科研成果 by Year: 2011

Studies have demonstrated that cis-pinonic acid (CPA) is an important product from the oxidation of pinenes with ozone. CPA has been measured on aerosols and is used as an aging indicator for secondary organic aerosols (SOA). CPA levels and formation in urban aerosols and its annual variability, however, are still poorly understood. Here, we present monthly CPA average concentrations on aerosols in Toronto, Ontario, Canada based on a two-year-period: 2000-2001. They displayed a seasonal pattern associated with temperature and ozone (O(3)) plus nitrogen dioxide (NO(2)) reflecting the influence these have on emissions of pinenes from forests and their atmospheric oxidation, respectively. However, in Toronto some months with higher CPA concentrations, especially in the winter, were inconsistent with the seasonality of temperature or/and O(3) + NO(2) levels. Instead these deviations were associated with increases in wood burning tracers such as dehydroabietic acid (DHAA) and sugars. Similar features were observed during a two-week-period comparing day and nighttime CPA concentrations in the Lower Fraser Valley (LFV) of British Columbia, Canada, in that the CPA concentrations clearly varied diurnally with temperature and O(3) + NO(2) on some days, but also showed a significant correspondence with variations in the wood burning tracer concentrations, such as levoglucosan. These findings demonstrate that CPA formation is strongly impacted by wood burning activity. Crown Copyright (C) 2011 Published by Elsevier Ltd. All rights reserved.

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.