Multiphase Reactions between Organic Peroxides and Sulfur Dioxide in Internally Mixed Inorganic and Organic Particles: Key Roles of Particle Phase Separation and Acidity.

ABSTRACT

Organic peroxides (POs) are ubiquitous in the atmosphere and particularly reactive toward dissolved sulfur dioxide (SO2), yet the reaction kinetics between POs and SO2, especially in complex inorganic-organic mixed particles, remain poorly constrained. Here, we report the first investigation of the multiphase reactions between SO2 and POs in monoterpene-derived secondary organic aerosol internally mixed with different inorganic salts (ammonium sulfate, ammonium bisulfate, or sodium nitrate). We find that when the particles are phase-separated, the PO-S(IV) reactivity is consistent with that measured in pure SOA and depends markedly on the water content in the organic shell. However, when the organic and inorganic phases are miscible, the PO-S(IV) reactivity varies substantially among different aerosol systems, mainly driven by their distinct acidities (not by ionic strength). The second-order PO-S(IV) rate constant decreases monotonically from 5 × 105 to 75 M-1 s-1 in the pH range of 0.1-5.6. Both proton catalysis and general acid catalysis contribute to S(IV) oxidation, with their corresponding third-order rate constants determined to be (6.4 ± 0.7) × 106 and (6.9 ± 4.6) × 104 M-2 s-1 at pH 2-6, respectively. The measured kinetics imply that the PO-S(IV) reaction in aerosol is an important sulfate formation pathway, with the reaction kinetics dominated by general acid catalysis at pH > 3 under typical continental atmospheric conditions.