Physical and chemical properties of submicrometer aerosol particles were measured in summer 2004 (June/July) and winter 2005 (January/February) in Beijing, Peoples Republic of China, using a Twin-Differential Mobility Particle Sizer (T-DMPS), a Hygroscopicity-Tandem Differential Mobility Analyzer (H-TDMA), and a Micro Orifice Uniform Deposit Impactor (MOUDI). Particle number-size distributions were measured in the diameter range Dp=3-800 nm and hygroscopic properties were determined at initial dry particle diameters of Dp(j) (j =30, 50, 80, 150, 250, and 350 nm) at a relative humidity (RH) of 90%. Hygroscopic properties were compared with chemical analyses of aerosol samples taken with the MOUDI. Based on the hygroscopicity data, the total hygroscopic particle volume was modeled, including dependence on dry particle size, season and level of pollution using a simple approach. Overall, the chemical analysis showed ammonium sulfate to be the major inorganic component of the urban submicrometer aerosol in Beijing along with relatively high fractions of elemental carbon (10-25%) and organic matter (15-60%) depending on particle size and season. The hygroscopic growth distributions (H-TDMA) subdivided the aerosol population into three different groups of particles with varying growth factors depending on dry particle size, namely nearly hydrophobic (growth factor=0.96-1.07), less hygroscopic (1.06-1.29) and more hygroscopic (1.26-1.62). Hydrophobic particle fractions indicating freshly emitted soot/carbonaceous particles varied between 10 and 32% depending on dry particle size and season. During heavily polluted times, a decreasing number of hydrophobic particle fractions indicated that the urban submicrometer aerosol in Beijing was highly influenced by more aged aerosol transported from the industrial regions around Beijing containing sulfate as a major component. Based on model calculations, the urban submicrometer aerosol in Beijing showed strong compositional variations. The calculated total hygroscopic volume fractions varied between 16 and 65% depending on size, level of pollution and season. (C) 2008 Elsevier Ltd. All rights reserved.
This study was part of the international field measurement Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing-2006). We investigated a new particle formation event in a highly polluted air mass at a regional site south of the megacity Beijing and its impact on the abundance and properties of cloud condensation nuclei (CCN). During the 1-month observation, particle nucleation followed by significant particle growth on a regional scale was observed frequently (similar to 30%), and we chose 23 August 2006 as a representative case study. Secondary aerosol mass was produced continuously, with sulfate, ammonium, and organics as major components. The aerosol mass growth rate was on average 19 mu g m(-3) h(-1) during the late hours of the day. This growth rate was observed several times during the 1-month intensive measurements. The nucleation mode grew very quickly into the size range of CCN, and the CCN size distribution was dominated by the growing nucleation mode ( up to 80% of the total CCN number concentration) and not as usual by the accumulation mode. At water vapor supersaturations of 0.07-0.86%, the CCN number concentrations reached maximum values of 4000-19,000 cm(-3) only 6-14 h after the nucleation event. During particle formation and growth, the effective hygroscopicity parameter kappa increased from about 0.1-0.3 to 0.35-0.5 for particles with diameters of 40-90 nm, but it remained nearly constant at similar to 0.45 for particles with diameters of similar to 190 nm. This result is consistent with aerosol chemical composition data, showing a pronounced increase of sulfate.
In the summers of 2002-2003, acidic gases, ammonia and water-soluble ions in PM10 were measured in Beijing. The mean concentrations of HCl, HONO, HNO3, SO2 and NH3 are 0.6, 3.6, 1.9, 14.1 and 16.6 mu g m(-3), respectively, and 2.2, 14.6, 19.3 and 8.9 mu g m(-3) for Cl-, NO-, SO2- and NH4+ in PM10. The concentrations of secondary ions in PM10 are found to have strong dependence on the pathway of trajectories. The most frequent southerly air flow is connected with high concentrations of secondary water-soluble ions during summertime. Other trajectories with northwest and north direction lead to lower concentrations of secondary ions. Hebei and Shandong Provinces and the Tianjin Municipality are the main source areas for sulfate as identified by Potential Source Contribution Function. This result emphasizes that the non-Beijing sources play an important role in the sulfate mass concentration in the urban atmosphere of Beijing and validates conclusions based on model calculations for the region. (C) 2009 Elsevier Ltd. All rights reserved.
An aerodyne high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) combined with a thermodenuder (TD) was used to investigate laboratory-generated aerosol particles with regard to their volatility and chemical content. The performance of the setup was tested first by using ammonium sulfate particles. Organic compounds have been measured including humic acid, fulvic acid, succinic acid and its disodium salt, 2-methylsuccinic acid, fumaric acid, alpha-ketoglutaric acid, and glutaric acid. Among them, humic acid, fulvic acid, and disodium succinate show a non-volatile fraction at 300 degrees C, while the other organic compounds are more volatile. Comparisons of mass spectra at different temperatures showed that significant differences in mass spectra of humic and fulvic acids are observed, indicating that their molecules changed during or after volatilization. At lower temperatures, the changes in humic acid are more likely due to the evaporation of small organic molecules or decomposition of aliphatic groups. The mass losses of the CO(2)(+) fragment for both humic and fulvic acids at higher temperatures may arise from decarboxylation processes. The different mass spectra for humic and fulvic acids before and after TD also suggest that one should be careful in interpretation of volatility measurements because some molecule structures may change after being heated, especially for the non-volatile multifunctional compounds. (C) 2009 Elsevier Ltd. All rights reserved.
The Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing-2006) were mainly focused on the influence of the regional aerosol on the air pollution in Beijing. The urban aerosol was characterized in detail. The particle size distributions were also compared to those measured at a regional site (Yufa) approximately 50 km south of the urban site at Peking University (PKU). At PKU, total particle number and volume concentrations were (1.8 +/- 0.8) x 10(4) cm(-3) and 83.5 +/- 57.9 mu m(3) cm(-3), respectively. Days in three consecutive summers of 2004, 2005, and 2006 were classified as polluted days with PM10 over 150 mu g m(-3) and nonpolluted days with lower PM10. On nonpolluted days, particle number size distributions showed a maximum at about 60 nm with Aitken mode particles dominating number concentration. On polluted days, the contribution of accumulation mode particles increased, shifting the maximum of the number size distribution to over 80 nm. On polluted days with stagnant meteorological conditions, secondary aerosol dominated, with SO42-, NO3-, and NH4+ accounting for over 60% of accumulation mode particle mass. Particle number size distributions at both sites were similar. Number and volume concentrations of total particles at Yufa were 6% and 12% lower, respectively; those of accumulation mode particles were 2% and 15% lower. This means that air pollution in Beijing is mainly a regional problem. The regional accumulation mode particles are a metric for assessing the air quality since they influence most the visibility and total mass concentration. Their number and volume concentrations on polluted days were 5 x 10(3) cm(-3) and 30 mu m(3) cm(-3), respectively. Five new particle formation (NPF) events with continuous smooth growth were observed at both PKU and Yufa during CAREBeijing-2006. These NPF events are regional or semiregional. Growth rates at PKU ranged from 1.2 to 5.6 nm h(-1), and formation rates ranged from 1.1 to 22.4 cm(-3) s(-1). SO42-, NH4+, and oxalate might be important contributors to NPF events.