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    Can Isoprene Oxidation Explain High Concentrations of Atmospheric Formic and Acetic Acid over Forests?

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    Authors
    Link, M.F.
    Nguyen, T.B.
    Bates, K.H.
    Müller, J.-F.
    Farmer, D.K.
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    Discipline
    Earth and related Environmental sciences
    Subject
    formic acid
    isoprene
    photochemical oxidation
    environmental chambers
    Audience
    Scientific
    Date
    2020
    Metadata
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    Description
    Formic and acetic acid concentrations are particularly high over forested areas of the world. However, the gas-phase mechanisms for producing these acids are poorly understood even for isoprene, the globally dominant biogenic hydrocarbon. We quantified formic and acetic acid production from reactions of hydroxyl radical (OH) (between high and low ranges of nitric oxide (NO) levels) with isoprene, methacrolein (MACR), isoprene epoxydiol (IEPOX), isoprene hydroxy hydroperoxide (ISOPOOH), and α-pinene from the focused isoprene experiments at California Institute of Technology (FIXCIT) laboratory chamber study. We find that (i) OH oxidation of MACR, IEPOX, and ISOPOOH are sources of formic acid, (ii) isoprene peroxy radical isomerization and associated photolysis oxidation products are potentially important sources of organic acids, and (iii) high levels of NO generally suppress organic acid formation from OH oxidation of isoprene. We modified existing chemical mechanisms for isoprene oxidation to account for organic acid production pathways observed in the FIXCIT study. We simulated organic acid production during the Southeastern Oxidant and Aerosol Study using the updated chemical mechanisms and represented acetic acid within a factor of 2 but still underpredicted formic acid by a factor of 6. While we cannot explain ambient formic acid with explicit chemical mechanisms, the FIXCIT results suggest that the oxidation of isoprene could account for as much as 70% of the global annual production of formic acid from gas-phase reactions.
    Citation
    Link, M.F.; Nguyen, T.B.; Bates, K.H.; Müller, J.-F.; Farmer, D.K. (2020). Can Isoprene Oxidation Explain High Concentrations of Atmospheric Formic and Acetic Acid over Forests?. , ACS Earth and Space Chemistry, Vol. 4, Issue 5, 730-740, DOI: 10.1021/acsearthspacechem.0c00010.
    Identifiers
    uri: https://orfeo.belnet.be/handle/internal/7528
    doi: http://dx.doi.org/10.1021/acsearthspacechem.0c00010
    Type
    Article
    Peer-Review
    Yes
    Language
    eng
    Links
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