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

Link, Michael F.; Nguyen, Tran B.; Bates, Kelvin; Müller, Jean-François; Farmer, Delphine K.

doi:10.1021/acsearthspacechem.0c00010

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

Journal Article · Mon Mar 30 00:00:00 EDT 2020 · ACS Earth and Space Chemistry

DOI:https://doi.org/10.1021/acsearthspacechem.0c00010· OSTI ID:1801701

^[1]; Nguyen, Tran B. ^[2]; ^[3]; Müller, Jean-François ^[4]; ^[5]

Colorado State Univ., Fort Collins, CO (United States); OSTI
Univ. of California, Davis, CA (United States)
Harvard Univ., Cambridge, MA (United States)
Royal Belgian Institute for Space Aeronomy, Brussels (Belgium)
Colorado State Univ., Fort Collins, CO (United States)

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.

View Accepted Manuscript (DOE)

Research Organization:: California Institute of Technology (CalTech), Pasadena, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: SC0006626

OSTI ID:: 1801701

Journal Information:: ACS Earth and Space Chemistry, Journal Name: ACS Earth and Space Chemistry Journal Issue: 5 Vol. 4; ISSN 2472-3452

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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

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