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

Abstract

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.

This is a preview of subscription content, log in to check access.

References

  1. Atkins, P.W.: 1986, Physical Chemistry, Oxford University Press.

  2. Battino, R., Clever, H.L., Fogg, P.G.T., and Young, C.L.: 1995, 'Introduction to the solubility data series. Solubility of gases in liquids', http://www.unileoben.ac.at/~eschedor/gl-intro.html.

  3. Betterton, E.A.: 1992, 'Henry's law constants of soluble and moderately soluble organic gases: Effects on aqueous phase chemistry', Adv. Environ. Sci. Technol. 24, 1-50.

    Google Scholar 

  4. Bower, K.N., Hill, T.A., Coe, H., and Choularton, T.W.: 1991, 'SO2 oxidation in an entraining cloud model with explicit microphysics', Atmos. Environ. 25A, 2401-2418.

    Google Scholar 

  5. Brimblecombe, P. and Clegg, S.L.: 1988, 'The solubility and behaviour of acid gases in the marine aerosol', J. Atmos. Chem. 7, 1-18.

    Google Scholar 

  6. Chameides, W.L. and Davis, D.D.: 1982, 'The free radical chemistry of cloud droplets and its impact upon the composition of rain', J. Geophys. Res. 87C, 4863-4877.

    Google Scholar 

  7. Chameides, W.L. and Stelson, A.W.: 1992, 'Aqueous phase chemical processes in deliquescent seasalt aerosols: A mechanism that couples the atmospheric cycles of S and sea salt', J. Geophys. Res. 97D, 20565-20580.

    Google Scholar 

  8. De Bruyn, W.J., Swartz, E., Hu, J.H., Shorter, J.A., Davidovits, P., Worsnop, D.R., Zahniser, M.S., and Kolb, C.E.: 1995, 'Henry's law solubilities and Śetchenow coefficients for biogenic reduced sulfur species obtained from gas-liquid uptake measurements', J. Geophys. Res. 100D, 7245-7251.

    Google Scholar 

  9. DeMore, W.B., Sander, S.P., Golden, D.M., Hampson, R.F., Kurylo, M.J., Howard, C.J., Ravishankara, A.R., Kolb, C.E., and Molina, M.J.: 1997, 'Chemical kinetics and photochemical data for use in stratospheric modeling', JPL Publication 97-4, Jet Propulsion Laboratory, Pasadena, CA.

    Google Scholar 

  10. Dubik, N.A., Titova, G.M., and Loshakova, E.I.: 1987, 'Partition coefficients of bromine and bromine chloride between air and natural brines', Issled. v Obl. Poluch. Magniya, Ioda, Broma i ikh Soed., M. pp. 53-57. (in Russian, see also Chem. Abstr., 109, 213154j).

  11. Frenzel, A., Scheer, V., Sikorski, R., George, C., Behnke, W., and Zetzsch, C.: 1998, 'Heterogeneous interconversion reactions of BrNO2, ClNO2, Br2, and Cl2', J. Phys. Chem. A 102, 1329-1337.

    Google Scholar 

  12. Fuchs, N.A. and Sutugin, A.G.: 1971, Highly Dispersed Aerosols, Ann Arbor Science, Ann Arbor, Mich.

    Google Scholar 

  13. Graedel, T.E. and Weschler, C.J.: 1981, 'Chemistry within aqueous atmospheric aerosols and raindrops', Rev. Geophys. Space Phys. 19, 505-539.

    Google Scholar 

  14. Jacob, D.J.: 1986, 'Chemistry of OH in remote clouds and its role in the production of formic acid and peroxymonosulfate', J. Geophys. Res. 91D, 9807-9826.

    Google Scholar 

  15. Jaenicke, R.: 1987, 'Aerosol physics and chemistry', In: Landolt-Börnstein New Series V/4b.

  16. Keene, W.C., Sander, R., Pszenny, A.A.P., Vogt, R., Crutzen, P.J., and Galloway, J.N.: 1998, 'Aerosol pH in the marine boundary layer: A review and model evaluation', J. Aerosol Sci. 29, 339-356.

    Google Scholar 

  17. Kojima, K., Zhang, S., and Hiaki, T.: 1997, 'Measuring methods of infinite dilution coefficients and a database for systems including water', Fluid Phase Equilib. 131, 145-179.

    Google Scholar 

  18. Lelieveld, J. and Crutzen, P.J.: 1991, 'The role of clouds in tropospheric photochemistry', J. Atmos. Chem. 12, 229-267.

    Google Scholar 

  19. Lide, D.R. and Frederikse, H.P.R. (eds.): 1995, CRC Handbook of Chemistry and Physics, 76th Edition. CRC Press, Inc., Boca Raton, FL.

    Google Scholar 

  20. Mackay, D. and Shiu, W.Y.: 1981, 'A critical review of Henry's law constants for chemicals of environmental interest', J. Phys. Chem. Ref. Data 10, 1175-1199.

    Google Scholar 

  21. Mackay, D., Shiu, W.Y., and Sutherland, R.P.: 1979, 'Determination of air-water Henry's law constants for hydrophobic pollutants', Environ. Sci. Technol. 13, 333-337.

    Google Scholar 

  22. Mills, I., Cvitaš, T., Homann, K., Kallay, N., and Kuchitsu, K.: 1993, International Union of Pure and Applied Chemistry: Quantities, Units and Symbols in Physical Chemistry, Blackwell Science, Boca Raton.

    Google Scholar 

  23. Müller, F.: 1998, 'Compilation of accommodation coefficients', http://www.mi.uni-hamburg.de/technische_meteorologie/Meso/homepages/fmueller.html.

  24. Nathanson, G.M., Davidovits, P., Worsnop, D.R., and Kolb, C.E.: 1996, 'Dynamics and kinetics at the gas-liquid interface', J. Phys. Chem. 100, 13007-13020.

    Google Scholar 

  25. Nielsen, F., Olsen, E., and Fredenslund, A.: 1994, 'Henry's law constants and infinite dilution activity coefficients for volatile organic compounds in water by a validated batch air stripping method', Environ. Sci. Technol. 28, 2133-2138.

    Google Scholar 

  26. Pandis, S.N. and Seinfeld, J.H.: 1989, 'Sensitivity analysis of a chemical mechanism for aqueousphase atmospheric chemistry', J. Geophys. Res. 94D, 1105-1126.

    Google Scholar 

  27. Pitzer, K.S. (ed.): 1991, Activity Coefficients in Electrolyte Solutions, 2nd Edition, CRC Press, Inc., Boca Raton, FL.

    Google Scholar 

  28. Régimbal, J.-M. and Mozurkewich, M.: 1997, 'Peroxynitric acid decay mechanisms and kinetics at low pH', J. Phys. Chem. A 101, 8822-8829.

    Google Scholar 

  29. Sahni, D.C.: 1966, 'The effect of a black sphere on the flux distribution in an infinite moderator', J. Nucl. Energy 20, 915-920.

    Google Scholar 

  30. Sander, R.: 1996, 'Compilation of Henry's law constants for inorganic and organic species of potential importance in environmental chemistry (version 2)', http://www.mpch-mainz.mpg.de/~sander/res/henry.html.

  31. Sander, R. and Crutzen, P.J.: 1996, 'Model study indicating halogen activation and ozone destruction in polluted air masses transported to the sea', J. Geophys. Res. 101D, 9121-9138.

    Google Scholar 

  32. Schwartz, S.E.: 1986, 'Mass-transport considerations pertinent to aqueous phase reactions of gases in liquid-water clouds', In: W. Jaeschke (ed.): Chemistry of Multiphase Atmospheric Systems, NATO ASI Series, Vol. G6. pp. 415-471.

  33. Schwartz, S.E. and Freiberg, J.E.: 1981, 'Mass-transport limitation to the rate of reaction of gases in liquid droplets: Application to oxidation of SO2 in aqueous solutions', Atmos. Environ. 15, 1129-1144.

    Google Scholar 

  34. Seinfeld, J.H. and Pandis, S.N.: 1998, Atmospheric Chemistry and Physics, John Wiley & Sons, Inc.

  35. Sievering, H., Boatman, J., Galloway, J., Keene, W., Kim, Y., Luria, M., and Ray, J.: 1991, 'Heterogeneous sulfur conversion in sea-salt aerosol particles: The role of aerosol water content and size distribution', Atmos. Environ. 25A, 1479-1487.

    Google Scholar 

  36. Staudinger, J. and Roberts, P.V.: 1996, 'A critical review of Henry's law constants for environmental applications', Crit. Rev. Environ. Sci. Technol. 26, 205-297.

    Google Scholar 

  37. Stephen, H. and Stephen, T.: 1963, Solubilities of inorganic and organic compounds, Vol. 1. Pergamon Press, Oxford.

    Google Scholar 

  38. Vogt, R., Crutzen, P.J., and Sander, R.: 1996, 'A mechanism for halogen release from sea-salt aerosol in the remote marine boundary layer', Nature 383, 327-330.

    Google Scholar 

  39. Wagman, D.D., Evans, W.H., Parker, V.B., Schumm, R.H., Halow, I., Bailey, S.M., Churney, K.L., and Nuttall, R.L.: 1982, 'The NBS tables of chemical thermodynamic properties; Selected values for inorganic and C1 and C2 organic substances in SI units', J. Phys. Chem. Ref. Data 11, suppl. 2.

  40. Wilhelm, E., Battino, R., and Wilcock, R.J.: 1977, 'Low-pressure solubility of gases in liquid water', Chem. Rev. 77, 219-262.

    Google Scholar 

Download references

Author information

Affiliations

Authors

Rights and permissions

Reprints and Permissions

About this article

Cite this article

Sander, R. Modeling Atmospheric Chemistry: Interactions between Gas-Phase Species and Liquid Cloud/Aerosol Particles. Surveys in Geophysics 20, 1–31 (1999). https://doi.org/10.1023/A:1006501706704

Download citation

  • heterogeneous atmospheric chemistry
  • chemistry
  • Henry′s law
  • accommodation coefficient
  • cloud droplet
  • aerosol particle
  • solubility
  • volatility
  • diffusion