Atmospheric evolution of organic aerosol

[1] We report here results of an experimental study of the OH-initiated oxidation of solid organics in the presence of O2, NOx and H2O, using two kinds of self-assembled organic monolayers (alkane and aromatic), paraffin and pyrene films as proxies for organic aerosol. We show that the OH-initiated oxidation of the alkane surfaces leads to rapid volatilization. The gas-phase products detected include HO2, H2O2, CO, CO2, HCO, CH2O, CH3CHO, CH3OH, and HCOOH. We conclude that volatilization is at least as efficient as wet deposition as a removal process for aliphatic particulates, whereas aromatic particulates show higher stability towards volatilization.

[1]  Glen R. Cass,et al.  Contribution of primary aerosol emissions from vegetation‐derived sources to fine particle concentrations in Los Angeles , 1996 .

[2]  R. Atkinson Atmospheric reactions of alkoxy and ?-hydroxyalkoxy radicals , 1997 .

[3]  V. Vaida,et al.  Processing of unsaturated organic acid films and aerosols by ozone , 2003 .

[4]  Yinon Rudich,et al.  Reactive Uptake of Ozone by Aerosol-Associated Unsaturated Fatty Acids: Kinetics, Mechanism, and Products , 2002 .

[5]  V. Vaida,et al.  Oxidation of organic films relevant to atmospheric aerosols , 2004 .

[6]  D. Murphy,et al.  Identification of a Surface Alkylperoxy Radical in the Photocatalytic Oxidation of Acetone/O2 over TiO2 , 2003 .

[7]  H. Cohen,et al.  Monolayer Damage in XPS Measurements As Evaluated by Independent Methods , 1997 .

[8]  M. Molina,et al.  The Reaction Probability of OH on Organic Surfaces of Tropospheric Interest , 2001 .

[9]  J. Penner,et al.  A global three‐dimensional model study of carbonaceous aerosols , 1996 .

[10]  R. Atkinson Gas-Phase Tropospheric Chemistry of Organic Compounds , 1994 .

[11]  Correction to ``Effect of peroxy radical reactions on the predicted concentrations of ozone, nitrogenous compounds, and radicals'' , 1996 .

[12]  C. Corrigan,et al.  Cloud condensation nucleus activity of the organic component of biomass smoke particles , 1996 .

[13]  Norman Cohen,et al.  Are reaction rate coefficients additive? Revised transition state theory calculations for OH + alkane reactions , 1991 .

[14]  H. Hansson,et al.  Organic atmospheric aerosols: Review and state of the science , 2000 .

[15]  D. M. Cunnold,et al.  Evidence for Substantial Variations of Atmospheric Hydroxyl Radicals in the Past Two Decades , 2001, Science.

[16]  V. Grassian Chemical Reactions of Nitrogen Oxides on the Surface of Oxide, Carbonate, Soot, and Mineral Dust Particles: Implications for the Chemical Balance of the Troposphere , 2002 .

[17]  Jacob N. Israelachvili,et al.  Contact angles on chemically heterogeneous surfaces , 1989 .

[18]  Glen R. Cass,et al.  Quantification of urban organic aerosols at a molecular level: Identification, abundance and seasonal variation , 1993 .

[19]  R. Atkinson Gas-phase tropospheric chemistry of organic compounds: a review , 1990 .

[20]  D. Briggs,et al.  High resolution XPS of organic polymers , 1992 .

[21]  H. Budzinski,et al.  Heterogeneous Reactivity of OH Radicals with Phenanthrene , 2003 .

[22]  Y. Rudich,et al.  Uptake of Cl and Br by organic surfaces—A perspective on organic aerosols processing by tropospheric oxidants , 2001 .

[23]  Jack G. Calvert,et al.  The mechanisms of atmospheric oxidation of aromatic hydrocarbons , 2002 .

[24]  J. Seinfeld,et al.  Atmospheric Chemistry and Physics: From Air Pollution to Climate Change , 1997 .

[25]  Roger Atkinson,et al.  Gas-Phase Tropospheric Chemistry of Volatile Organic Compounds: 1. Alkanes and Alkenes , 1997 .

[26]  G. Zaikov,et al.  Heterogeneous features of autooxidation of hydrocarbon polymers , 2001 .

[27]  G. Stenchikov,et al.  The impact of aerosols on solar ultraviolet radiation and photochemical smog. , 1997, Science.