Campaign Of Air Quality Research Research Articles

Model simulation of NO3, N2O5 and ClNO2 at a rural site in Beijing during CAREBeijing-2006

A chemical box model was used to study nitrate radical (NO3), dinitrogen pentoxide (N2O5) and nitryl chloride (ClNO2) in a rural site during the Campaign of Air Quality Research in Beijing 2006 (CAREBeijing-2006). The model was based on regional atmospheric chemistry mechanism version 2 (RACM2) with the heterogeneous uptake of N2O5 and the simplified chloride radical (Cl) chemistry mechanism. A high production rate of NO3 with a mean value of 0.8ppbv/h and low mixing ratios of NO3 and N2O5 (peak values of 17 pptv and 480 pptv, respectively) existed in this site. Budget analysis showed that NO emission suppressed the NO3 chemistry at the surface layer, the reaction of NO3 with VOCs made a similar contribution to NO3 loss as N2O5 heterogeneous uptake. The NO3 chemistry was predominantly controlled by isoprene, and NO3 oxidation produced organic nitrate with a mean value of 0.06ppbv/h during nighttime. The organic nitrate production initiated by NO3 was equal to that initiated by OH, implying the importance of nighttime chemistry for secondary organic aerosol (SOA) formation. We confirmed that the N2O5 heterogeneous reaction accounted for nighttime particle NO3− enhancement, with a large day to day variability, and made less of a contribution to NOx loss compared to that of OH reacting with NO2. Additionally, abundant ClNO2, up to 5.0 ppbv, was formed by N2O5 heterogeneous uptake. ClNO2 was sustained at a high level until noon in spite of the gradually increasing photolysis of ClNO2 after sunrise. Chlorine activation caused by N2O5 heterogeneous uptake increased primary ROx formation by 5% and accounted for 8% of the net ozone production enhancement in the morning.

Observation of regional air pollutant transport between the megacity Beijing and the North China Plain

Abstract. Megacities have strong interactions with the surrounding regions through transport of air pollutants. It has been frequently addressed that the air quality of Beijing is influenced by the influx of air pollutants from the North China Plain (NCP). Estimations of air pollutant cross-boundary transport between Beijing and the NCP are important for air quality management. However, evaluation of cross-boundary transport using long-term observations is very limited. Using the observational results of the gaseous pollutants SO2, NO, NO2, O3, and CO from August 2006 to October 2008 at the Yufa site, a cross-boundary site between the megacity Beijing and the NCP, together with meteorological parameters, we explored a method for evaluating the transport flux intensities at Yufa, as part of the “Campaign of Air Quality Research in Beijing and Surrounding Region 2006–2008” (CAREBeijing 2006–2008). The hourly mean ± SD (median) concentration of SO2, NO, NO2, NOx, O3, Ox, and CO was 15 ± 16 (9) ppb, 12 ± 25 (3) ppb, 24 ± 19 (20) ppb, 36 ± 39 (23) ppb, 28 ± 27 (21) ppb, 52 ± 24 (45) ppb, and 1.6 ± 1.4 (1.2) ppm during the observation period, respectively. The bivariate polar plots showed the dependence of pollutant concentrations on both wind speed and wind direction, and thus inferred their dominant transport directions. Surface flux intensity calculations further demonstrated the regional transport influence of Beijing and the NCP on Yufa. The net surface transport flux intensity (mean ± SD) of SO2, NO, NO2, NOx, O3, Ox, and CO was 6.2 ± 89.5, −4.3 ± 29.5, −0.6 ± 72.3, −4.9 ± 93.0, 14.7 ± 187.8, 14.8 ± 234.9, and 70 ± 2830 µg s−1 m−2 during the observation period, respectively. For SO2, CO, O3, and Ox the surface flux intensities from the NCP to Yufa surpassed those from Beijing to Yufa in all seasons except winter, with the strongest net fluxes largely in summer, which were about 4–8 times those of other seasons. The surface transport flux intensity of NOx from Beijing to Yufa was stronger than that from the NCP to Yufa except in summer, with the strongest net flux in winter, which was about 1.3–8 times that of other seasons. The flux intensities were then assigned to the corresponding trajectories in the potential source contribution function analysis (PSCF), which confirmed the results of flux intensity calculations. Our study also suggested that various factors, such as the wind field, emission inventory, and photochemical reactions, could influence transport of air pollutants. The decrease of surface flux intensity during the Olympic Games implied the role of both local emission reduction and regional cooperation in successful air quality management. Three dimensional observations are needed for further comprehensive discussion of the regional transport between Beijing and the NCP.

Dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid in PM<sub>2.5</sub> aerosol collected during CAREBeijing-2007: an effect of traffic restriction on air quality

Abstract. Thirty water-soluble organic species, including dicarboxylic acids, ketocarboxylic acids, α-dicarbonyls, fatty acids and benzoic acid were determined as well as organic carbon (OC), elemental carbon (EC) and water-soluble organic carbon (WSOC) in PM2.5 samples collected during the Campaign of Air Quality Research in Beijing 2007 (CAREBeijing-2007) in the urban and suburban areas of Beijing. The objective of this study is to identify the influence of traffic emissions and regional transport to the atmosphere in Beijing during summer. PM2.5 samples collected with or without traffic restriction in Beijing are selected to evaluate the effectiveness of local traffic restriction measures on air pollution reduction. The average concentrations of the total quantified bifunctional organic compounds (TQBOCs), total fatty acids and benzoic acid during the entire sampling period were 1184±241, 597±159 and 1496±511 ng m−3 in Peking University (PKU), and 1050±303, 475±114 and 1278±372 ng m−3 in Yufa, Beijing. Oxalic acid (C2) was found as the most abundant dicarboxylic acid at PKU and Yufa followed by phthalic acid (Ph). A strong even carbon number predominance with the highest level at stearic acid (C18:0), followed by palmitic acid (C16:0) was found for fatty acids. According to the back trajectories modeling results, the air masses were found to originate mainly from the northeast, passing over the southeast or south of Beijing (heavily populated, urbanized and industrialized areas), during heavier pollution events, whereas they are mainly from the north or northwest sector (mountain areas without serious anthropogenic pollution sources) during less pollution events. The data with wind only from the same sector (minimizing the difference from regional contribution) but with and without traffic restriction in Beijing were analyzed to evaluate the effectiveness of local traffic restriction measures on the reduction of local air pollution in Beijing. The results suggested that the traffic restriction measures can reduce the air pollutants, but the decrease of pollutants is generally smaller in Yufa compared to that in PKU. Moreover, an enhancement of EC value indicates more elevated primary emissions in Yufa during restriction periods than in non-restriction periods. This study demonstrates that even when primary exhaust was controlled by traffic restriction, the contribution of secondary organic species formed from photochemical processes was critical with long-range atmospheric transport of pollutants.

Daytime HONO formation in the suburban area of the megacity Beijing, China

Nitrous acid (HONO), as a primary precursor of OH radicals, has been considered one of the most important nitrogen-containing species in the atmosphere. Up to 30% of primary OH radical production is attributed to the photolysis of HONO. However, the major HONO formation mechanisms are still under discussion. During the Campaigns of Air Quality Research in Beijing and Surrounding Region (CAREBeijing2006) campaign, comprehensive measurements were carried out in the megacity Beijing, where the chemical budget of HONO was fully constrained. The average diurnal HONO concentration varied from 0.33 to 1.2 ppbv. The net OH production rate from HONO, P OH(HONO)net, was on average (from 05:00 to 19:00 h) 7.1 × 106 molecule/(cm3 s), 2.7 times higher than from O3 photolysis. This production rate demonstrates the important role of HONO in the atmospheric chemistry of megacity Beijing. An unknown HONO source (P unknown) with an average of 7.3 × 106 molecule/(cm3 s) was derived from the budget analysis during daytime. P unknown provided four times more HONO than the reaction of NO with OH did. The diurnal variation of P unknown showed an apparent photo-enhanced feature with a maximum around 12:00 h, which was consistent with previous studies at forest and rural sites. Laboratory studies proposed new mechanisms to recruit NO2 and J(NO2) in order to explain a photo-enhancement of of P unknown. In this study, these mechanisms were validated against the observation-constraint P unknown. The reaction of exited NO2 accounted for only 6% of P unknown, and P unknown poorly correlated with [NO2] (R = 0.26) and J(NO2)[NO2] (R = 0.35). These results challenged the role of NO2 as a major precursor of the missing HONO source.

Airborne measurements of gas and particle pollutants during CAREBeijing-2008

Abstract. Measurements of gaseous pollutants – including ozone (O3), sulfur dioxide (SO2), nitrogen oxides (NOX = NO + NO2), carbon monoxide (CO), particle number concentrations (5.6–560 nm and 0.47–30 μm) – and meteorological parameters (T, RH, P) were conducted during the Campaigns of Air Quality Research in Beijing and Surrounding Regions in 2008 (CAREBeijing-2008), from 27 August through 13 October 2008. The data from a total 18 flights (70 h flight time) from near the surface to 2100 m altitude were obtained with a Yun-12 aircraft in the southern surrounding areas of Beijing (38–40° N, 114–118° E). The objectives of these measurements were to characterize the regional variation of air pollution during and after the Olympics of 2008, determine the importance of air mass trajectories and to evaluate of other factors that influence the pollution characteristics. The results suggest that there are primarily four distinct sources that influenced the magnitude and properties of the pollutants in the measured region based on back-trajectory analysis: (1) southerly transport of air masses from regions with high pollutant emissions, (2) northerly and northeasterly transport of less pollutant air from further away, (3) easterly transport from maritime sources where emissions of gaseous pollutant are less than from the south but still high in particle concentrations, and (4) the transport of air that is a mixture from different regions; that is, the air at all altitudes measured by the aircraft was not all from the same sources. The relatively long-lived CO concentration is shown to be a possible transport tracer of long-range transport from the northwesterly direction, especially at the higher altitudes. Three factors that influenced the size distribution of particles – i.e., air mass transport direction, ground source emissions and meteorological influences – are also discussed.

The simulations of sulfuric acid concentration and new particle formation in an urban atmosphere in China

Abstract. Simulations of sulfuric acid concentration and new particle formation are performed by using the zero-dimensional version of the model MALTE (Model to predict new Aerosol formation in the Lower TropospherE) and measurements from the Campaign of Air Quality Research in Beijing and Surrounding areas (CAREBeijing) in 2008. Chemical reactions from the Master Chemical Mechanism version 3.2 (MCM v3.2) are used in the model. High correlation (slope = 0.72, R = 0.74) between the modelled and observed sulfuric acid concentrations is found during daytime (06:00–18:00). The aerosol dynamics are simulated by the University of Helsinki Multicomponent Aerosol (UHMA) model including several nucleation mechanisms. The results indicate that the model is able to predict the on- and offset of new particle formation in an urban atmosphere in China. In addition, the number concentrations of newly formed particles in kinetic-type nucleation including homogenous homomolecular (J=K[H2SO4]2) and homogenous heteromolecular nucleation involving organic vapours (J=Khet[H2SO4][Org]) are in satisfactory agreement with the observations. However, the specific organic compounds that possibly participate in the nucleation process should be investigated in further studies. For the particle growth, only a small fraction of the oxidized total organics condense onto the particles in polluted environments. Meanwhile, the OH and O3 oxidation mechanism contribute 5.5% and 94.5% to the volume concentration of small particles, indicating the particle growth is more controlled by the precursor gases and their oxidation by O3.

Quantitative evaluation of emission controls on primary and secondary organic aerosol sources during Beijing 2008 Olympics

Abstract. To assess the primary and secondary sources of fine organic aerosols after the aggressive implementation of air pollution controls during the 2008 Beijing Olympic Games, 12 h PM2.5 values were measured at an urban site at Peking University (PKU) and an upwind rural site at Yufa during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. The average PM2.5 concentrations were 72.5 ± 43.6 μg m−3 and 64.3 ± 36.2 μg m−3 (average ± standard deviation, below as the same) at PKU and Yufa, respectively, showing the lowest concentrations in recent years. Combining the results from a CMB (chemical mass balance) model and secondary organic aerosol (SOA) tracer-yield model, five primary and four secondary fine organic aerosol sources were compared with the results from previous studies in Beijing. The relative contribution of mobile sources to PM2.5 concentrations was increased in 2008, with diesel engines contributing 16.2 ± 5.9% and 14.5 ± 4.1% and gasoline vehicles contributing 10.3 ± 8.7% and 7.9 ± 6.2% to organic carbon (OC) at PKU and Yufa, respectively. Due to the implementation of emission controls, the absolute OC concentrations from primary sources were reduced during the Olympics, and the contributions from secondary formation of OC represented a larger relative source of fine organic aerosols. Compared with the non-controlled period prior to the Olympics, primary vehicle contributions were reduced by 30% at the urban site and 24% at the rural site. The reductions in coal combustion contributions were 57% at PKU and 7% at Yufa. Our results demonstrate that the emission control measures implemented in 2008 significantly alleviated the primary organic particle pollution in and around Beijing. However, additional studies are needed to provide a more comprehensive assessment of the emission control effectiveness on SOA formation.

Missing OH source in a suburban environment near Beijing: observed and modelled OH and HO<sub>2</sub> concentrations in summer 2006

Abstract. Measurements of ambient OH and HO2 radicals were performed by laser induced fluorescence (LIF) during CAREBeijing2006 (Campaigns of Air Quality Research in Beijing and Surrounding Region 2006) at the suburban site Yufa in the south of Beijing in summer 2006. On most days, local air chemistry was influenced by aged air pollution that was advected by a slow, almost stagnant wind from southern regions. Observed daily concentration maxima were in the range of (4–17) × 106 cm−3 for OH and (2–24) × 108 cm−3 for HO2 (including an estimated interference of 25% from RO2). During daytime, OH reactivities were generally high (10–30 s−1) and mainly contributed by observed VOCs and their calculated oxidation products. The comparison of modelled and measured HOx concentrations reveals a systematic underprediction of OH as a function of NO. A large discrepancy of a factor 2.6 is found at the lowest NO concentration encountered (0.1 ppb), whereas the discrepancy becomes insignificant above 1 ppb NO. This study extends similar observations from the Pearl-River Delta (PRD) in South China to a more urban environment. The OH discrepancy at Yufa can be resolved, if NO-independent additional OH recycling is assumed in the model. The postulated Leuven Isoprene Mechanism (LIM) has the potential to explain the gap between modelled and measured OH at Beijing taking into account conservative error estimates, but lacks experimental confirmation. This and the hereby unresolved discrepancy at PRD suggest that other VOCs besides isoprene might be involved in the required, additional OH recycling. Fast primary production of ROx radicals up to 7 ppb h−1 was determined at Beijing which was dominated by the photolysis of O3, HONO, HCHO, and dicarbonyls. For a special case, 20 August, when the plume of Beijing city was encountered, a missing primary HOx source (about 3 ppb h−1) was determined under high NOx conditions similar to other urban areas like Mexico City. CAREBeijing2006 emphasizes the important role of OVOCs as a radical source and sink, and the need for further investigation of the chemical degradation of VOCs in order to better understand radical chemistry in VOC-rich air.

Primary Sources and Secondary Formation of Organic Aerosols in Beijing, China

Ambient aerosol samples were collected at an urban site and an upwind rural site of Beijing during the CAREBEIJING-2008 (Campaigns of Air quality REsearch in BEIJING and surrounding region) summer field campaign. Contributions of primary particles and secondary organic aerosols (SOA) were estimated by chemical mass balance (CMB) modeling and tracer-yield method. The apportioned primary and secondary sources explain 73.8% ± 9.7% and 79.6% ± 10.1% of the measured OC at the urban and rural sites, respectively. Secondary organic carbon (SOC) contributes to 32.5 ± 15.9% of the organic carbon (OC) at the urban site, with 17.4 ± 7.6% from toluene, 9.7 ± 5.4% from isoprene, 5.1 ± 2.0% from α-pinene, and 2.3 ± 1.7% from β-caryophyllene. At the rural site, the secondary sources are responsible for 38.4 ± 14.4% of the OC, with the contributions of 17.3 ± 6.9%, 13.9 ± 9.1%, 5.6 ± 1.9%, and 1.7 ± 1.0% from toluene, isoprene, α-pinene, and β-caryophyllene, respectively. Compared with other regions in the world, SOA in Beijing is less aged, but the concentrations are much higher; between the sites, SOA is more aged and affected by regional transport at the urban site. The high SOA loading in Beijing is probably attributed to the high regional SOC background (~2 μg m(-3)). The toluene SOC concentration is high and comparable at the two sites, implying that some anthropogenic components, at least toluene SOA, are widespread in Beijing and represents a major factor in affecting the regional air quality. The aerosol gaseous precursor concentrations and temperature correlate well with SOA, both affecting SOA formation. The significant SOA enhancement with increasing water uptake and acidification indicates that the aqueous-phase reactions are largely responsible SOA formation in Beijing.

Chemical characteristics of inorganic ammonium salts in PM<sub>2.5</sub> in the atmosphere of Beijing (China)

Abstract. The atmospheric concentrations of gaseous HNO3, HCl and NH3 and their relative salts have been measured during two field campaigns in the winter and in the summer of 2007 at Beijing (China), as part of CAREBEIJING (Campaigns of Air Quality Research in Beijing and Surrounding Region). In this study, annular denuder technique used with integration times of 2 and 24h to collect inorganic and soluble PM2.5 without interferences from gas–particle and particle–particle interactions. The results were discussed from the standpoint of temporal and diurnal variations and meteorological effects. Fine particulate Cl−, NH4+ and SO42− exhibited distinct temporal variations, while fine particulate NO3− did not show much variation with respect to season. Daily mean concentrations of fine particulate NH4+ and SO42− were higher during summer (12.30 μg m−3 and 18.24 μg m−3, respectively) than during winter (6.51 μg m−3 and 7.50 μg m−3, respectively). Daily mean concentrations of fine particulate Cl− were higher during winter (2.94 μg m−3) than during summer (0.79 μg m−3), while fine particulate NO3− showed similar both in winter (8.38 μg m−3) and in summer (9.62 μg m−3) periods. The presence of large amounts of fine particulate NO3− even in summer are due to higher local and regional concentrations of NH3 in the atmosphere available to neutralize H2SO4 and HNO3, which is consistent with the observation that the measured particulate species were neutralized. The composition of fine particulate matter indicated the domination of (NH4)2SO4 during winter and summer periods. In addition, the high relative humidity conditions in summer period seemed to dissolve a significant fraction of HNO3 and NH3 enhancing fine particulate NO3− and NH4+ in the atmosphere. All measured particulate species showed diurnal similar patterns during the winter and summer periods with higher peaks in the early morning, especially in summer, when humid and stable atmospheric conditions occurred. These diurnal variations were affected by wind direction suggesting regional and local source influences. The fine particulate species were correlated with NOx and PM2.5, supporting the hypothesis that traffic may be also an important source of secondary particles.

Impact of new particle formation on the concentrations of aerosols and cloud condensation nuclei around Beijing

[1] New particle formation (NPF) is one of the most important processes in controlling the concentrations of aerosols (condensation nuclei, CN) and cloud condensation nuclei (CCN) in the atmosphere. In this study, we introduce a new aerosol model representation with 20 size bins between 1 nm and 10 μm and activation-type and kinetic nucleation parameterizations into the WRF-chem model (called NPF-explicit WRF-chem). Model calculations were conducted in the Beijing region in China for the periods during the Campaign of Air Quality Research in Beijing and Surrounding Region 2006 (CARE-Beijing 2006) campaign conducted in August and September 2006. Model calculations successfully reproduced the timing of NPF and no-NPF days in the measurements (21 of 26 days). Model calculations also reproduced the subsequent rapid growth of new particles with a time scale of half a day. These results suggest that once a reasonable nucleation rate at a diameter of 1 nm is given, explicit calculations of condensation and coagulation processes can reproduce the clear contrast between NPF and no-NPF days as well as further growth up to several tens of nanometers. With this reasonable representation of the NPF process, we show that NPF contributed 20%–30% of the CN concentrations (>10 nm in diameter) in and around Beijing on average. We also show that NPF increases CCN concentrations at higher supersaturations (S > 0.2%), while it decreases them at lower supersaturations (S < 0.1%). This is likely because NPF suppresses the increases in both the size and hygroscopicity of preexisting particles through the competition of condensable gases between new particles and preexisting particles. Sensitivity calculations show that a reduction of primary aerosol emissions, such as black carbon (BC), would not necessarily decrease CCN concentrations because of an increase in NPF. Sensitivity calculations also suggest that the reduction ratio of primary aerosol and SO2 emissions will be key in enhancing or damping the BC mitigation effect.

Measurements of gaseous H&amp;lt;sub&amp;gt;2&amp;lt;/sub&amp;gt;SO&amp;lt;sub&amp;gt;4&amp;lt;/sub&amp;gt; by AP-ID-CIMS during CAREBeijing 2008 Campaign

Abstract. As part of the 2008 Campaign of Air Quality Research in Beijing and Surrounding Regions (CAREBeijing 2008), measurements of gaseous sulfuric acid (H2SO4) have been conducted at an urban site in Beijing, China from 7 July to 25 September 2008 using atmospheric pressure ion drift – chemical ionization mass spectrometry (AP-ID-CIMS). This represents the first gaseous H2SO4 measurements in China. Diurnal profile of sulfuric acid is strongly dependent on the actinic flux, reaching a daily maximum around noontime and with an hourly average concentration of 5 × 106 molecules cm−3. Simulation of sulfuric acid on the basis of the measured sulfur dioxide concentration, photolysis rates of ozone and nitrogen dioxide, and aerosol surface areas captures the trend of the measured H2SO4 diurnal variation within the uncertainties, indicating that photochemical production and condensation onto preexisting particle surface dominate the observed diurnal H2SO4 profile. The frequency of the peak H2SO4 concentration exceeding 5 × 106 molecules cm−3 increases by 16 % during the period of the summer Olympic Games (8–24 August 2008), because of the implementation of air quality control regulations. Using a multivariate statistical method, the critical nucleus during nucleation events is inferred, containing two H2SO4 molecules (R2 = 0.85). The calculated condensation rate of H2SO4 can only account for 10–25 % of PM1 sulfate formation, indicating that either much stronger sulfate production exists at the SO2 source region or other sulfate production mechanisms are responsible for the sulfate production.

A numerical study of contributions to air pollution in Beijing during CAREBeijing-2006

Abstract. An online air pollutant tagged module has been developed in the Nested Air Quality Prediction Model System (NAQPMS) to investigate the impact of local and regional sources on the air pollutants in Beijing during the Campaign of Air Quality Research in Beijing 2006 (CAREBeijing-2006). The NAQPMS model shows high performance in simulating sulfur dioxide (SO2), particulate matter (PM10), nitrogen dioxide (NO2), and ozone (O3) with overall better agreements with the observations at urban sites than rural areas. With the tagged module, the air pollutant contributions from local and regional sources to the surface layer (about 30 m) and the upper layer (about 1.1 km) in Beijing are differentiated and estimated. The air pollutants at the surface layer in Beijing are dominated by the contributions from local sources, accounting for 65 % of SO2, 75 % of PM10 and nearly 90 % of NO2, respectively, comparatively, the 1.1 km layer has large source contributions from the surrounding regions (e.g., southern Beijing), accounting for more than 50 % of the SO2 and PM10 concentrations. County scale analysis is also performed and the results suggest that Tianjin is the dominant source of SO2 in Pinggu County, and Langfang, Hebei is the most important regional contributor to PM10 in Beijing. Moreover, the surrounding regions show larger impact on SO2, PM10 and NO2 in the eastern counties of Beijing (e.g., Pinggu, Tongzhou and Daxing) than those in western Beijing, which is likely due to the Beijing's semi-basin topography and the summer monsoon. Our results indicate that the efforts to control the air pollutants in Beijing should focus on controlling both local and regional emissions.

Dicarboxylic acids, ketocarboxylic acids, α‐dicarbonyls, fatty acids, and benzoic acid in urban aerosols collected during the 2006 Campaign of Air Quality Research in Beijing (CAREBeijing‐2006)

Ground‐based studies of PM2.5 were conducted for determination of 30 water‐soluble organic species, including dicarboxylic acids, ketocarboxylic acids and dicarbonyls, nine fatty acids, and benzoic acid, during the Campaign of Air Quality Research in Beijing 2006 (CAREBeijing‐2006; 21 August to 4 September 2006) at urban (Peking University, PKU) and suburban (Yufa) sites of Beijing. Molecular distributions of dicarboxylic acids demonstrated that oxalic acid (C2) was the most abundant species, followed by phthalic acid (Ph) and succinic acid (C4) at both sites. The sum of three dicarboxylic acids accounted for 71% and 74% of total quantified water‐soluble organics (327–1552 and 329–1124 ng m−3) in PKU and Yufa, respectively. Positive correlation was found between total quantified water‐soluble species and water‐soluble organic compounds (WSOC). On a carbon basis, total quantified dicarboxylic acids and ketocarboxylic acids and dicarbonyls account for up to 14.2% and 30.4% of the WSOC in PKU and Yufa, respectively, suggesting that they are the major WSOC fractions in Beijing. The distributions of fatty acids are characterized by a strong even carbon number predominance with maximum at hexadecanoic acid (C16:0). The ratio of octadecanoic acid (C18:0) to hexadecanoic acid (C16:0) (0.39–0.85, with an average of 0.36) suggests that in addition to vehicular emissions, an input from cooking emissions is important, as is biogenic emission. Benzoic acid that has been proposed as a primary pollutant from vehicular exhaust and a secondary product from photochemical reactions was found to be abundant: 72.2 ± 58.1 ng m−3 in PKU and 78.0 ± 47.3 ng m−3 in Yufa. According to the 72 hour back trajectory analysis, when the air mass passed over the southern or southeastern part of Beijing (24–25 August and 1–2 September), the highest concentrations of organic compounds were observed. On the contrary, when the clean air masses came straight from the north during 3–4 September, the lowest levels of organic compounds were recorded. This study demonstrates that pollution episodes in Beijing were strongly controlled by wind direction; that is, air quality in Beijing is good when air masses originate from the north and northwest, whereas it deteriorates when the air mass originates from the south and southeast.

Highly time-resolved chemical characterization of atmospheric submicron particles during 2008 Beijing Olympic Games using an Aerodyne High-Resolution Aerosol Mass Spectrometer

Abstract. As part of Campaigns of Air Quality Research in Beijing and Surrounding Region-2008 (CAREBeijing-2008), an Aerodyne High-Resolution Time-of-Flight Aerosol Mass Spectrometer (HR-ToF-AMS) was deployed in urban Beijing to characterize submicron aerosol particles during the time of 2008 Beijing Olympic Games and Paralympic Games (24 July to 20 September 2008). The campaign mean PM1 mass concentration was 63.1 ± 39.8 μg m−3; the mean composition consisted of organics (37.9%), sulfate (26.7%), ammonium (15.9%), nitrate (15.8%), black carbon (3.1%), and chloride (0.87%). The average size distributions of the species (except BC) were all dominated by an accumulation mode peaking at about 600 nm in vacuum aerodynamic diameter, and organics was characterized by an additional smaller mode extending below 100 nm. Positive Matrix Factorization (PMF) analysis of the high resolution organic mass spectral dataset differentiated the organic aerosol into four components, i.e., hydrocarbon-like (HOA), cooking-related (COA), and two oxygenated organic aerosols (OOA-1 and OOA-2), which on average accounted for 18.1, 24.4, 33.7 and 23.7% of the total organic mass, respectively. The HOA was identified to be closely associated with primary combustion sources, while the COA mass spectrum and diurnal pattern showed similar characteristics to that measured for cooking emissions. The OOA components correspond to aged secondary organic aerosol. Although the two OOA components have similar elemental (O/C, H/C) compositions, they display differences in mass spectra and time series which appear to correlate with the different source regions sampled during the campaign. Back trajectory clustering analysis indicated that the southerly air flows were associated with the highest PM1 pollution during the campaign. Aerosol particles in southern airmasses were especially rich in inorganic and oxidized organic species. Aerosol particles in northern airmasses contained a large fraction of primary HOA and COA species, probably due to stronger influences from local emissions. The lowest concentration levels for all major species were obtained during the Olympic game days (8 to 24 August 2008), possibly due to the effects of both strict emission controls and favorable meteorological conditions.

Aerosol optical properties observed during Campaign of Air Quality Research in Beijing 2006 (CAREBeijing‐2006): Characteristic differences between the inflow and outflow of Beijing city air

Ground‐based measurements of aerosol optical properties were conducted during Campaign of Air Quality Research in Beijing 2006 (CAREBeijing‐2006) (11 August to 9 September 2006) at a suburban site ∼30 km south of Beijing. Averaged over the measurement campaign (arithmetic mean ± standard deviation), the total scattering coefficients (σs) were 469 ± 374 Mm−1 (450 nm), 361 ± 295 Mm−1 (550 nm), and 249 ± 206 Mm−1 (700 nm) and the absorption coefficient (σa) was 51.8 ± 36.5 Mm−1 (532 nm). The average Ångström exponent was 1.42 ± 0.19 (450 nm/700 nm) and the average single scattering albedo (ω532) was 0.86 ± 0.07 (532 nm) with minimum values as low as 0.5. Pronounced diurnal cycles were observed in σs, σa, and ω532 and can be explained by boundary layer mixing effects. Additionally, an enhancement of absorbing particles in the early morning (0500–0800 local time) was observed; this may be attributed to soot emissions from traffic activity. When the measured air masses originated in the north and passed over Beijing, the single scattering albedo was generally low (ω532 &lt; 0.8), which indicates that the local emissions of particulate matter in Beijing were dominated by primary particles from combustion sources (soot). The southerly inflow to Beijing had typically very high σs and higher than average ω532 values, suggesting a large amount of secondary aerosol (e.g., sulfate and oxidized organics). Overall, the results suggest that a majority of the particle pollution in Beijing is transported into the city from the south.

Optical properties of atmospheric aerosols obtained by in situ and remote measurements during 2006 Campaign of Air Quality Research in Beijing (CAREBeijing‐2006)

In order to investigate the optical properties of atmospheric aerosol in the urban area of Beijing, in situ and remote measurements of particulate pollutants were conducted at an urban site (39.98°N, 116.35°E, ∼20 m above ground level) in Beijing during the Campaign of Air Quality Research in Beijing (CAREBeijing) campaign from 16 August to 10 September 2006. During the intensive measurement period, average PM2.5 mass concentration and light extinction coefficient (bext) were measured to be 102.1 ± 55.0 μg m−3 and 880.7 ± 685.9 Mm−1, respectively. Average mass scattering efficiency of PM10 and PM2.5 particle were found to be 2.5 ± 1.1 and 3.4 ± 1.2 m2 g−1, respectively. Average single scattering albedo (SSA) of dry PM10 was characterized to be 0.82 ± 0.09. It was found that SSA decreased to lower values of ∼0.75 during the relatively clean condition while it increased up to ∼0.86 during polluted condition mainly owing to the increases of ammonium sulfate, ammonium nitrate, and organic mass by carbon's contributions to PM mass concentrations. Pollution episodes in Beijing were strongly related to wind speed and wind direction. Stagnant weather conditions with southerly wind and low wind speed accelerated the accumulation of the pollutants in Beijing, which led to severe haze. It has been found that high PM2.5/AOT (aerosol optical thickness) ratio of 228.2 μg m−3 was observed when air mass was transported from western or northern China while significantly lower PM2.5/AOT of 107.6 μg m−3 was observed when it was affected mostly by local air pollutants in Beijing.

Rapid aerosol particle growth and increase of cloud condensation nucleus activity by secondary aerosol formation and condensation: A case study for regional air pollution in northeastern China

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 (∼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 μg 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 κ 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 ∼0.45 for particles with diameters of ∼190 nm. This result is consistent with aerosol chemical composition data, showing a pronounced increase of sulfate.

Spatial and temporal variations of aerosols around Beijing in summer 2006: Model evaluation and source apportionment

Regional aerosol model calculations were made using the Weather Research and Forecasting (WRF)‐Community Multiscale Air Quality (CMAQ) and WRF‐chem models to study spatial and temporal variations of aerosols around Beijing, China, in the summer of 2006, when the Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing) intensive campaign was conducted. Model calculations captured temporal variations of primary (such as elemental carbon (EC)) and secondary (such as sulfate) aerosols observed in and around Beijing. The spatial distributions of aerosol optical depth observed by the MODIS satellite sensors were also reproduced over northeast China. Model calculations showed distinct differences in spatial distributions between primary and secondary aerosols in association with synoptic‐scale meteorology. Secondary aerosols increased in air around Beijing on a scale of about 1000 × 1000 km2 under an anticyclonic pressure system. This air mass was transported northward from the high anthropogenic emission area extending south of Beijing with continuous photochemical production. Subsequent cold front passage brought clean air from the north, and polluted air around Beijing was swept to the south of Beijing. This cycle was repeated about once a week and was found to be responsible for observed enhancements/reductions of aerosols at the intensive measurement sites. In contrast to secondary aerosols, the spatial distributions of primary aerosols (EC) reflected those of emissions, resulting in only slight variability despite the changes in synoptic‐scale meteorology. In accordance with these results, source apportionment simulations revealed that primary aerosols around Beijing were controlled by emissions within 100 km around Beijing within the preceding 24 h, while emissions as far as 500 km and within the preceding 3 days were found to affect secondary aerosols.

Hygroscopic growth of tropospheric particle number size distributions over the North China Plain

The hygroscopic growth of atmospheric submicrometer particle size distributions (diameter Dp ranging from 22 to 900 nm) was studied at a rural/suburban site in the North China Plain within the framework of the international Campaigns of Air Quality Research in Beijing and Surrounding Region 2006 (CAREBeijing‐2006) research project. The goal was to characterize the regional aerosol in the polluted northeastern plain in China. Size descriptive hygroscopic growth factors (DHGFs) were determined as a function of relative humidity (RH) by relating the particle number size distribution at a dry condition (&lt;30%) to those measured at higher RHs (RH = 56, 76, 85, and 91%) for the diameter range from 30 to 300 nm. In the size range of the accumulation mode (Dp &gt; 100 nm), the DHGF are substantially higher than in the Aitken particle mode (Dp &lt; 100 nm) as a result of different chemical composition. The size‐dependent behavior of the DHGF highlights the relevance of particulate sulfate production over the North China Plain, accomplished by secondary formation from the gas phase and, potentially, liquid phase processes in convective clouds. Furthermore, all results concerning the DHGF show a significant dependency on meteorological air masses. The hygroscopic growth of accumulation mode particles correlates significantly with the PM1‐mass fraction of sulfate ions determined by chemical analysis. Finally, this investigation provides a parameterization of the hygroscopic growth of 250‐nm particles, which might be useful when predicting visibility and radiative forcing and performing atmospheric aerosol model validations.