Ionic Strength Effect Alters the Heterogeneous Ozone Oxidation of Methoxyphenols in Going from Cloud Droplets to Aerosol Deliquescent Particles.

Abstract

Methoxyphenols are one of the most abundant classes of biomarker tracers for atmospheric wood smoke pollution. The reactions of atmospheric oxidants (ozone, OH) with methoxyphenols can contribute to the formation of secondary organic aerosols (SOA). Here, for the first time, we use the well-established vertical wetted wall flow tube (VWWFT) reactor to assess the effect of ionic strength (I), pH, temperature, and ozone concentration on the reaction kinetics of ozone with acetosyringone (ACS), as a representative methoxyphenol compound. At fixed pH 3, typical for acidic atmospheric deliquescent particles, and at I = 0.9 M adjusted by Na2SO4, the uptake coefficient (γ) of O3 increases by 2 orders of magnitude from γ = (5.0 ± 0.8) × 10-8 on neat salt solution (Na2SO4) to γ = (6.0 ± 0.01) × 10-6 on a mixture of ACS and Na2SO4. The comparison of the uptake coefficients of O3 at different pH values indicates that the reaction kinetics strongly depends on the acidity of the phenolic group of ACS. The observed different reactivity of gas-phase ozone with ACS has implications for ozone uptake by the dilute aqueous phase of cloud droplets and by aerosol deliquescent particles loaded with inorganic salts, and it can affect the formation of SOA in the atmosphere.