Advertisement

Experimental and Theoretical Study of the Atmospheric Degradation of Aldehydes

  • Barbara D'Anna
  • Claus J. Nielsen
Part of the NATO Science Series book series (NAIV, volume 16)

Abstract

Aldehydes are ubiquitous key components in the chemistry of the troposphere. They are common primary pollutants from biogenic emissions and in residues of incomplete combustion (Ciccioli et al., 1993). Relevant natural sources are vegetation, forest fires and microbiological processes (Kotzias et al, 1997). Aldehydes are also nearly mandatory intermediates in the photo-oxidation processes of most organic compounds in the troposphere (Kerr and Sheppard, 1981; Carlier et al, 1986). Formaldehyde (HCHO) and acetaldehyde (CH3CHO) are among the most abundant carbonyls in the atmosphere. Ambient levels are in the order of a few tens of pptv in clean background conditions (Zhou et al., 1996; Ayers et al., 1997) but may reach tens of ppbv in polluted urban areas as a consequence of the elevated anthropogenic emissions of aldehydes and their precursors from automobile traffic, industrial and domestic heating, and industrial activity (Carlier et al, 1986; Yokouchi et al, 1990). The atmospheric loss processes include photolysis, day-time reaction with OH radicals and with Cl and Br atoms in the marine boundary layer, and reaction with NO3 radicals during the night-time. The photolytic cleavage of aldehydes constitute an important source of free radicals, particularly in the moderately and strongly polluted areas (Carlier et al, 1986; Yokouchi et al, 1990). Aldehydes are toxic compounds themselves, and some of their photo-oxidation products, the peroxyacylnitrates, are phytotoxic and strong eye-irritant compounds (Carlier et al, 1986; Carter et al, 1981). Further, peroxyacylnitrates, such as peroxyacetyl-nitrate (PAN), are long-lived species, which can act as a NO2 reservoir in the troposphere.

Keywords

Rate Coefficient Kinetic Isotope Effect Aliphatic Aldehyde Marine Boundary Layer Minimum Energy Path 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. Alvarez-Idaboy, J. R., N. Mora-Diez, R. J. Boyd and A. Vivier-Bunge; On the importance of prereactive complexes in molecule-radical reactions: Hydrogen abstraction from aldehydes by OH, J. Am. Chem. Soc. 123 (2001) 2018–2024.CrossRefGoogle Scholar
  2. Atkinson, R.; Kinetics and mechanisms of the gas-phase reactions of the NO3 radical with organic compounds, J. Phys. Chem. Ref. Data 20 (1991) 459–507.CrossRefGoogle Scholar
  3. Atkinson, R.; Gas-phase tropospheric chemistry of organic compounds, J. Phys. Chem. Ref. Data Monograph 2 (1994).Google Scholar
  4. Atkinson, R., D. L. Baulch, R. A. Cox, R. F. Hampson Jr., J. A. Kerr, M. J. Rossi and J. Troe; Evaluated kinetic, photochemical and heterogeneous data for atmospheric chemistry. 5. IUPAC Subcommittee on Gas Kinetic Data Evaluation for Atmospheric Chemistry, J. Phys. Chem. Ref. Data 26 (1997) 521–1011.CrossRefGoogle Scholar
  5. Ayers, G. P., R. W. Gillet, H. Granek, C. de Serves and R. A Cox; Formaldehyde production in clean marine air, Geophys. Res. Lett. 24 (1997) 401–404.CrossRefGoogle Scholar
  6. Beukes, J. A., B. D’Anna, V. Bakken and C. J. Nielsen; Experimental and theoretical study of the F, Cl and Br reactions with formaldehyde and acetaldehyde, Phys. Chem. Chem. Phys. 2 (2000) 4049–4060.CrossRefGoogle Scholar
  7. Carlier, P., H. Hannachi and G. Mouvier; The chemistry of carbonyl compounds in the atmosphere — a review, Atmos. Environ. 20 (1986) 2079–2099.CrossRefGoogle Scholar
  8. Carter, W. P. L., A. M. Winer and J. N. Pitts; Effect of peroxyacetyl nitrate on the initiation of photochemical smog. Environ. Sci. Technol. 15 (1981) 831–834.CrossRefGoogle Scholar
  9. CATOME “Carbonyls in Tropospheric Oxidation Mechanisms”, CEC Environment and Climate program contract ENV4-CT97-0416, Coordinated by C. Dye (2000).Google Scholar
  10. Ciccioli, P., E. Brancaleoni, M. Frattoni, A. Cecinato and A. Brachetti; Ubiquitous occurrence of semivolatile carbonyl-compounds in tropospheric samples and their possible sources, Atmos. Environ. 27A (1993) 1891–1901.Google Scholar
  11. D’Anna, B. and C. J. Nielsen; Kinetic study of the vapour-phase reaction between aliphatic aldehydes and the nitrate radical, J Chem. Soc. Faraday Trans. 93 (1997) 3479–3483.CrossRefGoogle Scholar
  12. D’Anna, B., S. Langer, E. Ljungstrom, C. J. Nielsen and M. Ullerstam; Rate coefficients and Arrhenius parameters for the reaction of the NO3 radical with acetaldehyde and acetaldehyde-1d, Phys. Chem. Chem. Phys. 3 (2001a) 1631–1637.CrossRefGoogle Scholar
  13. D’Anna, B., Ø. Andresen, Z. Gefen and C. J. Nielsen; Kinetic study of OH and NO3 radical reactions with 14 aliphatic aldehydes, Phys. Chem. Chem. Phys. 3 (2001b) 3057–3063.CrossRefGoogle Scholar
  14. D’Anna, B. V. Bakken, J. A. Beukes, J. T. Jodkowski and C. J. Nielsen; Experimental and theoretical study of gas phase NO3 and OH radical reactions with formaldehyde, acetaldehyde and their isotopomers, Phys. Chem. Chem. Phys. 4 (2002) submitted.Google Scholar
  15. Kerr, J. A. and D. W. Sheppard; Kinetics of the reactions of hydroxyl radicals with aldehydes studied under atmospheric conditions. Environ. Sci. Technol. 8 (1981) 960–963.CrossRefGoogle Scholar
  16. Kotzias, D., C. Konidari and C. Spartà; Volatile carbonyl compounds of biogenic origin — emission and concentration in the atmosphere, in Biogenic Volatile Organic Compouns in the Atmosphere — Summary of present knowledge (Eds. G. Helas, S. Slanina and R. Steinbrecher), SPB Academic Publishers, Amsterdam, 1997, 67–78.Google Scholar
  17. Morris, E. D. Jr. and H. Niki; Mass spectrometric study of the reaction of hydroxyl radical with formaldehyde, J. Chem. Phys. 55 (1971) 1991–1992.CrossRefGoogle Scholar
  18. Niki, H., P. D. Maker, L. P. Breitenbach and C. M. Savage; FTIR studies of the kinetics and mechanism for the reaction of chlorine atom with formaldehyde, Chem. Phys. Lett. 57 (1978) 596–599.CrossRefGoogle Scholar
  19. Niki, H., P. D. Maker, C. M. Savage and L. P. Breitenbach; An Fourier transform infrared study of the kinetics and mechanism for the reaction of hydroxyl radical with formaldehyde, J Phys. Chem. 88 (1984) 5342–5344.CrossRefGoogle Scholar
  20. Niki, H., P. D. Maker, C. M. Savage and L. P. Breitenbach; FTIR study of the kinetics and mechanism for chlorine-atom-initiated reactions of acetaldehyde, J. Phys. Chem. 89 (1985) 588–591.CrossRefGoogle Scholar
  21. Papagni, C, J. Arey and R. Atkinson; Rate constants for the gas-phase reactions of a series of C-3 — C-6 aldehydes with OH and NO3 radicals. Int. J. Chem. Kin. 32 (2000) 79–84.CrossRefGoogle Scholar
  22. RADICAL “Evaluation of Radical Sources in Atmospheric Chemistry through Chamber and Laboratory Studies”, CEC Environment and Climate program contract ENV4-CT97-0419, Coordinated by G. Moortgat (2000).Google Scholar
  23. Soto, M. R. and M. Page; Features of the potential energy surface for reactions of hydroxyl with formaldehyde, J. Phys. Chem. 94 (1990) 3242–3246.CrossRefGoogle Scholar
  24. Taylor, P. H., M. S. Rahman, M. Arif, B. Dellinger and P. Marshall; Kinetics and mechanistic studies of the reaction of hydroxyl radicals with acetaldehyde over an extended temperature range, 26th International Symposium on Combustion (1996) 497–504.Google Scholar
  25. Ullerstam, M., S. Langer and E. Ljungström, Gas phase rate coefficients and activation energies for the reaction of butanal and 2-methyl-propane with nitrate radicals, Int. J. Chem. Kit. 32 (2000) 294–303.CrossRefGoogle Scholar
  26. Wallington, T. J., L. M. Skewes, W. O. Siegel, C. H. Wu and S. M. Japar; Gas phase reaction of chlorine atoms with a series of oxygenated organic species at 295 K, Int. J. Chem. Kin. 20 (1988) 867–875.CrossRefGoogle Scholar
  27. Yokouchi, Y., H. Mukai, K. Nakajima and Y. Ambe; Semivolatile aldehydes as predominant organic gases in remote areas, Atmospheric Environment 24A (1990) 439–442.Google Scholar
  28. Zhou, X. L., Y-N. Lee, L. Newman, X. H. Chen and K. Mopper; Tropospheric formaldehyde concentration at the Mauna Loa observatory during the Mauna Loa observatory photochemistry experiment 2, J. Geophys. Res. 101 (1996) 14711–14719.CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2002

Authors and Affiliations

  • Barbara D'Anna
    • 1
  • Claus J. Nielsen
    • 1
  1. 1.Department of ChemistryUniversity of OsloOsloNorway

Personalised recommendations