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The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater

Abstract

Elevated concentrations of S(IV) and formaldehyde were observed in fog- and cloudwater at sites in California. The highest concentrations (up to 3 mM S(IV) and 0.7 mM CH2O) were measured at Bakersfield, during a prolonged period of repeated fog. In Bakersfield [S(IV)] generally exceeded [CH2O], while in the Los Angeles area the reverse was observed. The lowest concentrations of both species were observed at marine and high altitude sites away from local emissions. Equilibrium computations indicate that high concentrations of S(IV) cannot be achieved without the formation of S(IV)-RCHO adducts.

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References

  • Bell, R. P., 1966, The reversible hydration of carbonyl compounds, in V.Gold (ed.),Advances in Physical Organic Chemistry, vol. 4, Academic Press, London, pp. 1–29.

    Google Scholar 

  • Bell, R. P., Evans, F. R. S., and Evans, P. G., 1966, Kinetics of the dehydration of methylene glycol in aqueous solution,Proc. Roy. Soc. A. 291, 297–323.

    Google Scholar 

  • Bordwell, F. G., 1963,Organic Chemistry, Macmillan, New York.

    Google Scholar 

  • Boyce, S. D. and Hoffmann, M. R., 1984. Kinetics and mechanism of the formation of hydroxy-methanesulfonic acid at low pH,J. Phys. Chem., in press.

  • Buschmann, H. J., Fulderner, H. H., and Knoche, W., 1980, The reversible hydration of carbonyl compounds in aqueous solution. Part I, the ketol gem-diol equilibrium,Ber. Bunsenges Phys. Chem. 84, 41–44.

    Google Scholar 

  • California Air Resources Board (CARB), 1982,Emissions Inventory, California Air Resources Board, Sacramento, California.

    Google Scholar 

  • Calvert, J. G. and Pitts, J. N. Jr., 1966,Photochemistry, John Wiley, New York.

    Google Scholar 

  • Calvert, J. G., 1980, The homogeneous chemistry of formaldehyde generation and destruction within the atmosphere, inProceedings of the NATO Advanced Study Institute on Atmospheric Ozone: Its Variation and Human Influences, Federal Aviation Administration, Washington, D.C., pp. 153–190.

  • Chameides, W. L. and Davis, D. D., 1983. Aqueous-phase source of formic acid in clouds,Nature 304, 427–429.

    Google Scholar 

  • Cleveland, W. S., Graedel, T. E., and Kleiner, B., 1977, Urban formaldehyde: Observed correlation with source emissions and photochemistry,Atmos. Environ. 11, 357–360.

    Google Scholar 

  • Dasgupta, P. K., DeCesare, K., and Ullrey, J. C., 1980, Determination of atmospheric sulfur dioxide without tetrachlormercurate(II) and the mechanism of the Schiff Reactions,Anal. Chem. 52, 1912–1922.

    Google Scholar 

  • Demerjian, K. L., Kerr, J. A., and Calvert, J. G., 1974, The mechanism of photochemical smog formation,Adv. Environ. Sci. Technol. 4, 1–262.

    Google Scholar 

  • Eatough, D. J. and Hansen, L. D., 1983, Organic and inorganic S(IV) compounds in airborne particulate matter,Adv. Environ. Sci. Technol. 12, 221–268.

    Google Scholar 

  • Fortune, C. R. and Dellinger, B., 1982, Stabilization and analysis of S(IV) aerosols in environmental samples,Environ. Sci. Tech. 16, 62–66.

    Google Scholar 

  • Grosjean, D., 1982, Formaldehyde and other carbonyls in Los Angeles ambient air,Environ. Sci. Technol. 16, 254–262.

    Google Scholar 

  • Grosjean, D. and Wright, B., 1983, Carbonyls in urban fog, ice fog, cloudwater and rainwater,Atmos. Environ. 17, 2093–2096.

    Google Scholar 

  • Hering, S. V. and Blumenthal, D. L., 1983, Field comparison of fog/cloud water collectors: Preliminary results,Proc. APCA Specialty Conference on the Meteorology of Acid Deposition, Hartford, Connecticut, October, 1983.

  • Hoffmann, M. R. and Boyce, S. D., 1983, Catalytic autoxidation of aqueous sulfur dioxide in relationship to atmospheric systems,Adv. Environ. Sci. Technol. 12, 149–189.

    Google Scholar 

  • Humphrey, R. E., Ward, M. H., and Hinze, W., 1970, Spectrophotometric determination of sulfite with 4,4-Dithiopyridine and 5,5′-Dithiobis (2-Nitrobenzoic acid),Anal. Chem. 42, 698–702.

    Google Scholar 

  • Izatt, R. M., Eatough, D. J., Lee, M. L., Major, T., Richter, B. E., Hansen, L. D., Meisenheimer, R. G., and Fischer, J. W., 1978, The formation of inorganic and organic S(IV) species in aerosols,Proc. 4th Joint Conf. on Sensing Environ. Pollutants, Amer. Chem. Soc., Washington, D.C., pp. 821–824.

  • Jacob, D. J. and Hoffmann, M. R., 1983, A dynamic model for the production of H+, NO3 , and SO4 2− in urban fog,J. Geophys. Res. 88C, 6611–6621.

    Google Scholar 

  • Jacob, D. J., Wang, R-F. T., and Flagan, R. C., 1984, Fogwater collector design and characterization,Environ. Sci. Technol., in press.

  • Jacob, D. J., Waldman, J. M., Munger, J. W., and Hoffmann, M. R., 1984, A field investigation of physical and chemical mechanisms affecting pollutant concentrations in fog droplets,Tellus, in press.

  • Klippel, W. and Warneck, P., 1978, Formaldehyde in rain water and on the atmospheric aerosol,Geophys. Res. Lett. 5, 177–179.

    Google Scholar 

  • Klippel, W. and Warneck, 1980, The formaldehyde content of the atmospheric aerosol,Atmos. Environ. 14, 809–818.

    Google Scholar 

  • Ledbury, W. and Blair, E. W., 1925, The partial formaldehyde vapour pressure of aqueous solutions of formaldehyde. Part II.J. Am. Chem. Soc. 127, 2832–2839.

    Google Scholar 

  • McArdle, J. V. and Hoffmann, M. R., 1983, Kinetics and mechanism of the oxidation of aquated sulfur dioxide by hydrogen peroxide at low pH,J. Phys. Chem. 87, 5425–5429.

    Google Scholar 

  • Munger, J. W., Jacob, D. J., Waldman, J. M., and Hoffmann, M. R., 1983, Fogwater chemistry in an urban atmosphere,J. Geophys. Res. 88, 5109–5121.

    Google Scholar 

  • Nash, T., 1953, The colorimetric estimation of formaldehyde by means of the Hantzsch Reaction,Biochem. J. 55, 416–421.

    Google Scholar 

  • National Research Council (NRC), 1981,Formaldehyde and Other Aldehydes, National Academy Press, Washington, D.C.

    Google Scholar 

  • Niki, H., Maker, P. D., Savage, C. M., and Breitenbach, L. P., 1978, Mechanism for hydroxyl radical initiated oxidation of olefin-nitric oxide mixtures in parts per million concentrations,J. Phys. Chem. 82, 135–137.

    Google Scholar 

  • Reible, D. D., Shair, F. H., Smith, T. B., Lehrman, D. E., 1983, The origin and fates of air pollutants in California's San Joaquin Valley I. Winter.Atmos. Environ., in press.

  • Reitz, E. B., 1980, The stabilization of small concentrations of formaldehyde in aqueous solutions,Anal. Lett. 13, 1073–1084.

    Google Scholar 

  • Richards, L. W., Anderson, J. A., Blumenthal, D. L., McDonald, J. A., Kok, G. L., and Lazrus, A. L., 1983, Hydrogen peroxide and sulfur(IV) in Los Angeles cloudwater,Atmos. Environ. 17, 911–914.

    Google Scholar 

  • Roberts, J. D., Stewart, R., and Caserio, M. C., 1971,Organic Chemistry, W.A. Benjamin, Menlo Park, CA.

    Google Scholar 

  • Sillén, G. L. and Martell, A. E., 1964,Stability Constants of Metal-ion Complexes, special publication No. 17, Chemical Society, London.

    Google Scholar 

  • Smith, R. H., 1978, Rate constant and activation energy for the gaseous reaction between hydroxyl and formaldehyde,Int. J. Chem. Kinet. 10, 519–528.

    Google Scholar 

  • Smith, R. V. and Erhardt, P. W., 1975, Nash determination for formaldehyde in the presence of bisulfite,Anal. Chem. 47, 2462–2454.

    Google Scholar 

  • Sørensen, P. E. and Andersen, V. S., 1970, The formaldehyde-hydrogen sulphite system in alkaline aqueous solution. Kinetics, mechanisms, and equilibria,Acta Chem. Scand. 24, 1301–1306.

    Google Scholar 

  • Su, F., Calvert, J. G., and Shaw, J. H., 1979, Mechanism of the photooxidation of gaseous formaldehyde,J. Phys. Chem. 83, 3185–3191.

    Google Scholar 

  • Stewart, T. D. and Donnally, L. H., 1932, The aldehyde bisulfite compounds II. The effect of varying hydrogen ion and of varying temperature upon the equilibrium between benzaldehyde and bisulfite ion.J. Am. Chem. Soc. 54, 3555–3558.

    Google Scholar 

  • Waldman, J. M., Munger, J. W., Jacob, D. J., Flagan, R. C., Morgan, J. J., and Hoffmann, M. R., 1982, Chemical composition of acid fog.,Science 218, 677–680.

    Google Scholar 

  • Zafiriou, O. C., Alford, J., Herrera, M., Peltzer, E. T., and Gagosian, R. B., 1980, Formaldehyde in remote marine air and rain: Flux measurements and estimates,Geophys. Res. Lett. 5, 341–344.

    Google Scholar 

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Munger, J.W., Jacob, D.J. & Hoffmann, M.R. The occurrence of bisulfite-aldehyde addition products in fog- and cloudwater. J Atmos Chem 1, 335–350 (1984). https://doi.org/10.1007/BF00053799

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  • DOI: https://doi.org/10.1007/BF00053799

Key words

  • Formaldehyde
  • sulfur (IV)
  • sulfonic acids
  • sulfur oxidation
  • air pollution
  • fogwater chemistry