Biomass burning releases highly reactive methoxyphenols into the atmosphere, which can undergo heterogeneous oxidation and act as precursors for secondary organic aerosol (SOA) formation. Understanding the reactivity of such methoxyphenols at the air–water interface is a matter of major atmospheric interest. Online electrospray ionization mass spectrometry (OESI-MS) is used here to study the oxidation of two methoxyphenols among three phenolic aldehydes, 4-hydroxybenzaldehyde, vanillin, and syringaldehyde, on the surface of water. The OESI-MS results together with cyclic voltammetry measurements at variable pH are integrated into a mechanism describing the heterogeneous oxidative processing of methoxyphenols by gaseous ozone (O3) and hydroxyl radicals (HO). For a low molar ratio of O3 ≤ 66 ppbv, the OESI-MS spectra show that the oxidation is dominated by in situ produced HO and results in the production of polyhydroxymethoxyphenols. When the level of O3 increases (i.e., ≥78 times), the ion count of polyhydroxymethoxyphenols increases, while new ring fragmentation products are generated, including conjugated aldehydes and double bonds as well as additional carboxylic acid groups. The interfacial reactivity of methoxyphenols with O3 and HO is enhanced as the number of methoxy (−OCH3) groups increases (4-hydroxybenzaldehyde < vanillin < syringaldehyde). The experimental observations are summarized in two reaction pathways, leading to the formation of (1) hydroxylated methoxyphenols and (2) multifunctional carboxylic acids from fragmentation of the aromatic ring. The new highly oxygenated products with low volatility are excellent precursors for aqueous SOA formation.

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Published in The Journal of Physical Chemistry. A, v. 124, issue 42.

Copyright © 2020 American Chemical Society ACS AuthorChoice with CC-BY-NC-ND license

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M.I.G. acknowledges funding from the U.S.A. National Science Foundation under award 1903744.

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The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.jpca.0c05944. It is also available for download as the additional file listed at the end of this record.

jp0c05944_si_001.pdf (354 kB)
Supporting information: Control experiments, cyclic voltammograms at variable pH, cyclic voltammetry processing to obtain their second derivative, methodology for inflection potential determination, and experimental redox potentials versus Ag/AgCl reference electrode