Reactive uptake of pinonaldehyde on acidic aerosols

Abstract

The reactive uptake of pinonaldehyde, a monoterpene oxidation product, on aerosols has been studied in a reaction chamber. Monodisperse inorganic seed aerosols, consisting of acidic mixtures of (NH4)2SO4 and H2SO4, were exposed to gaseous pinonaldehyde for several hours within the chamber under relative humidity conditions of 3–65%. The aerosol inorganic and organic mass were quantitatively monitored in real time with an aerosol mass spectrometer (AMS) which also measured the mass spectra of the aerosols. Numerous fragments in the mass spectra were observed with masses greater than what can be accounted for by pinonaldehyde alone and have arisen from oligomerization in reactive uptake processes. The evolution of the mass spectra also revealed a progression toward larger oligomers over time. Significant organic mass was added to the aerosols in most experiments immediately upon exposure, resulting in maximum organic mass loadings from 3.5–110 μgm−3 depending on the experiments. Organic mass to seed aerosol SO4= ratios were also highly variable (0.06–4.75), resulting in particles ranging in composition from primarily inorganic to mostly organic. This reactive uptake was highly dependent upon the aerosol water activity, and hence acidity and did not occur on neutral (NH4)2SO4 aerosols suggesting that acidity is necessary. Reactive uptake coefficients (γ) of pinonaldehyde were calculated by fitting a model of organic mass growth to the data. The coefficients spanned two orders of magnitude (1.2 × 10−5–1.3 × 10−3) and were primarily dependent upon aerosol water activity and acidity but independent of gas phase pinonaldehyde concentrations. These coefficients indicated that the heterogeneous reactions of pinonaldehyde are of little importance as a gas phase loss mechanism but potentially of major importance as a source of secondary organic aerosols (SOA). Estimates of SOA production via pinonaldehyde, using the derived γ, suggest that 1–750 ng m−3 of organic material can be formed in a short time, consistent with ambient measurements.