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Nitrate (NO3-) has become a major component of fine particulate matter (PM2.5) during hazy days in China. However, the role of the heterogeneous reactions of dinitrogen pentoxide (N2O5) in nitrate formation is not well constrained. In January 2017, a severe haze event occurred in the Pearl River Delta (PRD) of southern China during which high levels of PM2.5 (∼400 µg m−3) and O3 (∼160 ppbv) were observed at a semi-rural site (Heshan) in the western PRD. Nitrate concentrations reached 108 µg m−3 (1 h time resolution), and the contribution of nitrate to PM2.5 was nearly 40 %. Concurrent increases in NO3- and ClNO2 (with a maximum value of 8.3 ppbv at a 1 min time resolution) were observed in the first several hours after sunset, indicating an intense N2O5 heterogeneous uptake by aerosols. The formation potential of NO3- via N2O5 heterogeneous reactions was estimated to be between 29.0 and 77.3 µg m−3 in the early hours (2 to 6 h) after sunset based on the measurement data, which could completely explain the measured increase in the NO3- concentration during the same time period. Daytime production of nitric acid from the gas-phase reaction of OH+NO2 was calculated with a chemical box model built using the Master Chemical Mechanism (MCM v3.3.1) and constrained by the measurement data. The integrated nocturnal nitrate formed via N2O5 chemistry was comparable to or even higher than the nitric acid formed during the day. This study confirms that N2O5 heterogeneous chemistry was a significant source of aerosol nitrate during hazy days in southern China.

The heterogeneous reaction of dinitrogen pentoxide (N

Tropospheric ozone is of great importance with regard to air quality, atmospheric chemistry, and climate change. In this paper we report the first continuous record of surface ozone in the background atmosphere of South China. The data were obtained from 1994 to 2007 at a coastal site in Hong Kong, which is strongly influenced by the outflow of Asian continental air during the winter and the inflow of maritime air from the subtropics in the summer. Three methods are used to derive the rate of change in ozone. A linear fit to the 14-year record shows that the ozone concentration increased by 0.58 ppbv/yr, whereas comparing means in years 1994–2000 and 2001–2007 gives an increase of 0.87 ppbv/yr for a 7-year period. The ozone changes in air masses from various source regions are also examined. Using local wind and carbon monoxide (CO) data to filter out local influence, we find that ozone increased by 0.94 ppbv/yr from 1994–2000 to 2001–2007 in air masses from Eastern China, with similar changes in the other two continent-influenced air-mass groups, but no statistically significant change in the marine air. An examination of the nitrogen dioxide (NO2) column obtained from GOME and SCIAMACHY reveals an increase in atmospheric NO2 in China's three fastest developing coastal regions, whereas NO2 in other parts of Asia decreased during the same period, and no obvious trend over the main shipping routes in the South China Sea was indicated. Thus the observed increase in background ozone in Hong Kong is most likely due to the increased emissions of NO2 (and possibly volatile organic compounds (VOCs) as well) in the upwind coastal regions of mainland China. The CO data at Hok Tsui showed less definitive changes compared to the satellite NO2 column. The increase in background ozone likely made a strong contribution (81%) to the rate of increase in "total ozone" at an urban site in Hong Kong, suggesting the need to consider distant sources when developing long-term strategies to mitigate local ozone pollution.

This paper presents the first results of the measurements of trace gases and aerosols at three surface sites in and outside Beijing before and during the 2008 Olympics. The official air pollution index near the Olympic Stadium and the data from our nearby site revealed an obvious association between air quality and meteorology and different responses of secondary and primary pollutants to the control measures. Ambient concentrations of vehicle-related nitrogen oxides (NOx) and volatile organic compounds (VOCs) at an urban site dropped by 25% and 20–45% in the first two weeks after full control was put in place, but the levels of ozone, sulfate and nitrate in PM2.5 increased by 16%, 64%, 37%, respectively, compared to the period prior to the full control; wind data and back trajectories indicated the contribution of regional pollution from the North China Plain. Air quality (for both primary and secondary pollutants) improved significantly during the Games, which were also associated with the changes in weather conditions (prolonged rainfall, decreased temperature, and more frequent air masses from clean regions). A comparison of the ozone data at three sites on eight ozone-pollution days, when the air masses were from the southeast-south-southwest sector, showed that regional pollution sources contributed >34–88% to the peak ozone concentrations at the urban site in Beijing. Regional sources also contributed significantly to the CO concentrations in urban Beijing. Ozone production efficiencies at two sites were low (~3 ppbv/ppbv), indicating that ozone formation was being controlled by VOCs. Compared with data collected in 2005 at a downwind site, the concentrations of ozone, sulfur dioxide (SO2), total sulfur (SO2+PM2.5 sulfate), carbon monoxide (CO), reactive aromatics (toluene and xylenes) sharply decreased (by 8–64%) in 2008, but no significant changes were observed for the concentrations of PM2.5, fine sulfate, total odd reactive nitrogen (NOy), and longer lived alkanes and benzene. We suggest that these results indicate the success of the government's efforts in reducing emissions of SO2, CO, and VOCs in Beijing, but increased regional emissions during 2005–2008. More stringent control of regional emissions will be needed for significant reductions of ozone and fine particulate pollution in Beijing.

This paper presents the first results of the measurements of trace gases and aerosols at three surface sites in and outside Beijing before and during the 2008 Olympics. The official air pollution index near the Olympic Stadium and the data from our nearby site revealed an obvious association between air quality and meteorology and different responses of secondary and primary pollutants to the control measures. Ambient concentrations of vehicle-related nitrogen oxides (NOx) and volatile organic compounds (VOCs) at an urban site dropped by 25% and 20–45% in the first two weeks after full control was put in place, but the levels of ozone, sulfate and nitrate in PM2.5 increased by 16%, 64%, 37%, respectively, compared to the period prior to the full control; wind data and back trajectories indicated the contribution of regional pollution from the North China Plain. Air quality (for both primary and secondary pollutants) improved significantly during the Games, which were also associated with the changes in weather conditions (prolonged rainfall, decreased temperature, and more frequent air masses from clean regions). A comparison of the ozone data at three sites on eight ozone-pollution days, when the air masses were from the southeast-south-southwest sector, showed that regional pollution sources contributed >34–88% to the peak ozone concentrations at the urban site in Beijing. Regional sources also contributed significantly to the CO concentrations in urban Beijing. Ozone production efficiencies at two sites were low (~3 ppbv/ppbv), indicating that ozone formation was being controlled by VOCs. Compared with data collected in 2005 at a downwind site, the concentrations of ozone, sulfur dioxide (SO2), total sulfur (SO2+PM2.5 sulfate), carbon monoxide (CO), reactive aromatics (toluene and xylenes) sharply decreased (by 8–64%) in 2008, but no significant changes were observed for the concentrations of PM2.5, fine sulfate, total odd reactive nitrogen (NOy), and longer lived alkanes and benzene. We suggest that these results indicate the success of the government's efforts in reducing emissions of SO2, CO, and VOCs in Beijing, but increased regional emissions during 2005–2008. More stringent control of regional emissions will be needed for significant reductions of ozone and fine particulate pollution in Beijing.

[1] As a cooperative effort with the TRACE-P and ACE-Asia intensive in the spring of 2001, trace gases and aerosols were measured at a relatively remote coastal site (Hok Tsui) in southeastern Hong Kong. The main objective of the measurement program was to provide continuous ground-based data in the subtropical region of eastern Asia and to characterize the southward outflow of continental pollution that prevails in the lower atmosphere during early spring. In this paper, we present the results for ozone, CO, NO, NOy ,S O2, 222 Radon, methane and C2–C8 nonmethane hydrocarbons (NMHCs), C1–C2 halocarbons, and C1–C5 alkyl nitrate measurements obtained between 19 February and 30 April 2001. The average mixing ratios of O3, CO, SO2, and NOy were 45 ppbv, 404 ppbv, 1.8 ppbv, and 10.4 ppbv, respectively. The two dominant NMHCs were ethane (mean: 2368 pptv) and ethyne (mean: 1402 pptv), followed by propane (814 pptv), toluene (540 pptv), benzene (492 pptv), ethene (498 pptv), and n-butane (326 pptv). The most abundant halocarbon was CH3Cl (mean: 821 pptv), while 2-BuONO2 and i-PrONO2 were the two dominant alkyl nitrates species with a mean mixing ratio of 20 pptv and 19 pptv, respectively. The levels of trace gases were strongly influenced by the outflow of continental air masses initiated by the passage of cold fronts. The data are segregated into four air mass groups according to the levels of 222 Rn and wind direction, representing fresh continental outflow, coastal, perturbed maritime, and local urban air. Ozone and CO showed a moderate positive correlation (r 2 = 0.4) in the marine air group, characterized by low 222 Rn and CO levels, but they were poorly correlated in the other air mass groups. SO2 and NOy exhibited good correlations (r 2 > 0.6) with each other but were poorly correlated with CO, indicating differences in their emission sources and/or removal processes. CO very strongly correlated with ethyne and benzene (r 2 > 0.85) and also showed good correlations with several other NMHCs. Moreover, CO correlated moderately with a biomass burning tracer (CH3Cl) and an urban/industrial tracer (C2Cl4) indicating the impact of mixed pollution from urban and biomass burning sources. The relationship of CO, SO2, and NOy with the indicator of atmospheric processing, ethyne/ CO and propane/ethane, were also examined. The 2001 data were compared to the results obtained in the same period in 1994 during PEM-West B. The mean ozone level in the spring of 2001 was much higher than during PEM-West B. SO2 also had higher concentrations during TRACE-P, while CO and NOy were comparable during the two campaigns. The observed difference has been discussed in the context of emission changes and variations in meteorology. Although it is difficult to draw definitive conclusions about the extent of the influence of these two factors, it appears that clearer skies and drier conditions may have been responsible for the higher ozone concentrations during the TRACE-P period. INDEX TERMS: 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry