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An Aerodyne quadrupole aerosol mass spectrometer (AMS) was deployed in China in the summer of 2006. The measurements were made in the Pearl River Delta region in July 2006 (PRD campaign) and also in Beijing in August-September 2006 (CAREBEIJING campaign). The AMS successfully measured size-resolved chemical composition of submicron non-refractory aerosol (vaporized at 600°C in vacuum) with a time resolution of 10 min, although some quantification issues have been identified. We observed extremely large signals at m/z 39 (39K+) and 41 (41K+), which significantly exceeded m/z 28 (N+2) signals. We also found large signals of m/z 85 (85Rb+), 87 (87Rb+), and 133 (Cs+). Laboratory experiments suggest that the large enhancement of K+ could have been due to the presence of K-containing particles in ambient air. The interferences of alkali metals at m/z 41, 85, 87, and 133 were significant and need to be corrected for better quantification of organic aerosol. The AMS measurements are compared with other, collocated measurements: a particle-into-liquid sampler combined with an ion chromatograph (PILS-IC), a Sunset Laboratory semi-continuous carbonaceous aerosol analyzer, and a Berner impactor sampler followed by off-line ion chromatography analysis (for major inorganic ions). We have found good agreement between the AMS and the other instruments when we assume an AMS particle collection efficiency (CE) of 0.5 for the PRD data and CE = 1.0 for the CAREBEIJING data. These results suggest that the AMS CE could be significantly different in different locations. Possible factors affecting the variability in the CE values are discussed. [ABSTRACT FROM AUTHOR]

Atmospheric hydrogen peroxide (H2O2) and organic hydroperoxides were measured from 18 to 30 July in 2006 during the PRIDE-PRD'06 campaign at Backgarden, a rural site located 48 km north of Guangzhou, a mega-city in southern China. A ground-based instrument was used as a scrubbing coil collector to sample ambient air, followed by on-site analysis by high-performance liquid chromatography (HPLC) coupled with post-column derivatization and fluorescence detection. The H2O2 mixing ratio over the 13 days ranged from below the detection limit to a maximum of 4.6 ppbv, with a mean (and standard deviation) of (1.26±1.24) ppbv during the daytime (08:00-20:00 LT). Methyl hydroperoxide (MHP), with a maximum of 0.8 ppbv and a mean (and standard deviation) of (0.28±0.10) ppbv during the daytime, was the dominant organic hydroperoxide. Other organic peroxides, including bis-hydroxymethyl hydroperoxide (BHMP), peroxyacetic acid (PAA), hydroxymethyl hydroperoxide (HMHP), 1-hydroxy-ethyl hydroperoxide (1-HEHP) and ethyl hydroperoxide (EHP), were detected occasionally. The concentration of H2O2 exhibited a pronounced diurnal variation on sunny days, with a peak mixing ratio in the afternoon (12:00-18:00 LT), but lacked an explicit diurnal cycle on cloudy days. Sometimes a second peak mixing ratio of H2O2 was observed during the evening, suggesting that H2O2 was produced by the ozonolysis of alkenes. The diurnal variation profile of MHP was, in general, consistent with that of H2O2. The estimation indicated that in the morning the H2O2 detected was formed mostly through local photochemical activity, with the rest probably attributable to vertical transport. It is notable that relatively high levels of H2O2 and MHP were found in polluted air. The unexpectedly high level of HO2 radicals detected in this region can account for the production of hydroperoxides, while the moderate level of NOx suppressed the formation of hydroperoxides. High concentrations of hydroperoxides were detected in samples of rainwater collected in a heavy shower on 25 July when a typhoon passed through, indicating that a considerable mixing ratio of hydroperoxides, particularly MHP, resided above the boundary layer, which might be transported on a regional scale and further influence the redistribution of HOx and ROx radicals. It was found that hydroperoxides, in particular H2O2, play an important role in the formation of secondary sulfate in the aerosol phase, where the heterogeneous reaction might contribute substantially. A negative correlation between hydroperoxides and water-soluble organic compounds (WSOC), a considerable fraction of the secondary organic aerosol (SOA), was observed, possibly providing field evidence for the importance of hydroperoxides in the formation of SOA found in previous laboratory studies. We suggest that hydroperoxides act as an important link between sulfate and organic aerosols, which needs further study and should be considered in current atmospheric models. [ABSTRACT FROM AUTHOR]

The scattering and absorption of solar radiation by atmospheric aerosols is a key element of the Earth's radiative energy balance and climate. The optical properties of aerosol particles are, however, highly variable and not well characterized, especially near newly emerging mega-cities. In this study, aerosol optical properties were measured at a rural site approximately 60 km northwest of the mega-city Guangzhou in southeast China. The measurements were part of the PRIDE-PRD2006 intensive campaign, covering the period of 1-30 July 2006. Scattering and absorption coefficients of dry aerosol particles with diameters up to 10 μm (PM10) were determined with a three-wavelength integrating nephelometer and with a photoacoustic spectrometer, respectively. Averaged over the measurement campaign (arithmetic mean ± standard deviation), the total scattering coefficients were 200±133Mm-1 (450 nm), 151±103Mm-1 (550 nm) and 104±72Mm-1 (700 nm) and the absorption coefficient was 34.3±26.5Mm-1 (532 nm). The average Å gström exponent was 1.46±0.21 (450 nm/700 nm) and the average single scattering albedo was 0.82±0.07 (532 nm) with minimum values as low as 0.5. The low single scattering albedo values indicate a high abundance, as well as strong sources, of light absorbing carbon (LAC). The ratio of LAC to CO concentration was highly variable throughout the campaign, indicating a complex mix of different combustion sources. The scattering and absorption coefficients, as well as the Ångström exponent and single scattering albedo, exhibited pronounced diurnal cycles, which can be attributed to boundary layer mixing effects and enhanced nighttime emissions of LAC (diesel soot from regulated truck traffic). The daytime average mid-visible single scattering albedo of 0.87 appears to be more suitable for climate modeling purposes than the 24-h average of 0.82, as the latter value is strongly influenced by fresh emissions into a shallow nocturnal boundary layer. In spite of high photochemical activity during daytime, we found no evidence for strong local production of secondary aerosol mass. The average mass scattering efficiencies with respect to PM10 and PM1 concentrations derived from particle size distribution measurements were 2.8m² g-1 and 4.1m² g-1, respectively. The Ångström exponent exhibited a wavelength dependence (curvature) that was related to the ratio of fine and coarse particle mass (PM1/PM10) as well as the surface mode diameter of the fine particle fraction. The results demonstrate consistency between in situ measurements and a remote sensing formalism with regard to the fine particle fraction and volume mode diameter, but there are also systematic deviations for the larger mode diameters. Thus we suggest that more data sets from in situ measurements of aerosol optical parameters and particle size distributions should be used to evaluate formalisms applied in aerosol remote sensing. Moreover, we observed a negative correlation between single scattering albedo and backscatter fraction, and we found that it affects the impact that these parameters have on aerosol radiative forcing efficiency and should be considered in model studies of the PRD and similarly polluted mega-city regions. [ABSTRACT FROM AUTHOR]

Abstract: Size-resolved chemical compositions of non-refractory submicron aerosols were measured using a quadrupole Aerodyne aerosol mass spectrometer at a rural site near Guangzhou in the Pearl River Delta (PRD) of China in the summer of 2006. Two cases characterized as the outflows from the PRD urban region with plumes of high SO2 concentration were investigated. The evolution of sulfate size distributions was observed on a timescale of several hours. Namely mass concentrations of sulfate in the condensation mode (with vacuum aerodynamic diameters (Dva ) < 300 nm) increased at a rate of about 0.17–0.37 ppbv h−1 during the daytime. This finding was consistent with the sulfuric acid production rates of about 0.17–0.3 ppbv h−1, as calculated from the observed gas-phase concentrations of OH (∼3.3 × 106–1.7 × 107 cm−3) and SO2 (∼3–21.2 ppbv). This implies that the growth of sulfate in the condensation mode was mainly due to gas-phase oxidation of SO2. The observed rapid increase was caused mainly by the concurrent high concentrations of OH and SO2 in the air mass. The evolution of the mass size distributions of m/z 44, a tracer for oxygenated organic aerosol (OOA), was very similar to that of sulfate. The mass loadings of m/z 44 were strongly correlated with those of sulfate (r 2 = 0.99) in the condensation mode, indicating that OOA might also be formed by the gas-phase oxidation of volatile organic compound (VOC) precursors. It is likely that sulfate and OOA were internally mixed throughout the whole size range in the air mass. [Copyright &y& Elsevier]