Chemical Composition of Secondary Organic Aerosol Formed from the Oxidation of Semivolatile Isoprene Epoxydiol Isomerization Products

3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C<sub>5</sub>-alkene triols", were recently confirmed as in-particle isomerization products of isoprene-derived β-IEPOX isomers that are formed upon acid-driven uptake and partition back into the gas phase. In chamber experiments, we have systematically explored their gas phase oxidation by hydroxyl radical (<sup>•</sup>OH) as a potential source of secondary organic aerosol (SOA). <sup>•</sup>OH-initiated oxidation of both compounds in the presence of ammonium bisulfate aerosol resulted in substantial aerosol volume growth. Compositions of low-volatility products in both the gas and particulate phases were established by high-resolution mass spectrometry measurements. Under conditions mimicking the Southeast USA (50% relative humidity, bulk seed aerosol pH 1.4), we estimate the SOA yield from <sup>•</sup>OH-initiated oxidation of 3-methylenebutane-1,2,4-triol to be 93.1%, equating to 1.95 ± 0.81 Tg C Yr<sup>-1</sup>, and from 3-methyltetrahydrofuran-2,4-diol oxidation to be 26.7%, equating to 1.76 ± 1.26 Tg C Yr<sup>-1</sup>. Previously unreported isoprene-derived oxidation products, 2,3-dihydroxy-2-(hydroxymethyl)propanal, 1,3,4-trihydroxybutan-2-one, and four organosulfates have been confirmed in ambient SOA, and aid in understanding isoprene oxidation pathways in HO<sub>2</sub><sup>•</sup> dominated environments as NO<sub><i>x</i></sub> levels continue to decline in the US. This work underlines the need for inclusion of partitioning of in-particle formed semivolatile products and their atmospheric oxidation pathways in atmospheric models.

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Publication Details

Journal
Environmental Science & Technology
Published
2024-12-12
DOI
https://doi.org/10.1021/acs.est.4c06850
Citations
3
Primary Topic
Atmospheric chemistry and aerosols
Type
article
Field-Weighted Citation Impact
1.13

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article

Chemical Composition of Secondary Organic Aerosol Formed from the Oxidation of Semivolatile Isoprene Epoxydiol Isomerization Products

Avram Gold, John H. Offenberg, Jason D. Surratt, Molly Frauenheim et al.
3 citations
Environmental Science & Technology
Atmospheric chemistry and aerosols
1.13
article

Chemical Composition of Secondary Organic Aerosol Formed from the Oxidation of Semivolatile Isoprene Epoxydiol Isomerization Products

Avram Gold, John H. Offenberg, Jason D. Surratt, Molly Frauenheim, Zhenfa Zhang
article en
3 citations

Abstract

3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C<sub>5</sub>-alkene triols", were recently confirmed as in-particle isomerization products of isoprene-derived β-IEPOX isomers that are formed upon acid-driven uptake and partition back into the gas phase. In chamber experiments, we have systematically explored their gas phase oxidation by hydroxyl radical (<sup>•</sup>OH) as a potential source of secondary organic aerosol (SOA). <sup>•</sup>OH-initiated oxidation of both compounds in the presence of ammonium bisulfate aerosol resulted in substantial aerosol volume growth. Compositions of low-volatility products in both the gas and particulate phases were established by high-resolution mass spectrometry measurements. Under conditions mimicking the Southeast USA (50% relative humidity, bulk seed aerosol pH 1.4), we estimate the SOA yield from <sup>•</sup>OH-initiated oxidation of 3-methylenebutane-1,2,4-triol to be 93.1%, equating to 1.95 ± 0.81 Tg C Yr<sup>-1</sup>, and from 3-methyltetrahydrofuran-2,4-diol oxidation to be 26.7%, equating to 1.76 ± 1.26 Tg C Yr<sup>-1</sup>. Previously unreported isoprene-derived oxidation products, 2,3-dihydroxy-2-(hydroxymethyl)propanal, 1,3,4-trihydroxybutan-2-one, and four organosulfates have been confirmed in ambient SOA, and aid in understanding isoprene oxidation pathways in HO<sub>2</sub><sup>•</sup> dominated environments as NO<sub><i>x</i></sub> levels continue to decline in the US. This work underlines the need for inclusion of partitioning of in-particle formed semivolatile products and their atmospheric oxidation pathways in atmospheric models.

Environmental Science & TechnologyVol. 58(51)
University of North Carolina at Chapel Hill (US), Environmental Protection Agency (US), Research Triangle Park Foundation (US)
National Science Foundation, National Institute of Environmental Health Sciences, Division of Atmospheric and Geospace Sciences
Openalex Percentile: Top 23%
Atmospheric chemistry and aerosols
1.13
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