Understanding hygroscopic growth and phase transformation of aerosols using single particle Raman spectroscopy in an electrodynamic balance.

Hygroscopic growth is one of the most fundamental properties of atmospheric aerosols. By absorbing or evaporating water, an aerosol particle changes its size, morphology, phase, chemical composition and reactivity and other parameters such as its refractive index. These changes affect the fate and the environmental impacts of atmospheric aerosols, including global climate change. The ElectroDynamic Balance (EDB) has been widely accepted as a unique tool for measuring hygroscopic properties and for investigating phase transformation of aerosols via single particle levitation. Coupled with Raman spectroscopy, an EDB/Raman system is a powerful tool that can be used to investigate both physical and chemical changes associated with the hygroscopic properties of individually levitated particles under controlled environments. In this paper, we report the use of an EDB/Raman system to investigate (1) contact ion pairs formation in supersaturated magnesium sulfate solutions; (2) phase transformation in ammonium nitrate/ammonium sulfate mixed particles; (3) hygroscopicity of organically coated inorganic aerosols; and (4) heterogeneous reactions altering the hygroscopicity of organic aerosols.

[1]  John H Seinfeld,et al.  Thermodynamic models of aqueous solutions containing inorganic electrolytes and dicarboxylic acids at 298.15 K. 1. The acids as nondissociating components. , 2006, The journal of physical chemistry. A.

[2]  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 .

[3]  P. Chuang Measurement of the timescale of hygroscopic growth for atmospheric aerosols , 2003 .

[4]  Hugh Coe,et al.  A curved multi-component aerosol hygroscopicity model framework: Part 2 - Including organic compounds , 2005 .

[5]  W. Seidl Model for a surface film of fatty acids on rain water and aerosol particles , 2000 .

[6]  C. Esen,et al.  Raman Investigation of Photopolymerization Reactions of Single Optically Levitated Microparticles , 1996 .

[7]  J. Popp,et al.  Observation of a phase transition in an electrodynamically levitated NH4NO3 microparticle by Mie and Raman scattering , 2000 .

[8]  P. Buseck,et al.  Wet and dry sizes of atmospheric aerosol particles: An AFM‐TEM Study , 1998 .

[9]  Chak K. Chan,et al.  Understanding the Hygroscopic Properties of Supersaturated Droplets of Metal and Ammonium Sulfate Solutions Using Raman Spectroscopy , 2002 .

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

[11]  Y. Rudich Laboratory perspectives on the chemical transformations of organic matter in atmospheric particles. , 2003, Chemical reviews.

[12]  M. Facchini,et al.  Water soluble organic compounds formed by oxidation of soot , 2002 .

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

[14]  C. Chan,et al.  Heterogeneous reactions of linoleic acid and linolenic acid particles with ozone: reaction pathways and changes in particle mass, hygroscopicity, and morphology. , 2007, The journal of physical chemistry. A.

[15]  C. Chan,et al.  Relating Hygroscopic Properties of Magnesium Nitrate to the Formation of Contact Ion Pairs , 2004 .

[16]  S. Kreidenweis,et al.  Water uptake of internally mixed particles containing ammonium sulfate and dicarboxylic acids , 2003 .

[17]  W. Kiefer,et al.  Structural resonances observed in the Raman spectra of optically levitated liquid droplets. , 1985, Applied optics.

[18]  R. A. Cox,et al.  Phase transitions and hygroscopic growth of aerosol particles containing humic acid and mixtures of humic acid and ammonium sulphate , 2005 .

[19]  Bernhard Lendl,et al.  Direct monitoring of lipid oxidation in edible oils by Fourier transform Raman spectroscopy. , 2005, Chemistry and physics of lipids.

[20]  C. L. Aardahl,et al.  Gas/Aerosol Chemical Reactions in the NaOH-SO2-H2O System , 1996 .

[21]  J. Popp,et al.  Investigations of chemical reactions between single levitated magnesium chloride microdroplets with SO2 and NOx by means of Raman spectroscopy and elastic light scattering , 1999 .

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

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

[24]  J. Seinfeld,et al.  Water activities of NH4NO3/(NH4)2SO4 solutions , 1992 .

[25]  D. Donaldson,et al.  Enhanced uptake of water by oxidatively processed oleic acid , 2004 .

[26]  J. Leszczynski,et al.  Initiation Reactions of Lipid Peroxidation: A Raman Spectroscopic and Quantum-Mechanical Study , 1998 .

[27]  Richard C. Flagan,et al.  Single-particle levitation system for automated study of homogeneous solute nucleation , 2006 .

[28]  J. Seinfeld,et al.  Studies of concentrated electrolyte solutions using the electrodynamic balance. 1. Water activities for single-electrolyte solutions , 1987 .

[29]  J. Popp,et al.  Investigations of the composition changes of an evaporating, single binary-mixture microdroplet by inelastic and elastic light scattering , 1998 .

[30]  Cory C. Pye,et al.  Raman Spectroscopic Measurements and ab Initio Molecular Orbital Studies of Cadmium(II) Hydration in Aqueous Solution , 1998 .

[31]  Jonathan P. Reid,et al.  Cavity Enhanced Droplet Spectroscopy: Principles, Perspectives and Prospects , 2004 .

[32]  John B. Anderson,et al.  Changes in Antarctic stratospheric aerosol characteristics due to volcanic eruptions as monitored by the Stratospheric Aerosol and Gas Experiment II satellite , 1995 .

[33]  Chak K. Chan,et al.  Study of Contact Ion Pairs of Supersaturated Magnesium Sulfate Solutions Using Raman Scattering of Levitated Single Droplets , 2000 .

[34]  Zong-ci Zhao,et al.  Climate change 2001, the scientific basis, chap. 8: model evaluation. Contribution of Working Group I to the Third Assessment Report of the Intergovernmental Panel on Climate Change IPCC , 2001 .

[35]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1998 .

[36]  P. Buseck,et al.  Individual aerosol particles from biomass burning in southern Africa: 1. Compositions and size distributions of carbonaceous particles , 2003 .

[37]  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 .

[38]  Cory C. Pye,et al.  An ab Initio and Raman Investigation of Magnesium(II) Hydration , 1998 .

[39]  K. H. Fung,et al.  Hydration and Raman scattering studies of levitated microparticles: Ba(NO3)2, Sr(NO3)2, and Ca(NO3)2 , 1997 .

[40]  K. H. Fung,et al.  Raman scattering from single solution droplets. , 1988, Applied optics.

[41]  Erik Swietlicki,et al.  Organic aerosol and global climate modelling: a review , 2004 .

[42]  Peter Brimblecombe,et al.  Thermodynamic Model of the System H+−NH4+−SO42-−NO3-−H2O at Tropospheric Temperatures , 1998 .

[43]  C. Chan,et al.  The hygroscopic properties of dicarboxylic and multifunctional acids: measurements and UNIFAC predictions. , 2001, Environmental science & technology.

[44]  G. Socrates,et al.  Infrared and Raman characteristic group frequencies : tables and charts , 2001 .

[45]  A. Bertram,et al.  Deliquescence and crystallization of ammonium sulfate‐glutaric acid and sodium chloride‐glutaric acid particles , 2004 .

[46]  J. Seinfeld,et al.  Organics alter hygroscopic behavior of atmospheric particles , 1995 .

[47]  N. Porter,et al.  Mechanisms of free radical oxidation of unsaturated lipids , 1995, Lipids.

[48]  C. Chan,et al.  Responses of ammonium sulfate particles coated with glutaric acid to cyclic changes in relative humidity: hygroscopicity and Raman characterization. , 2006, Environmental science & technology.

[49]  T. Lettieri,et al.  Characterization of single levitated droplets by Raman spectroscopy , 1985 .

[50]  C. Chan,et al.  The Water Activities of MgCl2, Mg(NO3)2, MgSO4, and Their Mixtures , 1999 .

[51]  W. Rudolph,et al.  A Raman spectroscopic study of hydration and water‐ligand replacement reaction in aqueous cadmium(II)‐sulfate solution: Inner‐sphere and outer‐sphere complexes , 1998 .

[52]  John H Seinfeld,et al.  Thermodynamic models of aqueous solutions containing inorganic electrolytes and dicarboxylic acids at 298.15 K. 2. Systems including dissociation equilibria. , 2006, The journal of physical chemistry. A.

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

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

[55]  Gert Irmer,et al.  Raman and infrared spectroscopic investigation of contact ion pair formation in aqueous cadmium sulfate solutions , 1994 .

[56]  C. Chan,et al.  Hygroscopic properties of two model humic-like substances and their mixtures with inorganics of atmospheric importance. , 2003, Environmental science & technology.

[57]  K. H. Fung,et al.  Phase transformation and metastability of hygroscopic microparticles , 1995 .

[58]  G. Schweiger,et al.  Investigation of the desorption of acetylene from acetone microdroplets by Raman spectroscopy , 1996 .

[59]  Barry G. Oliver,et al.  Raman spectroscopic evidence for contact ion pairing in aqueous magnesium sulfate solutions , 1973 .

[60]  C. Chan,et al.  Mass transfer effects on the hygroscopic growth of ammonium sulfate particles with a water-insoluble coating , 2007 .

[61]  E. James Davis,et al.  A History of Single Aerosol Particle Levitation , 1997 .

[62]  D. Lin-Vien The Handbook of Infrared and Raman Characteristic Frequencies of Organic Molecules , 1991 .