chemistry. B.

[28]  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.

[29]  P. Ziemann Aerosol products, mechanisms, and kinetics of heterogeneous reactions of ozone with oleic acid in pure and mixed particles. , 2005, Faraday discussions.

[30]  Roger E. Miller,et al.  Reactive Uptake of Ozone by Oleic Acid Aerosol Particles: Application of Single-Particle Mass Spectrometry to Heterogeneous Reaction Kinetics , 2002 .

[31]  C. O'Dowd,et al.  Marine aerosol production: a review of the current knowledge , 2007, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

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

[33]  Claudia Marcolli,et al.  Do atmospheric aerosols form glasses , 2008 .

[34]  Douglas R. Worsnop,et al.  Products and Mechanisms of Ozone Reactions with Oleic Acid for Aerosol Particles Having Core−Shell Morphologies , 2004 .

[35]  Glen R. Cass,et al.  Sources of fine organic aerosol. 1. Charbroilers and meat cooking operations , 1991 .

[36]  Jonathan P. Reid,et al.  Optical control and characterisation of aerosol , 2009 .

[37]  Michael J. Kleeman,et al.  Measurement of Emissions from Air Pollution Sources. 1. C1 through C29 Organic Compounds from Meat Charbroiling , 1999 .

[38]  U. Pöschl,et al.  Amorphous and crystalline aerosol particles interacting with water vapor: conceptual framework and experimental evidence for restructuring, phase transitions and kinetic limitations , 2009 .

[39]  Giuseppe A. Petrucci,et al.  The oleic acid-ozone heterogeneous reaction system : products , kinetics , secondary chemistry , and atmospheric implications of a model system – a review , 2007 .

[40]  Hugh Coe,et al.  A curved multi-component aerosol hygroscopicity model framework: Part 1 Inorganic compounds , 2005 .

[41]  S. Rushworth,et al.  Measurements of the equilibrium size of supersaturated aqueous sodium chloride droplets at low relative humidity using aerosol optical tweezers and an electrodynamic balance. , 2010, The journal of physical chemistry. A.

[42]  D. M. Carey,et al.  Measurement of the Raman Spectrum of Liquid Water , 1996 .

[43]  J. Seinfeld,et al.  Organic atmospheric particulate material. , 2003, Annual review of physical chemistry.

[44]  A. J. Campillo,et al.  Input/output resonance correlation in laser-induced emission from microdroplets , 1995 .

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

[46]  E. Weingartner,et al.  Changes of fatty acid aerosol hygroscopicity induced by ozonolysis under humid conditions , 2007 .

[47]  G. Biskos,et al.  Ozonolysis of mixed oleic-acid/stearic-acid particles: reaction kinetics and chemical morphology. , 2005, The journal of physical chemistry. A.

[48]  Tami C. Bond,et al.  Critical assessment of the current state of scientific knowledge, terminology, and research needs concerning the role of organic aerosols in the atmosphere, climate, and global change , 2005 .

[49]  A. Bertram,et al.  Predicting the relative humidities of liquid-liquid phase separation, efflorescence, and deliquescence of mixed particles of ammonium sulfate, organic material, and water using the organic-to-sulfate mass ratio of the particle and the oxygen-to-carbon elemental ratio of the organic component , 2011 .

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

[51]  Jonathan P. Reid,et al.  Direct measurements of the axial displacement and evolving size of optically trapped aerosol droplets , 2007 .

[52]  Y. Nojiri,et al.  Fatty acids in the marine atmosphere: Factors governing their concentrations and evaluation of organic films on sea‐salt particles , 2002 .

[53]  Jariya Buajarern,et al.  Spectroscopy of growing and evaporating water droplets: exploring the variation in equilibrium droplet size with relative humidity. , 2006, The journal of physical chemistry. A.

[54]  A. Ravishankara,et al.  Evaporation rates and vapor pressures of the even-numbered C8-C18 monocarboxylic acids. , 2008, The journal of physical chemistry. A.

[55]  D. Donaldson,et al.  Role of the aerosol substrate in the heterogeneous ozonation reactions of surface-bound PAHs. , 2007, The journal of physical chemistry. A.

[56]  John B. Nowak,et al.  Infrared spectroscopy of model tropospheric aerosols as a function of relative humidity: Observation of deliquescence and crystallization , 1997 .

[57]  K. Kupiainen,et al.  Identification of an organic coating on marine aerosol particles by TOF‐SIMS , 2002 .

[58]  Shao-Meng Li,et al.  Characterizations of cis-pinonic acid and n-fatty acids on fine aerosols in the Lower Fraser Valley during Pacific 2001 Air Quality Study , 2004 .

[59]  J. Reid,et al.  The morphology of aerosol particles consisting of hydrophobic and hydrophilic phases: hydrocarbons, alcohols and fatty acids as the hydrophobic component. , 2011, Physical chemistry chemical physics : PCCP.

[60]  Y. Rudich,et al.  Interaction of internally mixed aerosols with light. , 2010, Physical chemistry chemical physics : PCCP.