Modeling Atmospheric Chemistry: Interactions between Gas-Phase Species and Liquid Cloud/Aerosol Particles

For detailed modeling of atmospheric chemistry it is necessary to consider aqueous-phase reactions in cloud droplets and deliquesced aerosol particles. Often, the gas-phase concentration is in equilibrium with the aqueous phase. Then Henry′s law can be used to describe the distribution between the phases provided that the Henry′s law coefficient is known. In some cases, thermodynamic equilibrium will not be reached and it is necessary to use kinetic expressions of the rates involved. These rates depend on diffusion constants, accommodation coefficients, Henry′s law coefficients, particle size distributions, and several other parameters. This review describes how these processes can be treated in computer modeling and how the necessary data can be obtained. Even though it is written primarily for use in modeling atmospheric chemistry, some parts will also be useful for waste water and pesticide control and in other areas where the distribution of chemicals between the aqueous and the gas phase is important.

[1]  H. Stephen,et al.  Solubilities of inorganic and organic compounds , 1963 .

[2]  P. Brimblecombe,et al.  The solubility and behaviour of acid gases in the marine aerosol , 1988 .

[3]  C. Zetzsch,et al.  Heterogeneous Interconversion Reactions of BrNO2, ClNO2, Br2, and Cl2 , 1998 .

[4]  W. Shiu,et al.  A critical review of Henry’s law constants for chemicals of environmental interest , 1981 .

[5]  M. Mozurkewich,et al.  Peroxynitric Acid Decay Mechanisms and Kinetics at Low pH , 1997 .

[6]  Paul J. Crutzen,et al.  A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer , 1996 .

[7]  Paul J. Crutzen,et al.  Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea , 1996 .

[8]  Paul J. Crutzen,et al.  The role of clouds in tropospheric photochemistry , 1991 .

[9]  J. Galloway,et al.  Heterogeneous sulfur conversion in sea-salt aerosol particles: the role of aerosol water content and size distribution , 1991 .

[10]  T. Graedel,et al.  Chemistry within aqueous atmospheric aerosols and raindrops , 1981 .

[11]  M. Williams,et al.  CRC Handbook of Chemistry and Physics, 76th edition , 1996 .

[12]  D. Jacob Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate , 1986 .

[13]  E.,et al.  MASS-TRANSPORT LIMITATION TO THE RATE OF REACTION OF GASES IN LIQUID DROPLETS : APPLICATION TO OXIDATION OF SO 2 IN AQUEOUS SOLUTIONS , 1980 .

[14]  M. Zahniser,et al.  Henry's law solubilities and Śetchenow coefficients for biogenic reduced sulfur species obtained from gas‐liquid uptake measurements , 1995 .

[15]  H. Coe,et al.  SO2 oxidation in an entraining cloud model with explicit microphysics , 1991 .

[16]  Charles E. Kolb,et al.  Dynamics and Kinetics at the Gas−Liquid Interface , 1996 .

[17]  D. D. Wagman,et al.  The NBS tables of chemical thermodynamic properties : selected values for inorganic and C1 and C2 organic substances in SI units , 1982 .

[18]  E. Betterton Henry's law constants of soluble and moderately soluble organic gases : effects on aqueous phase chemistry , 1992 .

[19]  A. Fredenslund,et al.  Henry's Law Constants and Infinite Dilution Activity Coefficients for Volatile Organic Compounds in Water by a Validated Batch Air Stripping Method. , 1994, Environmental science & technology.

[20]  W. Shiu,et al.  Determination of air-water Henry's law constants for hydrophobic pollutants , 1979 .

[21]  P. Crutzen,et al.  Aerosol pH in the marine boundary layer: A review and model evaluation , 1998 .

[22]  D. Davis,et al.  The free radical chemistry of cloud droplets and its impact upon the composition of rain , 1982 .

[23]  Paul V. Roberts,et al.  A critical review of Henry's law constants for environmental applications , 1996 .

[24]  Stephen E. Schwartz,et al.  Mass-Transport Considerations Pertinent to Aqueous Phase Reactions of Gases in Liquid-Water Clouds , 1986 .

[25]  R. Battino,et al.  Low-pressure solubility of gases in liquid water , 1977 .

[26]  N. Fuchs,et al.  HIGH-DISPERSED AEROSOLS , 1971 .

[27]  Suojiang Zhang,et al.  Measuring methods of infinite dilution activity coefficients and a database for systems including water , 1997 .

[28]  R. C. Weast CRC Handbook of Chemistry and Physics , 1973 .

[29]  D. Sahni The effect of a black sphere on the flux distribution in an infinite moderator , 1966 .

[30]  M. Molina,et al.  Chemical kinetics and photochemical data for use in stratospheric modeling , 1985 .

[31]  W. Chameides,et al.  Aqueous‐phase chemical processes in deliquescent sea‐salt aerosols: A mechanism that couples the atmospheric cycles of S and sea salt , 1992 .