Using Ionic Liquids To Study the Migration of Semivolatile Organic Vapors in Smog Chamber Experiments.

Abstract

Atmospheric organic aerosols comprise complex mixtures of a myriad of compounds with a wide range of structures and volatilities. To understand the fate of atmospheric organic aerosols and their contribution to particulate matter pollution, we need to study the relative portion divided between semivolatile organic compounds (SVOCs) and low-volatility organic compounds (LVOCs). SVOCs can effectively migrate and exchange between aerosol populations and thus are more accessible for further reactions and removal processes, while LVOCs will essentially stay in the particle phase. Here, we introduce using ionic liquid droplets as novel sorbents for organic vapors in smog chamber experiments to study the transfer of constituents between aerosol populations and to separate SVOCs and LVOCs from chamber-produced secondary organic aerosols (SOAs). SOA was formed and condensed on the ammonium-sulfate seeds, and later ionic liquid droplets were introduced into the chamber. We show that there areconsiderable yields of both LVOCs and SVOCs produced from α-pinene ozonolysis, and the uptake of SVOCs into the ionic liquid increases as the amount of reacted α-pinene increases. We also show that the SVOCs absorbed into the ionic liquid re-evaporate more readily compared to SOA originally condensed on the ammonium-sulfate seeds. We are thus able to differentiate the semivolatile components that partition into the extremely polar ionic liquid aerosols from the demonstrably less volatile components also condensed on the ammonium-sulfate seeds. Combinedwith previous studies using other organic aerosols as solvents to probe SVOC transfer between aerosol populations, we provide a wide set of measurements to probe and constrain the physical and thermodynamic properties of chamber-produced SOA complex.