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.

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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

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article

2-Methyltetrol Sulfate Oxidation by Hydroxyl Radical in Atmospheric Water Mimics and Implications for the Fate of Isoprene-Derived Secondary Organic Aerosol

Haley M. Royer, Avram R. Gold, Cade M. Christensen, Andrew Ault et al.
ACS ES&T Air
Atmospheric chemistry and aerosols
article

2-Methyltetrol Sulfate Oxidation by Hydroxyl Radical in Atmospheric Water Mimics and Implications for the Fate of Isoprene-Derived Secondary Organic Aerosol

Haley M. Royer, Avram R. Gold, Cade M. Christensen, Andrew Ault, Ashley Harrill, Yuzhi Chen, Jason D. Surratt, Barbara J. Turpin
article en

Abstract

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.

ACS ES&T AirVol. 3(3)
University of North Carolina at Chapel Hill (US), University of Michigan (US), Institute for Literature (BG)
National Science Foundation, National Institute of Environmental Health Sciences
Clean water and sanitation
Openalex Percentile: Top 76%
Atmospheric chemistry and aerosols
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