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Kinetics and Oligomer Products of the Multiphase Reactions of Hydroxyacetone with Atmospheric Amines, Ammonium Sulfate, and Cloud Processing

Year: 2024

Type: article

Abstract: High Resolution Image Download MS PowerPoint Slide Hydroxyacetone (HA) is an atmospheric oxidation product of isoprene and other organic precursors that can form brown carbon (BrC). Measured bulk aqueous-phase reaction rates of HA with ammonium sulfate, methylamine, and glycine suggest that these reactions cannot compete with aqueous-phase hydroxyl radical oxidation. In cloud chamber photooxidation experiments with either gaseous or particulate HA in the presence of the same N-containing species, BrC formation was minor, with similar mass absorption coefficients at 365 nm (<0.05 m 2 g –1 ). However, rapid changes observed in aerosol volume and gas-phase species concentrations suggest that the lack of BrC was not due to slow reactivity. Filter-based UHPLC/(+)ESI-HR-QTOFMS analysis revealed that the SOA became heavily oligomerized, with average molecular masses of ∼400 amu in all cases. Oligomers contained, on average, 3.9 HA, 1.5 ammonia, and 1.6 other small aldehydes, including, in descending order of abundance, acetaldehyde, glycolaldehyde, glyoxal, and methylglyoxal. PTR-ToF-MS confirmed the production of these aldehydes. We identify C 17 H 26 O 5, C 10 H 22 O 9, C 15 H 27 NO 7, C 17 H 23 NO 5, and C 18 H 32 N 2 O 9 as potential tracer ions for HA oligomers. We hypothesize that efficient oligomerization without substantial BrC production is due to negligible N-heterocycle (e.g., imidazoles/pyrazines) formation. While HA photooxidation is unlikely a significant atmospheric BrC source, it may contribute significantly to aqueous SOA formation.

Source: ACS Earth and Space Chemistry

DOI: 10.1021/acsearthspacechem.4c00237