title: Catechol oxidation by ozone and hydroxyl radicals at the air-water interface.
abstract: Anthropogenic emissions of aromatic hydrocarbons promptly react with hydroxyl radicals undergoing oxidation to form phenols and polyphenols (e.g., catechol) typically identified in the complex mixture of humic-like substances (HULIS). Because further processing of polyphenols in secondary organic aerosols (SOA) can continue mediated by a mechanism of ozonolysis at interfaces, a better understanding about how these reactions proceed at the air-water interface is needed. This work shows how catechol, a molecular probe of the oxygenated aromatic hydrocarbons present in SOA, can contribute interfacial reactive species that enhance the production of HULIS under atmospheric conditions. Reactive semiquinone radicals are quickly produced upon the encounter of 40 ppbv-6.0 ppmv O3(g) with microdroplets containing [catechol] = 1-150 μM. While the previous pathway results in the instantaneous formation of mono- and polyhydroxylated aromatic rings (PHA) and chromophoric mono- and polyhydroxylated quinones (PHQ), a different channel produces oxo- and dicarboxylic acids of low molecular weight (LMW). The cleavage of catechol occurs at the 1,2 carbon-carbon bond at the air-water interface through the formation of (1) an ozonide intermediate, (2) a hydroperoxide, and (3) cis,cis-muconic acid. However, variable [catechol] and [O3(g)] can affect the ratio of the primary products (cis,cis-muconic acid and trihydroxybenzenes) and higher order products observed (PHA, PHQ, and LMW oxo- and dicarboxylic acids). Secondary processing is confirmed by mass spectrometry, showing the production of crotonic, maleinaldehydic, maleic, glyoxylic, and oxalic acids. The proposed pathway can contribute precursors to aqueous SOA (AqSOA) formation, converting aromatic hydrocarbons into polyfunctional species widely found in tropospheric aerosols with light-absorbing brown carbon.
authors.affiliation: Department of Chemistry, University of Kentucky , Lexington, Kentucky 40506, United States.
authors.forename: Elizabeth A
authors.initials: EA
authors.lastname: Pillar-Little
authors.forename: Robert C
authors.initials: RC
authors.lastname: Camm
authors.forename: Marcelo I
authors.initials: MI
authors.lastname: Guzman
mesh_terms: D000336:Aerosols / Q000737:chemistry; D000388:Air; D002244:Carbon / Q000737:chemistry; D002396:Catechols / Q000737:chemistry*; D006812:Humic Substances; D017665:Hydroxyl Radical / Q000737:chemistry*; D016877:Oxidants / Q000737:chemistry*; D010084:Oxidation-Reduction; D010126:Ozone / Q000737:chemistry*; D014867:Water / Q000737:chemistry
chemical_list: D000336:Aerosols; D002396:Catechols; D006812:Humic Substances; D016877:Oxidants; D014867:Water; D017665:Hydroxyl Radical; D010126:Ozone; D002244:Carbon; C034221:catechol