Direct Sampling and Analysis of Atmospheric Particulate Organic Matter by Proton-Transfer-Reaction Mass Spectrometry.

We report on a new method for analyzing atmospheric submicrometer particulate organic matter which combines direct particle sampling and volatilization with online chemical ionization mass spectrometric analysis. Technically, the method relies on the combined use of a CHARON ("Chemical Analysis of Aerosol Online") particle inlet and a proton-transfer-reaction time-of-flight mass spectrometer (PTR-ToF-MS). Laboratory studies on target analytes showed that the ionization conditions in the PTR-ToF-MS lead to extensive fragmentation of levoglucosan and cis-pinonic acid, while protonated oleic acid and 5α-cholestane molecules remain intact. Potential problems and biases in quantitative and qualitative analyses are discussed. Side-by-side atmospheric comparison measurements of total particulate organic mass and levoglucosan with an aerosol mass spectrometer (AMS) were in good agreement. Complex and clearly distinct organic mass spectra were obtained from atmospheric measurements in three European cities (Lyon, Valencia, Innsbruck). Data visualization in reduced-parameter frameworks (e.g., oxidation state of carbon vs carbon number) revealed that the CHARON-PTR-ToF-MS technique adds significant analytical capabilities for characterizing particulate organic carbon in the Earth's atmosphere. Positive matrix factorization (PMF) was used for apportioning sources of atmospheric particles in late fall in Innsbruck. The m/z signatures of known source marker compounds (levoglucosan and resin acids, polycyclic aromatic hydrocarbons, nicotine) in the mass spectra were used to assign PMF factors to biomass burning, traffic, and smoking emission sources.