Isomer-Resolved Mobility-Mass Analysis of α-Pinene Ozonolysis Products.

Highly oxygenated organic molecules (HOMs) are important sources of atmospheric aerosols. Resolving the molecular-level formation mechanisms of these HOMs from freshly emitted hydrocarbons improves the understanding of aerosol properties and their influence on the climate. In this study, we measure the electrical mobility and mass-to-charge ratio of α-pinene oxidation products using a secondary electrospray-differential mobility analyzer-mass spectrometer (SESI-DMA-MS). The mass-mobility spectrum of the oxidation products is measured with seven different reagent ions generated by the electrospray. We analyzed the mobility-mass spectra of the oxidation products C9-10H14-18O2-6. Our results show that acetate and chloride yield the highest charging efficiencies. Analysis of the mobility spectra suggests that the clusters have 1-5 isomeric structures (i.e., ion-molecule cluster structures with distinct mobilities), and the number is affected by the reagent ion. Most of the isomers are likely cluster isomers originating from binding of the reagent ion to different sites of the molecule. By comparing the number of observed isomers and measured mobilities and collision cross sections between standard pinanediol and pinonic acid to the values observed for C10H18O2 and C10H16O3 produced from oxidation of α-pinene, we confirm that pinanediol and pinonic acid are the only isomers for these elemental compositions in our experimental conditions. Our study shows that the SESI-DMA-MS produces new information from the first steps of oxidation of α-pinene.

Electrical Mobility as an Indicator for Flexibly Deducing the Kinetics of Nanoparticle Evaporation.

Condensation and evaporation of vapor species on nanoparticle surfaces drive the aerosol evolution in various industrial/atmospheric systems, but probing these transient processes is challenging due to related time and length scales. Herein, we present a novel methodology for deducing nanoparticle evaporation kinetics using electrical mobility as a natural size indicator. Monodispersed nanoparticles are fed to a differential mobility analyzer which serves simultaneously as an evaporation flowtube and an instrument for measuring the electrical mobility, realizing measurements of evaporation processes with time scales comparable to the instrument response time. A theoretical framework is derived for deducing the evaporation kinetics from instrument responses through analyzing the nanoparticle trajectory and size-mobility relationship, which considers the coupled mass and heat transfer effect and is applicable to the whole Knudsen number range. The methodology is demonstrated against evaporation but can potentially be extended to condensation and other industrial/atmospheric processes involving rapid size change of nanoparticles.