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Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere

Author

Listed:
  • Miranda F. Shaw

    (University of Sydney)

  • Bálint Sztáray

    (University of the Pacific)

  • Lisa K. Whalley

    (University of Leeds)

  • Dwayne E. Heard

    (University of Leeds)

  • Dylan B. Millet

    (University of Minnesota)

  • Meredith J. T. Jordan

    (University of Sydney)

  • David L. Osborn

    (Sandia National Laboratories)

  • Scott H. Kable

    (University of New South Wales)

Abstract

Organic acids play a key role in the troposphere, contributing to atmospheric aqueous-phase chemistry, aerosol formation, and precipitation acidity. Atmospheric models currently account for less than half the observed, globally averaged formic acid loading. Here we report that acetaldehyde photo-tautomerizes to vinyl alcohol under atmospherically relevant pressures of nitrogen, in the actinic wavelength range, λ = 300–330 nm, with measured quantum yields of 2–25%. Recent theoretical kinetics studies show hydroxyl-initiated oxidation of vinyl alcohol produces formic acid. Adding these pathways to an atmospheric chemistry box model (Master Chemical Mechanism) demonstrates increased formic acid concentrations by a factor of ~1.7 in the polluted troposphere and a factor of ~3 under pristine conditions. Incorporating this mechanism into the GEOS-Chem 3D global chemical transport model reveals an estimated 7% contribution to worldwide formic acid production, with up to 60% of the total modeled formic acid production over oceans arising from photo-tautomerization.

Suggested Citation

  • Miranda F. Shaw & Bálint Sztáray & Lisa K. Whalley & Dwayne E. Heard & Dylan B. Millet & Meredith J. T. Jordan & David L. Osborn & Scott H. Kable, 2018. "Photo-tautomerization of acetaldehyde as a photochemical source of formic acid in the troposphere," Nature Communications, Nature, vol. 9(1), pages 1-7, December.
    • Handle: RePEc:nat:natcom:v:9:y:2018:i:1:d:10.1038_s41467-018-04824-2
    DOI: 10.1038/s41467-018-04824-2
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