Characterization of particulate products for aging of ethylbenzene secondary organic aerosol in the presence of ammonium sulfate seed aerosol

Aging of secondary organic aerosol（SOA） particles formed from OH– initiated oxidation of ethylbenzene in the presence of high mass（100–300 μg/m^3） concentrations of（NH_4）_2SO_4seed aerosol was investigated in a home-made smog chamber in this study.The chemical composition of aged ethylbenzene SOA particles was measured using an aerosol laser time-of-flight mass spectrometer（ALTOFMS） coupled with a Fuzzy C-Means（FCM） clustering algorithm.Experimental results showed that nitrophenol,ethyl-nitrophenol,2,4-dinitrophenol,methyl glyoxylic acid,5-ethyl-6-oxo-2,4-hexadienoic acid,2-ethyl-2,4-hexadiendioic acid,2,3-dihydroxy-5-ethyl-6-oxo-4-hexenoic acid,1H-imidazole,hydrated N-glyoxal substituted1H-imidazole,hydrated glyoxal dimer substituted imidazole,1H-imidazole-2-carbaldehyde,N-glyoxal substituted hydrated 1H-imidazole-2-carbaldehyde and high-molecular-weight（HMW） components were the predominant products in the aged particles.Compared to the previous aromatic SOA aging studies,imidazole compounds,which can absorb solar radiation effectively,were newly detected in aged ethylbenzene SOA in the presence of high concentrations of（NH_4）_2SO_4seed aerosol.These findings provide new information for discussing aromatic SOA aging mechanisms.

Infrared spectroscopic probing of dimethylamine clusters in an Ar matrix

Amines have many atmospheric sources and their clusters play an important role in aerosol nucleation processes. Clusters of a typical amine, dimethylamine（DMA）, of different sizes were measured with matrix isolation IR（infrared） and NIR（near infrared）spectroscopy. The NIR vibrations are more separated and therefore it is easier to distinguish different sizes of clusters in this region. The DMA clusters, up to DMA tetramer, have been optimized using density functional methods, and the geometries, binding energies and thermodynamic properties of DMA clusters were obtained. The computed frequencies and intensities of NH-stretching vibrations in the DMA clusters were used to interpret the experimental spectra. We have identified the fundamental transitions of the bonded NH-stretching vibration and the first overtone transitions of the bonded and free NH-stretching vibration in the DMA clusters. Based on the changes in vibrational intensities during the annealing processes, the growth of clusters was clearly observed. The results of annealing processes indicate that DMA molecules tend to form larger clusters with lower energies under matrix temperatures, which is also supported by the calculated reaction energies of cluster formation.