Wentai Chen

Chemical composition, sources, and aging process of submicron aerosols in Beijing: Contrast between summer and winter

To investigate the seasonal characteristics of submicron aerosol (PM1) in Beijing urban areas, a high-resolution time-of-flight aerosol-mass-spectrometer (HR-ToF-AMS) was utilized at an urban site in summer (August to September 2011) and winter (November to December 2010), coupled with multiple state of the art online instruments. The average mass concentrations of PM1 (60–84 µg m−3) and its chemical compositions in different campaigns of Beijing were relatively consistent in recent years. In summer, the daily variations of PM1 mass concentrations were stable and repeatable. Eighty-two percent of the PM1 mass concentration on average was composed of secondary species, where 62% is secondary inorganic aerosol and 20% secondary organic aerosol (SOA). In winter, PM1 mass concentrations changed dramatically because of the different meteorological conditions. The high average fraction (58%) of primary species in PM1 including primary organic aerosol (POA), black carbon, and chloride indicates primary emissions usually played a more important role in the winter. However, aqueous chemistry resulting in efficient secondary formation during occasional periods with high relative humidity may also contribute substantially to haze in winter. Results of past OA source apportionment studies in Beijing show 45–67% of OA in summer and 22–50% of OA in winter can be composed of SOA. Based on the source apportionment results, we found 45% POA in winter and 61% POA in summer are from nonfossil sources, contributed by cooking OA in both seasons and biomass burning OA (BBOA) in winter. Cooking OA, accounting for 13–24% of OA, is an important nonfossil carbon source in all years of Beijing and should not be neglected. The fossil sources of POA include hydrocarbon-like OA from vehicle emissions in both seasons and coal combustion OA (CCOA) in winter. The CCOA and BBOA were the two main contributors (57% of OA) for the highest OA concentrations (>100 µg m−3) in winter. The POA/ΔCO ratios in winter and summer are 11 and 16 µg m−3 ppm−1, respectively, similar to ratios from western cities. Higher OOA/Ox (= NO2 + O3) ratio (0.49 µg m−3 ppb−1) in winter study than these ratios from western cities (0.03–0.16 µg m−3 ppb−1) was observed, which may be due to the aqueous reaction or extra SOA formation contributed by semivolatile organic compounds from various primary sources (e.g., BBOA or CCOA) in Beijing. The evolution of oxygen to carbon ratio (O/C) with photochemical age allows to estimate an equivalent rate constant for chemical aging of OA in summer as kOH ~ 4.1 × 10−12 cm3 molecule−1 s−1, which is of the same order as obtained in other anthropogenic influenced areas and may be useful for OA modeling.

Development and validation of a cryogen-free automatic gas chromatograph system (GC-MS/FID) for online measurements of volatile organic compounds

An automatic gas chromatograph system equipped with a mass spectrometer and a flame ionization detector (GC-MS/FID) was developed for online measurements of volatile organic compounds (VOCs) in the atmosphere. This system consisted of a custom-built cryogen-free cooling device that can create an ultra-low temperature of −165 °C, a two-channel sampling and pre-concentration system, and a commercial GC-MS/FID. One channel in the sampling and pre-concentration system was designated to trap C2–C5 hydrocarbons, whereas the other was designed to trap other VOC species. The newly developed GC-MS/FID system was then employed to measure VOCs in ambient air, and its observation data were compared with those from three well-established techniques, including an offline GC-MS/FID coupled with canister sampling, a proton transfer reaction-mass spectrometer (PTR-MS), and an online gas chromatograph system equipped with an FID and a photo ionization detector (GC-FID/PID). The online and offline GC-MS/FID measurements for alkanes, acetylene, C2–C3 alkenes, C6–C8 aromatics, and halocarbons showed good agreement. In addition, the online GC-MS/FID measurements for C6–C9 aromatics, acetone, and methacrolein + methylvinylketone (MACR + MVK) agreed well with the PTR-MS observations. Mixing ratios of C2–C7 alkanes, C3–C5 alkenes, and C6–C8 aromatics also showed good agreement between the online GC-MS/FID and GC-FID/PID techniques. These inter-comparison results demonstrated the accuracy of online GC-MS/FID measurements for C2–C12 NMHCs, C3–C4 carbonyls, and halocarbons.

Emission factors of gaseous carbonaceous species from residential combustion of coal and crop residue briquettes

Experiments were performed to measure the emission factors (EFs) of gaseous carbonaceous species, such as CO2, CO, CH4, and non-methane volatile organic compounds (NMVOCs), from the combustion of five types of coal of varying organic maturity and two types of biomass briquettes under residential burning conditions. Samples were collected in stainless steel canisters and 2,4-dinitrophenylhydrazine (DNPH) cartridges and were analyzed by GC-FID/MS and HPLC, respectively. The EFs from crop residue briquette burning were generally higher than those from coals, with the exception of CO2. The dominant NMVOC species identified in coal smoke were carbonyls (41.7%), followed by C2 unsaturated hydrocarbons (29.1%) and aromatics (12.1%), while C2 unsaturated hydrocarbons were the dominant species (68.9%) emitted from the combustion of crop residue briquettes, followed by aromatics (14.4%). A comparison of burning normal crop residues in stoves and the open field indicated that briquettes emitted a larger proportion of ethene and acetylene. Both combustion efficiency and coal organic maturity had a significant impact on NMVOC EFs from burning coal: NMVOC emissions increased with increasing coal organic maturity but decreased as the combustion efficiency improved. Emissions from the combustion of crop residue briquettes from stoves occurred mainly during the smoldering process, with low combustion efficiency. Therefore, an improved stove design to allow higher combustion efficiency would be beneficial for reducing emissions of carbonaceous air pollutants.

Investigation of carbonyl compound sources at a rural site in the Yangtze River Delta region of China

Carbonyl compounds are important intermediates in atmospheric photochemistry, but their primary sources are still not understood well. In this work, carbonyls, hydrocarbons, and alkyl nitrates were continuously measured during November 2011 at a rural site in the Yangtze River Delta region of China. Mixing ratios of carbonyls and hydrocarbons showed large fluctuations during the entire measurement. The average level for total measured volatile organic compounds during the pollution episode from 25th to 27th November, 2011 was 91.6 ppb, about 7 times the value for the clean period of 7th-8th, November, 2011. To preliminarily identify toluene sources at this site, the emission ratio of toluene to benzene (T/B) during the pollution episode was determined based on photochemical ages derived from the relationship of alkyl nitrates to their parent alkanes. The calculated T/B was 5.8 ppb/ppb, significantly higher than the values of 0.2-1.7 ppb/ppb for vehicular exhaust and other combustion sources, indicating the dominant influence of industrial emissions on ambient toluene. The contributions of industrial sources to ambient carbonyls were then calculated using a multiple linear regression fit model that used toluene and alkyl nitrates as respective tracers for industrial emission and secondary production. During the pollution episode, 18.5%, 69.0%, and 52.9% of measured formaldehyde, acetaldehyde, and acetone were considered to be attributable to industrial emissions. The emission ratios relative to toluene for formaldehyde, acetaldehyde, and acetone were determined to be 0.10, 0.20 and 0.40 ppb/ppb, respectively. More research on industrial carbonyl emission characteristics is needed to understand carbonyl sources better.