Time-resolved molecular characterization of organic aerosols by PILSÂ +Â UPLC/ESI-Q-TOFMS

•We integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol.•We apply this technique to study the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.

Real-time and quantitative measurement of particulate matter chemical composition represents one of the most challenging problems in the field of atmospheric chemistry. In the present study, we integrate the Particle-into-Liquid Sampler (PILS) with Ultra Performance Liquid Chromatography/Electrospray ionization Quadrupole Time-of-Flight High-Resolution/Mass Spectrometry (UPLC/ESI-Q-TOFMS) for the time-resolved molecular speciation of chamber-derived secondary organic aerosol (SOA). The unique aspect of the combination of these two well-proven techniques is to provide quantifiable molecular-level information of particle-phase organic compounds on timescales of minutes. We demonstrate that the application of the PILS + UPLC/ESI-Q-TOFMS method is not limited to water-soluble inorganic ions and organic carbon, but is extended to slightly water-soluble species through collection efficiency calibration together with sensitivity and linearity tests. By correlating the water solubility of individual species with their O:C ratio, a parameter that is available for aerosol ensembles as well, we define an average aerosol O:C ratio threshold of 0.3, above which the PILS overall particulate mass collection efficiency approaches ∼0.7. The PILS + UPLC/ESI-Q-TOFMS method can be potentially applied to probe the formation and evolution mechanism of a variety of biogenic and anthropogenic SOA systems in laboratory chamber experiments. We illustrate the application of this method to the reactive uptake of isoprene epoxydiols (IEPOX) on hydrated and acidic ammonium sulfate aerosols.