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

Shaw, Miranda F.; Sztáray, Bálint; Whalley, Lisa K.; Heard, Dwayne E.; Millet, Dylan B.; Jordan, Meredith J.  T.; Osborn, David L.; Kable, Scott H.

doi:10.1038/s41467-018-04824-2

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

Journal Article · Tue Jul 03 00:00:00 EDT 2018 · Nature Communications

DOI:https://doi.org/10.1038/s41467-018-04824-2· OSTI ID:1618092

Shaw, Miranda F. ^[1]; Sztáray, Bálint ^[2]; Whalley, Lisa K. ^[3]; ^[3]; Millet, Dylan B. ^[4]; Jordan, Meredith J. T. ^[1]; ^[5]; ^[6]

Univ. of Sydney, NSW (Australia)
Univ. of the Pacific, Stockton, CA (United States)
Univ. of Leeds, Leeds (United Kingdom)
Univ. of Minnesota, Minneapolis, MN (United States)
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Univ. of New South Wales, Sydney, NSW (Australia)

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.

View Accepted Manuscript (DOE)

Research Organization:: Sandia National Laboratories (SNL-CA), Livermore, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); National Science Foundation (NSF); National Aeronautic and Space Administration (NASA)

Grant/Contract Number:: AC04-94AL85000; NA0003523; NA0003525

OSTI ID:: 1618092

Report Number(s):: SAND--2020-0678J; 683003

Journal Information:: Nature Communications, Journal Name: Nature Communications Journal Issue: 1 Vol. 9; ISSN 2041-1723

Publisher:: Nature Publishing GroupCopyright Statement

Country of Publication:: United States

Language:: English

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