Second-generation products contribute substantially to the particle-phase organic material produced by beta-caryophyllene ozonolysis

by Y J Li, Q Chen, M I Guzman, C K Chan, S T Martin
Atmospheric Chemistry and Physics ()


The production of secondary organic aerosol (SOA) by the dark ozonolysis of gas-phase beta-caryophyllene was studied. The experiments were conducted in a continuous-flow environmental chamber for organic particle mass concentrations of 0.5 to 30 mu g m(-3) and with ozone in excess, thereby allowing the study of second-generation particle-phase products under atmospherically relevant conditions. The particle-phase products were characterized by an ultra-performance liquid chromatograph equipped with an electrospray ionization time-of-flight mass spectrometer (UPLC-ESI-ToF-MS). Fragmentation mass spectra were used for the structural elucidation of each product, and the structures were confirmed as consistent with the accurate m/z values of the parent ions. In total, fifteen products were identified. Of these, three are reported for the first time. The structures showed that 9 out of 15 particle-phase products were second generation, including all three of the new products. The relative abundance of the second-generation products was approximately 90% by mass among the 15 observed products. The O:C and H:C elemental ratios of the 15 products ranged from 0.13 to 0.50 and from 1.43 to 1.60, respectively. Fourteen of the products contained 3 to 5 oxygen atoms. A singular product, which was one of the three newly identified ones, had 7 oxygen atoms, including 1 carboxylic group, 2 carbonyl groups, and 3 hydroxyl groups. It was identified as 2, 3-dihydroxy-4-[2-(4-hydroxy-3-oxobutyl)3, 3-dimethylcyclobutyl]-4-oxobutanoic acid (C14H22O7). The estimated saturation vapor pressure of this product is 3.3x10(-13) Pa, making this product a candidate contributor to new particle formation in the atmosphere.

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