Real-time, single-particle measurements of oligomers in aged ambient aerosol particles

Unique high mass negative ions in the -200 to -400 mass/charge range with repetitive spacings of 12, 14, and 16 units, representative of oligomeric species, have been detected in single ambient submicrometer aerosol particles using real-time single-particle mass spectrometry during the Study of Organic Aerosols field campaign conducted in Riverside, CA (SOAR) in August and November 2005. These oligomer-containing particles represented 33-40% of the total detected particles and contained other indicators of aging including oxidized organic carbon, amine, nitrate, and sulfate ion markers. Overall, the highest mass oligomeric patterns were observed in small acidic 140-200 nm particles in the summer. Also during the summer, increased oligomer intensities were observed when the particles were heated with a thermodenuder. We hypothesize that heat removed semivolatile species, thereby increasing particle acidity, while concentrating the oligomeric precursors and accelerating oligomer formation. Differences in oligomer behavior with respect to particle size and heating can be attributed to seasonal differences in photochemical oxidation, the relative amount of ammonium, and particle acidity.