Organic aerosol formation during the atmospheric oxidation of toluene was investigated using smog chamber systems. Toluene oxidation was initiated by the UV irradiation of either toluene/air/NOx or toluene/air/CH3ONO/NO mixtures. Aerosol formation was monitored using scanning mobility particle sizers and toluene loss was monitored by in-situ FTIR spectroscopy or GC-FID techniques. The experimental results show that the reaction of OH radicals, NO3 radicals and/or ozone with the first generation products of toluene oxidation are sources of organic aerosol during the atmospheric oxidation of toluene. The aerosol results fall into two groups, aerosol formed in the absence and presence of ozone. An analytical expression for aerosol formation is developed and values are obtained for the yield of the aerosol species. In the absence of ozone the aerosol yield, defined as aerosol formed per unit toluene consumed once a threshold for aerosol formation has been exceeded, is 0.075 +/- 0.004. In the presence of ozone the aerosol yield is 0.108 +/- 0.004. This work provides experimental evidence and a simple theory confirming the formation of aerosol from secondary reactions.
In the last 10 yr, Beijing has made a great effort to improve its air quality. However, it is still suffering from regional coarse particulate matter (PM 10 ) pollution that could be a challenge to the promise of clean air during the 2008 Olympics. To provide scientific guidance on regional air pollution control, the Mesoscale Modeling System Generation 5 (MM5) and the Models-3/Community Multiscale Air Quality Model (CMAQ) air quality modeling system was used to investigate the contributions of emission sources outside the Beijing area to pollution levels in Beijing. The contributions to the PM 10 concentrations in Beijing were assessed for the following sources: power plants, industry, domestic sources, transportation, agriculture, and biomass open burning. In January, it is estimated that on average 22% of the PM 10 concentrations can be attributed to outside sources, of which domestic and industrial sources contributed 37 and 31%, respectively. In August, as much as 40% of the PM 10 concentrations came from regional sources, of which approximately 41% came from industry and 31% from power plants. However, the synchronous analysis of the hourly concentrations, regional contributions, and wind vectors indicates that in the heaviest pollution periods the local emission sources play a more important role. The implications are that long-term control strategies should be based on regional-scale collaborations, and that emission abatement of local sources may be more effective in lowering the PM 10 concentration levels on the heavy pollution days. Better air quality can be attained during the Olympics by placing effective emission controls on the local sources in Beijing and by controlling emissions from industry and power plants in the surrounding regions.
α-Pinene/NOx and α-pinene/HONO photooxidation experiments at varying humidity were conducted in smog chambers in the presence or absence of FeSO4 seed particles. FeSO4 seed particles decrease SOA mass as long as water was present on the seed particle surface, but FeSO4 seed particles have no decreasing effect on SOA under dryer conditions at 12% relative humidity (RH). The decreasing effect of FeSO4 seed particles on the SOA mass is proposed to be related to oxidation processes in the surface layer of water on the seed particles. Free radicals, including OH, can be formed from catalytic cycling of Fe(2+) and Fe(3+) in the aqueous phase. These radicals can react further with the organic products of α-pinene oxidation on the seed particles. The oxidation may lead to formation of smaller molecules which have higher saturation vapor pressures and favor repartitioning to the gas phase, and therefore, reduces SOA mass.
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