2-Methyltetrol Sulfate Oxidation by Hydroxyl Radical in Atmospheric Water Mimics and Implications for the Fate of Isoprene-Derived Secondary Organic Aerosol
2-Methyltetrol sulfate diastereomers (2-MTS) form from acid-driven multiphase chemical conversion of inorganic sulfate (Sulf<sub>inorg</sub>) aerosol by isoprene-derived epoxydiols (IEPOX). Studies have explored 2-MTS sinks within aerosols, but observations of 2-MTS in atmospheric waters indicate a need to understand the fate of 2-MTS in clouds and fogs. In batch reactor experiments, we oxidized 2-MTS in 30, 300, and 3000 μM solutions to understand 2-MTS fate in cloud, fog, and aerosol water. Ion chromatography (IC) revealed production of acetate, oxalate, and Sulf<sub>inorg</sub> with 2-MTS oxidation. Our 30, 300, and 3000 μM experiments revealed a 5%, 20%, and 32% gap in the sulfur mass balance, respectively, suggesting organosulfates (OSs) formed from 2-MTS oxidation. OSs produced by 2-MTS oxidation were detected by hydrophilic liquid interaction chromatography interfaced to electrospray ionization high-resolution tandem mass spectrometry at mass-to-charge ratios 139 (C<sub>2</sub>H<sub>3</sub>O<sub>5</sub>S<sup>-</sup>), 169 (C<sub>3</sub>H<sub>5</sub>O<sub>6</sub>S<sup>-</sup>), 185 (C<sub>3</sub>H<sub>5</sub>O<sub>7</sub>S<sup>-</sup>), 199 (C<sub>4</sub>H<sub>7</sub>O<sub>7</sub>S<sup>-</sup>), 211 (C<sub>5</sub>H<sub>7</sub>O<sub>7</sub>S<sup>-</sup>), 213 (C<sub>5</sub>H<sub>9</sub>O<sub>7</sub>S<sup>-</sup>), 227 (C<sub>5</sub>H<sub>7</sub>O<sub>8</sub>S<sup>-</sup>), and 229 (C<sub>5</sub>H<sub>9</sub>O<sub>8</sub>S<sup>-</sup>). 2-MTS oxidation was then accurately predicted with a rate constant of 1.5×10<sup>9</sup> M<sup>-1</sup>s<sup>-1</sup>. Results emphasize the utility of 2-MTS for sulfur cycling in the atmosphere, and the potential for IC to measure 2-MTS in atmospheric waters.
Authors
- Haley M. Royer (ORCID: https://orcid.org/0000-0002-0481-4496)
- Avram R. Gold (ORCID: https://orcid.org/0000-0001-8618-0118)
- Cade M. Christensen (ORCID: https://orcid.org/0009-0002-7663-2736)
- Andrew Ault (ORCID: https://orcid.org/0000-0003-1276-1360)
- Ashley Harrill
- Yuzhi Chen
- Jason D. Surratt
- Barbara J. Turpin
Institutions
- University of North Carolina at Chapel Hill (US)
- University of Michigan (US)
- Institute for Literature (BG)
Publication Details
- Journal
- ACS ES&T Air
- Published
- 2026-02-04
- DOI
- https://doi.org/10.1021/acsestair.5c00406
- Primary Topic
- Atmospheric chemistry and aerosols
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- National Science Foundation
- National Institute of Environmental Health Sciences