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Soot particles are the most efficient light absorbing aerosol species in the atmosphere, playing an important role as a driver of global warming. Their climate effects strongly depend on their mixing state, which significantly changes their light absorbing capability and cloud condensation nuclei (CCN) activity. Therefore, knowledge about the mixing state of soot and its aging mechanism becomes an important topic in the atmospheric sciences. The size-resolved (30-320 nm diameter) mixing state of soot particles in polluted megacity air was measured at a suburban site (Yufa) during the CAREBeijing 2006 campaign in Beijing, using a volatility tandem differential mobility analyzer (VTDMA). Particles in this size range with non-volatile residuals at 300 °C were considered to be soot particles. On average, the number fraction of internally mixed soot in total soot particles (Fin), decreased from 0.80 to 0.57 when initial Dp increased from 30 to 320 nm. Further analysis reveals that: (1) Fin was well correlated with the aerosol hygroscopic mixing state measured by a CCN counter. More externally mixed soot particles were observed when particles showed more heterogeneous features with regard to hygroscopicity. (2) Fin had pronounced diurnal cycles. For particles in the accumulation mode (Dp at 100-320 nm), largest Fin were observed at noon time, with "apparent" turnover rates (kex→in) up to 7.8%h-1. (3) Fin was subject to competing effects of both aging and emissions. While aging increases Fin by converting externally mixed soot particles into internally mixed ones, emissions tend to reduce Fin by emitting more fresh and externally mixed soot particles. Similar competing effects were also found with air mass age indicators. (4) Under the estimated emission intensities, actual turnover rates of soot (kex→in) up to 20%h-1 were derived, which showed a pronounced diurnal cycle peaking around noon time. This result confirms that (soot) particles are undergoing fast aging/coating with the existing high levels of condensable vapors in the megacity Beijing. (5) Diurnal cycles of Fin were different between Aitken and accumulation mode particles, which could be explained by the faster growth of smaller Aitken mode particles into larger size bins. To improve the Fin prediction in regional/global models, we suggest parameterizing Fin by an air mass aging indicator, i.e., Fin = α + bx, where a and b are empirical coefficients determined from observations, and x is the value of an air mass age indicator. At the Yufa site in the North China Plain, fitted coefficients (a, b) were determined as (0.57, 0.21), (0.47, 0.21), and (0.52, 0.0088) for x (indicators) as [NOz]/[NOy], [E]/[X] ([ethylbenzene]/[m,p-xylene]) and ([IM] + [OM])/[EC] ([inorganic + organic matter]/[elemental carbon]), respectively. Such a parameterization consumes little additional computing time, but yields a more realistic description of Fin compared with the simple treatment of soot mixing state in regional/global models. [ABSTRACT FROM AUTHOR]

Both organic carbon (OC) and elemental carbon (EC) were measured during PRIDE-PRD 2006 summer campaign by using a semi-continuous thermal-optical carbon analyzer at a rural site, Back Garden (BG), which is located 50 km to the northwest of Guangzhou City. Together with the online EC/OC analyzer, various kinds of instruments related to aerosol chemical properties were employed here, which provided a good opportunity to check data quality. The concentrations of OC correlated well with the mass of organic matter (OM) and water soluble organic carbon (WSOC), implying the reliability of the data measured in this campaign. The average OC concentrations in fine particle for three typical periods during the campaign (local emission influence, typhoon and precipitation and normal days) were 28.1 µgCm-3, 4.0 µgCm-3 and 5.7 µgCm-3, respectively; and EC were 11.6 µgCm-3, 1.8 µgCm-3, and 3.3 µgCm-3, respectively. The diurnal patterns of EC and OC during the campaign were higher at night and in early morning than daytime, which was probably caused by the primary emission and accumulation in the occurrence of low boundary layer. Compared with the constant diurnal enhancement ratios of EC, the enhancement ratio of OC (OC versus (COCObackground)) kept in a relative high level in the afternoon, with a similar diurnal profile to oxygenated organic aerosol (OOA), due to the strong photochemical formation of OC. Here, a modified EC tracer method was used to estimate the formation of secondary organic carbon (SOC). These results showed that the average SOC concentration (normal days) at BG site was about 2.0±2.3 µgCm-3, and the SOC fraction in OC could reach up to 80% with the average of 47 %. The modified approach in this study proved to be effective and reliable for SOC estimation based on good correlations between estimated SOC versus OOA or WSOC, and estimated POC versus hydrocarbon-like organic aerosol (HOA). [ABSTRACT FROM AUTHOR]

We performed measurements of nitrous acid (HONO) during the PRIDE-PRD2006 campaign in the Pearl River Delta region 60 km north of Guangzhou, China, for 4 weeks in June 2006. HONO was measured by a LOPAP in-situ instrument which was setup in one of the campaign supersites along with a variety of instruments measuring hydroxyl radicals, trace gases, aerosols, and meteorological parameters. Maximum diurnal HONO mixing ratios of 1-5 ppb were observed during the nights. We found that the nighttime build-up of HONO can be attributed to the heterogeneous NO2 to HONO conversion on ground surfaces and the OH+NO reaction. In addition to elevated nighttime mixing ratios, measured noontime values of ≈ 200 ppt indicate the existence of a daytime source higher than the OH+NO→HONO reaction. Using the simultaneously recorded OH, NO, and HONO photolysis frequency, a daytime additional source strength of HONO (PM) was calculated to be 0.77 ppb h-1 on average. This value compares well to previous measurements in other environments. Our analysis of PM provides evidence that the photolysis of HNO3 adsorbed on ground surfaces contributes to the HONO formation. [ABSTRACT FROM AUTHOR]

Atmospheric aerosol particles serving as cloud condensation nuclei (CCN) are key elements of the hydrological cycle and climate. CCN properties were measured and characterized during the CAREBeijing-2006 campaign at a regional site south of the megacity of Beijing, China. Size-resolved CCN efficiency spectra recorded for a supersaturation range of S =0.07% to 0.86% yielded average activation diameters in the range of 190 nm to 45 nm. The corresponding effective hygroscopicity parameters (κ) exhibited a strong size dependence ranging from ~0.25 in the Aitken size range to ~0.45 in the accumulation size range. The campaign average value (κ = 0.3±0.1) was similar to the values observed and modeled for other populated continental regions. The hygroscopicity parameters derived from the CCN measurements were consistent with chemical composition data recorded by an aerosol mass spectrometer (AMS) and thermo-optical measurements of apparent elemental and organic carbon (EC and OC). The CCN hygroscopicity and its size dependence could be parameterized as a function of only AMS based organic and inorganic mass fractions (forg, finorg) using the simple mixing rule κp ≈ 0.1 ⋅ forg +0.7 ⋅ finorg. When the measured air masses originated from the north and passed rapidly over the center of Beijing (fresh city pollution), the average particle hygroscopicity was reduced (κ = 0.2±0.1), which is consistent with enhanced mass fractions of organic compounds (~50 %) and EC (~30 %) in the fine particulate matter (PM1). Moreover, substantial fractions of externally mixed weakly CCN-active particles were observed at low supersaturation (S =0.07 %), which can be explained by the presence of freshly emitted soot particles with very low hygroscopicity (κ <0.1). Particles in stagnant air from the industrialized region south of Beijing (aged regional pollution) were on average larger and more hygroscopic, which is consistent with enhanced mass fractions (~60 %) of soluble inorganic ions (mostly sulfate, ammonium, and nitrate). Accordingly, the number concentration of CCN in aged air from the megacity region was higher than in fresh city out- flow ((2.5-9.9)x10³ cm-3 vs. (0.4-8.3)x10³ cm-3 for S = 0.07-0.86 %) although the total aerosol particle number concentration was lower (1.2x104 cm-3 vs. 2.3x104 cm-3). A comparison with related studies suggests that the fresh outflow from Chinese urban centers generally may contain more, but smaller and less hygroscopic aerosol particles and thus fewer CCN than the aged outflow from megacity regions. [ABSTRACT FROM AUTHOR]

Size-resolved chemical composition, mixing state, and cloud condensation nucleus (CCN) activity of aerosol particles in polluted mega-city air and biomass burning smoke were measured during the PRIDE-PRD2006 campaign near Guangzhou, China, using an aerosol mass spectrometer (AMS), a volatility tandem differential mobility analyzer (VTDMA), and a continuous-flow CCN counter (DMT-CCNC). The size-dependence and temporal variations of the effective average hygroscopicity parameter for CCN-active particles (κa) could be parameterized as a function of organic and inorganic mass fractions (forg, finorg) determined by the AMS: κa,p,=κorg ⋅ forg + κinorg ⋅ finorg. The characteristic κ values of organic and inorganic components were similar to those observed in other continental regions of the world: κorg≈0.1 and κinorg≈0.6. The campaign average κa values increased with particle size from ∼0.25 at ∼50 nm to ∼0.4 at ∼200 nm, while forg decreased with particle size. At ∼50 nm, forg was on average 60% and increased to almost 100% during a biomass burning event. The VTDMA results and complementary aerosol optical data suggest that the large fractions of CCN-inactive particles observed at low supersaturations (up to 60% at S≤0.27%) were externally mixed weakly CCN-active soot particles with low volatility (diameter reduction <5% at 300 °C) and effective hygroscopicity parameters around κLV≈0.01. A proxy for the effective average hygroscopicity of the total ensemble of CCN-active particles including weakly CCN-active particles (κt) could be parameterized as a function of κa,p and the number fraction of low volatility particles determined by VTDMA (ΦLV):κt,p=κa,p--ΦLV ⋅ (κa,p--κLV). Based on κ values derived from AMS and VTDMA data, the observed CCN number concentrations (NCCN,S≈10²-- 104 cm--3 at S = 0.068--0.47%) could be efficiently predicted from the measured particle number size distribution. The mean relative deviations between observed and predicted CCN concentrations were ∼10% when using κt,p, and they increased to ∼20% when using only κa,p. The mean relative deviations were not higher (∼20%) when using an approximate continental average value of κ ≈0.3, although the constant κ value cannot account for the observed temporal variations in particle composition and mixing state (diurnal cycles and biomass burning events). Overall, the results confirm that on a global and climate modeling scale an average value of κ≈0.3 can be used for approximate predictions of CCN number concentrations in continental boundary layer air when aerosol size distribution data are available without information about chemical composition. Bulk or size-resolved data on aerosol chemical composition enable improved CCN predictions resolving regional and temporal variations, but the composition data need to be highly accurate and complemented by information about particle mixing state to achieve high precision (relative deviations <20%). [ABSTRACT FROM AUTHOR]

In situ measurements of the mass concentration of black carbon (BC) and mixing ratios of carbon monoxide (CO) and carbon dioxide (CO2) were made at Guangzhou, an urban measurement site in the Pearl River Delta (PRD), China, in July 2006. The average ± standard deviation (SD) concentrations of BC, CO, and CO2 were 4.7±2.3 μgC m-3, 798±459 ppbv, and 400±13 ppmv, respectively. The trends of these species were mainly controlled by synoptic-scale changes in meteorology during the campaign. Based on back trajectories, data are analyzed separately for two different air mass types representing northerly and southerly flows. The northerly air masses, which constituted ~25% of the campaign, originated mostly in the PRD and hence represent observations on regional scales. On the other hand, during southerly flow (~75%), the measurements were influenced by dilution due to cleaner marine air. The diurnal patterns of BC, CO, and CO2 exhibited peak concentrations during the morning and evening hours coinciding with rush-hour traffic. The ratios of OC/BC were lower during the morning hour peaks in the concentrations of primary pollutants due to their fresh emissions mainly from vehicular traffic in Guangzhou. The diurnal variations of BC observed in southerly air masses tended to follow the traffic patterns of heavy-duty vehicles (HDV) in Guangzhou, while the roles of other sources need to be investigated. The slopes of ΔBC/1CO, ΔBC/ΔCO2, and ΔCO/ΔCO2 observed during northerly flows were 0.0045 μgC m-3/ppbv, 0.13 μgC m-3/ppmv, and 49.4 ppbv/ppmv, respectively, agreeing reasonably with their respective emission ratios derived from regional emission inventories. [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]

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]