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

Abstract

3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated “C₅-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 (^•OH) as a potential source of secondary organic aerosol (SOA). ^•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 ^•OH-initiated oxidation of 3-methylenebutane-1,2,4-triol to be 93.1%, equating to 1.95 ± 0.81 Tg C Yr^-1, and from 3-methyltetrahydrofuran-2,4-diol oxidation to be 26.7%, equating to 1.76 ± 1.26 Tg C Yr^-1. 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 HO₂^• dominated environments as NO_x 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.