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Estimation of the rate constant for the reaction of acid sulphate aerosol with NH3 gas from atmospheric measurements

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Abstract

Horizontal gradients in atmospheric aerosol strong acidity have been interpreted in terms of the rate of neutralisation of aerosol H+ by gaseous ammonia. The results indicate a pseudo-first-order rate constant for this reaction within the range 4×10-6 s-1 to 4.1×10-4 s-1 consistent with model results and experimental data derived by other methods. The rate constant is reduced as the aerosol becomes less acidic, which is reflected in a positive correlation between rate constant and aerosol H+/NH4 + ratio.

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References

  • Allen A. G., Harrison R. M., and Wake M. T., 1988, A meso-scale study of the behaviour of atmospheric ammonia and ammonium, Atmos. Environ. 22, 1347–1353.

    Google Scholar 

  • Allen A. G., Harrison R. M., and Erisman J. W., 1989, Field measurements of the dissociation of ammonium nitrate and ammonium chloride aerosols, Atmos. Environ. 23, 1591–1599.

    Google Scholar 

  • ApSimon H. M., Kruse M., and Bell J. N., 1987, Ammonia emissions and their role in acid deposition, Atmos. Environ. 21, 1939–1946.

    Google Scholar 

  • Asman W. A. H. and Janssen A. J., 1987, A long-range transport model for ammonia and ammonium ion for Europe, Atmos. Environ. 21, 2099–2119.

    Google Scholar 

  • Asman W. A. H. van Jaarsveld H. A., 1990, A variable-resolution statistical transport model applied for ammonia and ammonium. Report No. 228471007, National Institute of Public Health and Environmental Protection, Bilthoven, The Netherlands.

    Google Scholar 

  • Asman W. A. H., Drukker B., and Janssen A. J., 1988, Modelled historical concentration and depositions of ammonia and ammonium in Europe, Atmos. Environ. 22, 825–735.

    Google Scholar 

  • Baldwin A. C. and Golden D. M., 1979, Heterogeneous atmospheric reactions: sulphuric acid as tropospheric sink, Science 206, 562–563.

    Google Scholar 

  • Bassett M. E. and Seinfeld J. H., 1983, Atmospheric equilibrium model of sulphate and nitrate aerosols, Atmos. Environ. 18, 1163–1170.

    Google Scholar 

  • Bassett M. E. and Seinfeld J. H., 1984, Atmospheric equilibrium model of sulphate and nitrate aerosols-II. Particle size analysis, Atmos. Environ. 18, 1163–1170.

    Google Scholar 

  • Brosset C. and Ferm M., 1978, Man-made airborne acidity and its determination, Atmos. Environ. 12, 909–916.

    Google Scholar 

  • Brosset C., 1978, Water soluble sulphur compounds in aerosols, Atmos. Environ. 12, 25–38.

    Google Scholar 

  • Buijsman E. D. Maas H. F. M., and Asman W. A. H., 1987, Anthropogenic NH3 emissions in Europe, Atmos. Environ. 21, 1009–1022.

    Google Scholar 

  • Cass G. R., Gharib S., Peyerson M., and Tilder J. W., 1982, The origin of ammonia emission to the atmosphere in urban area. Open file report 82–6. Environmental Quality Laboratory, Calif. U.S.A.

    Google Scholar 

  • Cobourn W. G., Hjukic-Husar J., and Husar R. B., 1980, Monitoring of sulphuric acid episodes in St. Louis, Missouri, J. Geophys. Res. 85, 4487–4494.

    Google Scholar 

  • Daumer, B., Niessner, R. and Klockow, D., 1987, Interaction of gaseous ammonia with coated sulphuric aerosol: laboratory results in Ammonia and Acidification, W. A. H. Asman and S. M. A. Diederen (eds.), Bilthoven, The Netherlands.

  • Elshout A. J., Viljeer J. W., and Duuren H., 1978, Sulphates and sulphuric acid in the atmosphere in the years 1971–1976 in The Netherlands, Atmos. Environ. 12, 785–790.

    Google Scholar 

  • Erisman J. W., Vermetten A. W. M., Asman W. A. H., Waijers-Ijpelaan A., and Slanina J., 1988, Vertical distribution of gases and aerosols: The behaviour of ammonia and related components in the lower atmosphere, Atmos. Environ. 22, 1153–1160.

    Google Scholar 

  • Erisman J. W., Vermetten A. W. M., Asman W. A. H., and Waijers-Ijpelaan A., 1989b, Deposition of the most acidifying components in the Netherlands in 1980–1986, Atmos. Environ. 23, 1051–1062.

    Google Scholar 

  • Ferek R. J., Lazrus A. L., Haagenson P. L., and Winchester J. W., 1983, Strong and weak acidity of aerosols collected over the north eastern United States, Environ. Sci. Technol. 17, 315–325.

    Google Scholar 

  • Gill P. S., Graedel T. E., and Weschler C. J., 1983, Organic films on atmospheric aerosol particles, fog droplets, cloud droplets, raindrops and snow flakes, Rev. Geophys. Space Phys. 21, 903–920.

    Google Scholar 

  • Gran G., 1952, Determination of equivalence point in potentiometric titrations, Analyst 17, 661–671.

    Google Scholar 

  • Harrison R. M., Rapsomanikis S., and Turnbull A., 1989, Land-surface exchange in a chemically-reactive system: surface fluxes of HNO3, HCl and NH3, Atmos. Environ. 23, 1900–1905.

    Google Scholar 

  • Huntzicker J. J., Cary R. A., and Ling C.-S., 1980, Neutralization of sulphuric acid aerosol by ammonia, Environ. Sci. Technol. 14, 819–824.

    Google Scholar 

  • Klarenbeek, J. V., 1987, Ammonia emissions from livestock operations in the Netherlands, in W. A. H. Asman and H. S. M. A. Diederen (eds.), Ammonia and Acidification, Bilthoven, The Netherlands.

  • Keeler G. J., Spengler J. D., Koutrakis P., Allen G. A., Raizenne M., and Stern B., 1990, Transported acid aerosols measured in Southern Ontario, Atmos. Environ. 24A, 2935–2950.

    Google Scholar 

  • Kitto, A. M.-N. and Harrison, R. M., 1992, Processes affecting concentrations of aerosol strong acid acidity (H2SO4) at sites in eastern England, Atmos. Environ. in press.

  • Koutrakis P., Wolfson J. M., and Spengler J. D., 1988, An improved method for measuring aerosol strong acidity: results from a nine-month study in St. Louis, Missouri and Kingston, Tennessee, Atmos. Environ. 22, 157–162.

    Google Scholar 

  • Lenhard U. and Gravenhorst G., 1980, Evaluation of ammonia fluxes into free atmosphere over western Germany, Tellus 32, 48–55.

    Google Scholar 

  • McMurry P. H., Takano H. and Anderson G. R., 1983, Study of the ammonia (gas)-sulphuric acid (aerosol) reaction rate, Environ Sci. Technol. 17, 347–352.

    Google Scholar 

  • McQuaker N. R. and Sandberg D. K., 1988, Gran's titration and ion balance: some analytical control limits for precipitation and surface water, Environ. Sci. Technol. 22, 590–592.

    Google Scholar 

  • Morandi M. T., Kneip T. J., Cobourn W. G., Husar R. B., and Lioy P. J., 1983, The measurements of H2SO4 and other sulphate species at Tuxedo, New York with a thermal analysis flame photometric detector, Atmos. Environ. 17, 843–848.

    Google Scholar 

  • Phillips M. E., Gaffrey J. S., Goodrich R. W., and Tanner R. L., 1984, Computer-assisted Gran titration procedure for strong acid determination, Brookhaven National Laboratory, Upton N.Y. Report BNL. 35734.

    Google Scholar 

  • Pierson W. R., Brachaczek W. W., Gorse R. A., Japar S. M., Norbeck J. M., and Keeler G. J., 1989, Atmospheric acidity measurements on Allegheny mountain and the origins of the ambient acidity in the northeastern United States, Atmos. Environ. 23, 431–459.

    Google Scholar 

  • Rapsomanikis S., Wake M., Kitto A. M.-N., and Harrison R. M., 1988, Analysis of atmospheric ammonia and particulate ammonium by a sensitive fluorescence method, Environ. Sci. Technol. 22, 948–952.

    Google Scholar 

  • Robbins R. C. and Cadle R. D., 1958, Kinetics of the reaction between gaseous ammonia and sulphuric acid droplets in an aerosol, Phys. Chem. 62, 469–471.

    Google Scholar 

  • Schwartz S. E. and Freidberg J. E., 1981, Mass-transport limitation to the rate of the reaction og gases in liquid droplets, Atmos. Environ. 15, 1129–1144.

    Google Scholar 

  • Smith R. A., 1872, Air and Rain: The Beginnings of a Chemical Climatology, Longmans, Green & Co., London.

    Google Scholar 

  • Stelson A. W. and Seinfeld J. H., 1982a, Relative humidity and temperature dependence of the ammonium nitrate dissociation constant, Atmos. Environ. 16, 983–992.

    Google Scholar 

  • Stelson A. W. and Seinfeld J. H., 1982b, Relative humidity and pH dependence of the vapour pressure of ammonium nitrate-nitric acid solutions at 25 °C, Atmos. Environ. 16, 993–1000.

    Google Scholar 

  • Tanner R. L., Cederwall R., Garber R., Leahy D., Marlow W., and Newman L., 1977, Separation and analysis of aerosol sulphate species at ambient concentrations, Atmos. Environ. 11, 955–966.

    Google Scholar 

  • Tanner R. L., 1982, An ambient experiment study of phase equilibrium in the atmospheric system aerosol H+, NH4 +, SO4 2-, NO3 -, NH3(g) and HNO3(g), Atmos. Environ. 16, 2935–2942.

    Google Scholar 

  • Tanner R. L., Kumar R., and Johnson S., 1984, Vertical distribution of strong aerosol, J. Geophys. Res. 89, 7149–7158.

    Google Scholar 

  • Van Breemen N., Burrough P. A., Velthorst E. J., van Dobben H. F., De Wit T., Ridder T. B., and Reijnders H. F. R., 1982, Soil acidification from atmospheric ammonium sulphate in forest canopy throughfall, Nature 299, 548–550.

    Google Scholar 

  • Vermetten A. W. M., Asman W. A. H., Buijsman E., Mulder W., Slanina J., and Waijers-Ijpelaan A., 1985, Concentration of NH3 and NH4 + over The Netherlands, VDI Berichte 560, 241–251.

    Google Scholar 

  • Waldman J. M., Lioy P. J., Thurston G. D., and Lippman M., 1990, Spatial and temporal patterns in summertime sulphate aerosol acidity and neutralization within metropolitan area, Atmos. Environ. 24A, 115–126.

    Google Scholar 

  • Wolfson J. M., 1980, Determination of microgram quantities of inorganic sulphate in atmospheric particulate, J. Air Poll. Control. Ass. 30, 688–690.

    Google Scholar 

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Authors and Affiliations

  1. Institute of Public and Environmental Health, School of Biological Sciences, The University of Birmingham, B15 2TT, Edgbaston, Birmingham, U.K.

    Roy M. Harrison

  2. Institute of Aerosol Science, University of Essex, Wivenhoe Park, CO4 3SQ, Colchester, U.K.

    Abdul-Massih N. Kitto

Authors
  1. Roy M. Harrison
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  2. Abdul-Massih N. Kitto
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Harrison, R.M., Kitto, AM.N. Estimation of the rate constant for the reaction of acid sulphate aerosol with NH3 gas from atmospheric measurements. J Atmos Chem 15, 133–143 (1992). https://doi.org/10.1007/BF00053755

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  • DOI: https://doi.org/10.1007/BF00053755

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