Hideto Takekawa

Temperature dependence of secondary organic aerosol formation by photo-oxidation of hydrocarbons

Photo-oxidation experiments on hydrocarbons were performed with a temperature-controlled smog chamber to study the temperature dependence of secondary organic aerosol (SOA) formation. A higher SOA yield was obtained at lower temperature and with a higher concentration of SOA generated. The relationship of SOA yield to temperature and SOA concentration is expressed by a gas/particle partitioning absorption model considered with temperature dependence. Under the condition of the same SOA concentration, the SOA yield at 283 K was approximately twice that at 303 K. It has been clarified experimentally that temperature is one of the most important factors in SOA formation. The experiments were performed not only with three aromatic hydrocarbons (toluene, m-xylene and 1,2,4-trimethylbenzene) and one biogenic alkene (α-pinene), but also with one alkane (n-undecane) on which few experiments for SOA formation have been performed. n-Undecane indicates a lower SOA yield than any other hydrocarbon investigated in this study.

A modeling study of coarse particulate matter pollution in Beijing: regional source contributions and control implications for the 2008 Summer Olympics.

Abstract 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 (PM10) 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 PM10 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 PM10 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 PM10 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 PM10 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.

Decreasing effect and mechanism of FeSO4 seed particles on secondary organic aerosol in α-pinene photooxidation

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.

Effects of two transition metal sulfate salts on secondary organic aerosol formation in toluene/NOx photooxidation

Aerosol phase reactions play a very important role on secondary organic aerosol (SOA) formation, and metal-containing aerosols are important components in the atmosphere. In this study, we tested the effects of two transition metal sulfate salts, manganese sulfate (MnSO4) and zinc sulfate (ZnSO4), on the photochemical reactions of a toluene/NOx photooxidation system in a 2 m3 smog chamber. By comparing photochemical reaction products of experiments with and without transition metal sulfate seed aerosols, we evaluated the effects of transition metal sulfate seed aerosols on toluene consumption, NOx conversion and the formation of ozone and SOA. MnSO4 and ZnSO4 seed aerosols were found to have similar effects on photochemical reactions, both enhance the SOA production, while showing negligible effects on the gas phase compounds. These observations are consistent when varying metal sulfate aerosol concentrations. This is attributed to the catalytic effects of MnSO4 and ZnSO4 seed aerosols which may enhance the formation of condensable semivolatile compounds. Their subsequent partitioning into the aerosol phase leads to the observed SOA formation enhancement.

Hygroscopicity of particles generated from photooxidation of α-pinene under different oxidation conditions in the presence of sulfate seed aerosols

Smog chamber experiments were conducted to investigate the hygroscopicity of particles generated from photooxidation of alpha-pinene/NO(x) with different sulfate seed aerosols or oxidation conditions. Hygroscopicity of particles was measured by a tandem differential mobility analyzer (TDMA) in terms of hygroscopic growth factor (Gf), with a relative humidity of 85%. With sulfate seed aerosols present, Gf of the aerosols decreased very fast before notable secondary organic aerosols (SOA) formation was observed, indicating a heterogeneous process between inorganic seeds and organic products might take place as soon as oxidation begins, rather than only happening after gas-aerosol partition of organic products starts. The final SOA-coated sulfate particles had similar or lower Gf than seed-free SOA. The hygroscopicity of the final particles was not dependent on the thickness but on the hygroscopicity properties of the SOA, which were influenced by the initial sulfate seed particles. In the two designed aging processes, Gf of the particles increased more significantly with introduction of OH radical than with ozone. However, the hygroscopicity of SOA was very low even after a long time of aging, implying that either SOA aging in the chamber was very slow or the Gf of SOA did not change significantly in aging. Using an aerosol composition speciation monitor (ACSM) and matrix factorization (PMF) method, two factors for the components of SOA were identified, but the correlation between SOA hygroscopicity and the proportion of the more highly oxidized factor could be either positive or negative depending on the speciation of seed aerosols present.

Influence of metal-mediated aerosol-phase oxidation on secondary organic aerosol formation from the ozonolysis and OH-oxidation of α-pinene

The organic component is the most abundant fraction of atmospheric submicron particles, while the formation mechanisms of secondary organic aerosol (SOA) are not fully understood. The effects of sulfate seed aerosols on SOA formation were investigated with a series of experiments carried out using a 9 m3 smog chamber. The presence of FeSO4 or Fe2(SO4)3 seed aerosols decreased SOA yields and increased oxidation levels in both ozonolysis and OH-oxidation of α-pinene compared to that in the presence of ZnSO4 or (NH4)2SO4. These findings were explained by metal-mediated aerosol-phase oxidation of organics: reactive radicals were generated on FeSO4 or Fe2(SO4)3 seed aerosols and reacted further with the organic mass. This effect would help to explain the high O/C ratios of organics in ambient particles that thus far cannot be reproduced in laboratory and model studies. In addition, the gap in the SOA yields between experiments with different seed aerosols was more significant in OH-oxidation experiments compared to ozonolysis experiments, while the gap in estimated O/C ratios was less obvious. This may have resulted from the different chemical compositions and oxidation levels of the SOA generated in the two systems, which affect the branching ratio of functionalization and fragmentation during aerosol oxidation.