Abstract
3-Methylenebutane-1,2,4-triol and 3-methyltetrahydrofuran-2,4-diols, previously designated "C(5)-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 HO(2)(•) 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.