Abstract. Ground-based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) measurements of nitrous acid (HONO) and its precursor NO 2 (nitrogen dioxide) as well as aerosols have been performed daily in Beijing city centre (39.98 • N, 116.38 • E) from July 2008 to April 2009 and at the suburban site of Xianghe (39.75 • N, 116.96 • E) located ∼ 60 km east of Beijing from March 2010 to December 2012. This extensive dataset allowed for the first time the investigation of the seasonal cycle of HONO as well as its diurnal variation in and in the vicinity of a megacity. Our study was focused on the HONO and NO 2 near-surface concentrations (0-200 m layer) and total vertical column densities (VCDs) and also aerosol optical depths (AODs) and extinction coefficients retrieved by applying the Optimal Estimation Method to the MAX-DOAS observations. Monthly averaged HONO near-surface concentrations at local noon display a strong seasonal cycle with a maximum in late fall/winter (∼ 0.8 and 0.7 ppb at Beijing and Xianghe, respectively) and a minimum in summer (∼ 0.1 ppb at Beijing and 0.03 ppb at Xianghe). The seasonal cycles of HONO and NO 2 appear to be highly correlated, with correlation coefficients in the 0.7-0.9 and 0.5-0.8 ranges at Beijing and Xianghe, respectively. The stronger correlation of HONO with NO 2 and also with aerosols observed in Beijing suggests possibly larger role of NO 2 conversion into HONO in the Beijing city center than at Xianghe. The observed diurnal cycle of HONO near-surface concentration shows a maximum in the early morning (about 1 ppb at both sites) likely resulting from night-time accumulation, followed by a decrease to values of about 0.1-0.4 ppb around local noon. The HONO / NO 2 ratio shows a similar pattern with a maximum in the early morning (values up to 0.08) and a decrease to ∼ 0.01-0.02 around local noon. The seasonal and diurnal cycles of the HONO near-surface concentration are found to be similar in shape and in relative amplitude to the corresponding cycles of the HONO total VCD and are therefore likely driven mainly by the balance between HONO sources and the photolytic sink, whereas dilution effects appear to play only a minor role. The estimation of OH radical production from HONO and O 3 photolysis based on retrieved HONO near-surface concentrations and calculated photolysis rates indicate that in the 0-200 m altitude range, HONO is by far the largest source of OH radicals in winter as well as in the early morning at all seasons, while the contribution of O 3 dominates in summer from mid-morning until mid-afternoon.

Abstract. Ground-based measurements of scattered sunlight by the Multi Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) have been carried out at an urban site (39.95° N, 116.32° E) in Beijing megacity since 6 August 2008. In this study, we retrieved the tropospheric NO2 vertical column densities (VCDs) over Beijing from these MAX-DOAS observations from August 2008 to September 2011. Over this period, the daytime (08:00–17:00 Beijing Time (BJT, which equals UTC + 8)) mean tropospheric NO2 VCDs varied from 0.5 to 13.3 with an average of 3.6 during summertime, and from 0.2 to 16.8 with an average of 5.8 during wintertime, all in units of 1016 molecules cm−2. The average diurnal variation patterns of tropospheric NO2 over Beijing appeared to be rather different from one season to another, indicating differences in the emission strength and atmospheric lifetime. In contrast to previous studies, we find a small weekly cycle of the tropospheric NO2 VCD over Beijing. The NO2 VCD in the late afternoon was the largest on Saturday and the lowest on Sunday, and in the morning it reached a clear maximum on Wednesday. We also find a post-Olympic Games effect, with 39–54% decrease in the tropospheric NO2 VCD over Beijing estimated for August of 2008, compared to the following years. The tropospheric NO2 VCDs derived by our ground MAX-DOAS measurements show a good correlation with SCIAMACHY and OMI satellite data. However, compared with the MAX-DOAS measurements, the satellite observations underestimate the tropospheric NO2 VCDs over Beijing systematically, by 43% for SCIAMACHY and 26–38% for OMI (DOMINO v2.0 and DOMINO v1.02). Based on radiative transfer simulations, we show that the aerosol shielding effect can explain this underestimation, while the gradient smoothing effect caused by the coarse spatial resolution of the satellite observations could play an additional role.

Huabei, located between 32° N and 42° N, is part of eastern China and includes administratively the Beijing and Tianjin Municipalities, Hebei and Shanxi Provinces, and Inner-Mongolia Autonomous Region. Over the past decades, the region has experienced dramatic changes in air quality and climate, and has become a major focus of environmental research in China. Here we present a new inventory of air pollutant emissions in Huabei for the year 2003 developed as part of the project Influence of Pollution on Aerosols and Cloud Microphysics in North China (IPAC-NC). <br><br> Our estimates are based on data from the statistical yearbooks of the state, provinces and local districts, including major sectors and activities of power generation, industrial energy consumption, industrial processing, civil energy consumption, crop straw burning, oil and solvent evaporation, manure, and motor vehicles. The emission factors are selected from a variety of literature and those from local measurements in China are used whenever available. The estimated total emissions in the Huabei administrative region in 2003 are 4.73 Tg SO₂, 2.72 Tg NO_x (in equivalent NO₂), 1.77 Tg VOC, 24.14 Tg CO, 2.03 Tg NH₃, 4.57 Tg PM₁₀, 2.42 Tg PM_2.5, 0.21 Tg EC, and 0.46 Tg OC. <br><br> For model convenience, we consider a larger Huabei region with Shandong, Henan and Liaoning Provinces included in our inventory. The estimated total emissions in the larger Huabei region in 2003 are: 9.55 Tg SO₂, 5.27 Tg NO_x (in equivalent NO₂), 3.82 Tg VOC, 46.59 Tg CO, 5.36 Tg NH₃, 10.74 Tg PM₁₀, 5.62 Tg PM_2.5, 0.41 Tg EC, and 0.99 Tg OC. The estimated emission rates are projected into grid cells at a horizontal resolution of 0.1° latitude by 0.1° longitude. Our gridded emission inventory consists of area sources, which are classified into industrial, civil, traffic, and straw burning sectors, and large industrial point sources, which include 345 sets of power plants, iron and steel plants, cement plants, and chemical plants. <br><br> The estimated regional NO₂ emissions are about 2–3% (administrative Huabei region) or 5% (larger Huabei region) of the global anthropogenic NO₂ emissions. We compare our inventory (IPAC-NC) with the global emission inventory EDGAR-CIRCE and the Asian emission inventory INTEX-B. Except for a factor of 3 lower EC emission rate in comparison with INTEX-B, the biases of the total emissions of most primary air pollutants in Huabei estimated in our inventory, with respect to EDGAR-CIRCE and INTEX-B, generally range from −30% to +40%. Large differences up to a factor of 2–3 for local emissions in some areas (e.g. Beijing and Tianjin) are found. It is recommended that the inventories based on the a...

Abstract. We investigated aerosol hygroscopic growth property and its influence on scattering coefficient using M9003 nephelometers in coupling with humidity controlled inlet system at a rural site near Beijing mega-city from 24 April to 15 May 2006. Inlet relative humidity was controlled in an increasing range of 40%-90% while aerosol hygroscopic growth factor of scattering coefficient, f (RH=80%) as ratio of scattering coefficient at RH=80% to "dry" scattering coefficient (RH<40%) varied in a range of 1.07-2.35 during the measurement. Further analysis indicated that under dust episode, measured f (RH=80%) is 1.2±0.02, and estimated periodic mean value of f (RH=80%) was 1.31±0.03 under clean periods; during urban pollution periods, the aerosol displayed relative strong water absorbing properties with f (RH=80%) of about 1.57±0.02. An examination of chemical composition of daily filter samples highlighted that aerosol hygroscopicity was generally depressed with the increasing ratio of organic matter (OMC)/ammonium sulfate (AS) in particle mass, similar with the results of many previous studies. However, a special case with high value of f (RH=80%)=2.21 and high OMC/AS ratio was also observed, this exception reflected physico-chemical particularities of organic matter and its complex interaction with other compounds during this episode.

Abstract. Sea-land and mount-valley circulations are the dominant mesoscale synoptic systems affecting the Beijing area during summertime. Under the influence of these two circulations, the prevailing wind is southwesterly from afternoon to midnight, and then changes to northeasterly till forenoon. In this study, surface ozone (O 3 ), carbon monoxide (CO), nitric oxide (NO), nitrogen dioxide (NO 2 ), nitrogen oxide (NO x ) and non-methane hydrocarbons (NMHCs) were measured at four sites located along the route of prevailing wind, including two upwind urban sites (Fengtai "FT" and Baolian "BL"), an upwind suburban site (Shunyi "SY") and a downwind rural site (Shangdianzi "SDZ") during 20 June-16 September 2007. The purpose is to improve our understanding of ozone photochemistry in urban and rural areas of Beijing and the influence of urban plumes on ozone pollution in downwind rural areas. It is found that ozone pollution was synchronism in the urban and rural areas of Beijing, coinciding with the regional-scale synoptic processes. Due to the high traffic density and local emissions, the average levels of reactive gases NO x and NMHCs at the non-rural sites were much higher than those at SDZ. The level of long-lived gas CO at SDZ was comparable to, though slightly lower than, at the urban sites. We estimate the photochemical reactivity (L OH ) and the ozone formation potential (OFP) in the urban (BL) and rural (SDZ) areas using measured CO and NMHCs. The OH loss rate coefficient (L OH ) by total NMHCs at the BL and SDZ sites are estimated to be 50.7 s −1Correspondence to: J. Z. Ma (mjz@cams.cma.gov.cn) and 15.8 s −1 , respectively. While alkenes make a major contribution to the L OH , aromatics dominate OFP at both urban and rural sites. With respect to the individual species, CO has the largest ozone formation potential at the rural site, and at the urban site aromatic species are the leading contributors. While the O 3 diurnal variations at the four sites are typical for polluted areas, the ozone peak values are found to lag behind one site after another along the route of prevailing wind from SW to NE. Intersection analyses of trace gases reveal that polluted air masses arriving at SDZ were more aged with both higher O 3 and O x concentrations than those at BL. The results indicate that urban plume can transport not only O 3 but its precursors, the latter leading more photochemical O 3 production when being mixed with background atmosphere in the downwind rural area.

In the past decades, regional air pollution characterized by photochemical smog and grey haze-fog has become a severe environmental problem in China. To investigate this, a field measurement campaign was performed in the Huabei region, located between 32–42° N latitude in eastern China, during the period 2 April–16 May 2006 as part of the project "Influence of Pollution on Aerosols and Cloud Microphysics in North China" (IPAC-NC). It appeared that strong pollution emissions from urban and industrial centers tend to accumulate in the lower atmosphere over the central area of Huabei. We observed widespread, very high SO₂ mixing ratios, about 20–40 ppbv at 0.5–1.5 km altitude and 10–30 ppbv at 1.5–3.0 km altitude. Average CO mixing ratios were 0.65–0.7 ppmv at 0.5–1.5 km altitude, and very high CO around 1 ppmv was observed during some flights, and even higher levels at the surface. We find the high pollution concentrations to be associated with enhanced levels of OH and HO₂ radicals, calculated with a chemical box model constrained by the measurements. In the upper part of the boundary layer and in the lower free troposphere, high CO and SO₂ compete with relatively less NO₂ in reacting with OH, being efficiently recycled through HO₂, preventing a net loss of HO_x radicals. In addition to reactive hydrocarbons and CO, the oxidation of SO₂ causes significant ozone production over Huabei (up to ~13% or 2.0 ppbv h⁻¹ at 0.8 km altitude). Our results indicate that the lower atmosphere over Huabei is not only strongly polluted but also acts as an oxidation pool, with pollutants undergoing very active photochemistry over this part of China

Abstract. Inter-annual variability and long-term trends in tropospheric ozone are both environmental and climate concerns. Ozone measured at Mt Waliguan Observatory (WLG, 3816 m a.s.l.) on the Tibetan Plateau over the period of 1994-2013 has increased significantly by 0.2-0.3 ppbv yr −1 during spring and autumn but shows a much smaller trend in winter and no significant trend in summer. Here we explore the factors driving the observed ozone changes at WLG using backward trajectory analysis, chemistry-climate model hindcast simulations (GFDL AM3), a trajectory-mapped ozonesonde data set, and several climate indices. A stratospheric ozone tracer implemented in GFDL AM3 indicates that stratosphere-to-troposphere transport (STT) can explain ∼ 60 % of the simulated springtime ozone increase at WLG, consistent with an increase in the NW air-mass frequency inferred from the trajectory analysis. Enhanced STT associated with the strengthening of the mid-latitude jet stream contributes to the observed high ozone anomalies at WLG during the springs of 1999 and 2012. During autumn, observations at WLG are more heavily influenced by polluted air masses originating from South East Asia than in the other seasons. Rising Asian anthropogenic emissions of ozone precursors are the key driver of increasing autumnal ozone observed at WLG, as supported by the GFDL AM3 model with time-varying emissions, which captures the observed ozone increase (0.26 ± 0.11 ppbv yr −1 ). AM3 simulates a greater ozone increase of 0.38 ± 0.11 ppbv yr −1 at WLG in autumn under conditions with strong transport from South East Asia and shows no significant ozone trend in autumn when anthropogenic emissions are held constant in time. During summer, WLG is mostly influenced by easterly air masses, but these trajectories do not extend to the polluted regions of eastern China and have decreased significantly over the last 2 decades, which likely explains why summertime ozone measured at WLG shows no significant trend despite ozone increases in eastern China. Analysis of the Trajectory-mapped Ozonesonde data set for the Stratosphere and Troposphere (TOST) and trajectory residence time reveals increases in direct ozone transport from the eastern sector during autumn, which adds to the autumnal ozone increase. We further examine the links of ozone variability at WLG to the quasibiennial oscillation (QBO), the East Asian summer monsoon (EASM), and the sunspot cycle. Our results suggest that the 2-3-, 3-7-, and 11-year periodicities are linked to the QBO, EASM index, and sunspot cycle, respectively. A multivariate regression analysis is performed to quantify the relative Published by Copernicus Publications on behalf of the European Geosciences Union. contributions of various factors to surface ozone concentrations at WLG. Through an observational and modelling analysis, this study demonstrates the complex relationships between surface ozone at remote locations and its dynamical and chemical influencing factors.

As part of the Tibet Ozone, Aerosol and Radiation (TOAR) project, a micropulse lidar was operated in Naqu (31.5°N, 92.1°E; 4508 m MSL) on the Tibetan Plateau to observe cirrus clouds continuously from 19 July to 26 August 2011. During the experiment, the time coverage of ice clouds only was 15% in the upper troposphere (above 9.5 km MSL). The cirrus top/bottom altitudes (mean values of 15.6/14.7 km) are comparable to those measured previously at tropical sites but relatively higher than those measured at midlatitude sites. The majority of the cloud layers yielded a lidar ratio between 10 and 40 sr, with a mean value of 28 ± 15 sr, characterized by a bimodal frequency distribution. Subvisible, thin, and opaque cirrus formation was observed in 16%, 34%, and 50% of all cirrus cases, respectively. A mean cirrus optical depth of 0.33 was observed over the Tibetan Plateau, slightly higher than those in the subtropics and tropics. With decreasing temperature, the lidar ratio increased slightly, whereas the mean extinction coefficient decreased significantly. The occurrence of clouds is highly correlated with the outgoing longwave radiation and the strong cold perturbations in the upper troposphere. Deep convective activity and Rossby waves are important dynamical processes that control cirrus variations over the Tibetan Plateau, where both anvil cirrus outflowing from convective cumulonimbus clouds and large-scale strong cold perturbations in the upper troposphere should play an important role in cirrus formation.