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Air stagnation is an important meteorological measure of unfavorable air pollution conditions, but little is known about it in China. We conducted a comprehensive investigation of air stagnation in China from January 1985 to December 2014 based on sounding and surface observations from 81 stations. The stagnation criteria were revised to account for the large topographical diversity in the country. It is found that the annual mean of air stagnation occurrences is closely related to general topography and climate features. Two basins in the northwest and southwest of China, the Tarim and Sichuan basins, exhibit the most frequent stagnation occurrence (50 % of days per year), whereas two plateaus (the Qinghai–Tibet Plateau and the Inner Mongolian plateau) and the eastern coastal areas experience the least (20 % of days per year). Over the whole country, air stagnation is at a maximum in summer and a minimum in winter, except for Urumchi, a major city in northwestern China where stagnation maintains a rather constant value year round with a minimum in spring. There is a nationwide positive trend in stagnation occurrence during 1985–2014, with the strongest increasing centers over Shandong Peninsula in eastern China and southern Shaanxi in central China. Changes in air stagnation occurrences are dependent on three components (upper- and lower-air winds and precipitation-free days). This shows that the behavior of upper-air wind speeds is the main driver of the spatial distribution and trends in air stagnation, followed by near-surface winds and dry days, which contribute the least.

When working, the geometric distribution shape of concrete in concrete mixing truck's rotary drum changes continuously, which cause a great difficulty for studying the dynamic performance of the mixing drum. In this paper, the mixing system of a certain type of concrete mixing truck is studied. A mathematical formulation has been derived through the force analysis to calculate the supporting force. The calculation method of the concrete distribution shape in the rotary drum is developed. A new transfer matrix is built with considering the concrete geometric distribution shape. The effects of rotating speed, inclination angle and concrete liquid level on the vibration performance of the mixing drum are studied with a specific example. Results show that with the increase of rotating speed, the vibration amplitude of the mixing drum decreases. The peak amplitude gradually moves to the right with the inclination angle increasing. The amplitude value of the peak's left side decreases when tilt angle increases, while the right side increases. The maximum unbalanced response amplitude of the drum increases with the decrease of concrete liquid level height, and the vibration peak moves to the left.

Atmospheric pollutants have both beneficial and detrimental effects on carbon uptake by land ecosystems. Surface ozone (O3) damages leaf photosynthesis by oxidizing plant cells, while aerosols promote carbon uptake by increasing diffuse radiation and exert additional influences through concomitant perturbations to meteorology and hydrology. China is currently the world's largest emitter of both carbon dioxide and short-lived air pollutants. The land ecosystems of China are estimated to provide a carbon sink, but it remains unclear whether air pollution acts to inhibit or promote carbon uptake. Here, we employ Earth system modeling and multiple measurement datasets to assess the separate and combined effects of anthropogenic O3 and aerosol pollution on net primary productivity (NPP) in China. In the present day, O3 reduces annual NPP by 0.6 Pg C (14 %) with a range from 0.4 Pg C (low O3 sensitivity) to 0.8 Pg C (high O3 sensitivity). In contrast, aerosol direct effects increase NPP by 0.2 Pg C (5 %) through the combination of diffuse radiation fertilization, reduced canopy temperatures, and reduced evaporation leading to higher soil moisture. Consequently, the net effects of O3 and aerosols decrease NPP by 0.4 Pg C (9 %) with a range from 0.2 Pg C (low O3 sensitivity) to 0.6 Pg C (high O3 sensitivity). However, precipitation inhibition from combined aerosol direct and indirect effects reduces annual NPP by 0.2 Pg C (4 %), leading to a net air pollution suppression of 0.8 Pg C (16 %) with a range from 0.6 Pg C (low O3 sensitivity) to 1.0 Pg C (high O3 sensitivity). Our results reveal strong dampening effects of air pollution on the land carbon uptake in China today. Following the current legislation emission scenario, this suppression will be further increased by the year 2030, mainly due to a continuing increase in surface O3. However, the maximum technically feasible reduction scenario could drastically relieve the current level of NPP damage by 70 % in 2030, offering protection of this critical ecosystem service and the mitigation of long-term global warming.

East China experiences extensive crop residue burnings in fields during harvest season. The direct radiative effect (DRE) of carbonaceous aerosols from crop residue burning in June 2013 in East China was investigated using the Weather Research and Forecasting Model coupled with Chemistry (WRF-Chem). Absorption of organic aerosol (OA) in the presence of brown carbon was considered using the parameterization of Saleh et al. (2014), in which the imaginary part of the OA refractive index is a function of wavelength and the ratio of black carbon (BC) and OA. The carbonaceous emissions from crop fires were estimated using the Moderate Resolution Imaging Spectroradiometer (MODIS) fire radiative power (FRP) product with a localized crop-burning-sourced BC-to-organic carbon (OC) ratio emission ratio of 0.27. Evaluation of the model results with in situ measurements of particulate matter with aerodynamic diameter less than 2.5 µm (PM2. 5) chemical composition, MODIS aerosol optical depth (AOD) detections and meteorological observations showed that this model was able to reproduce the magnitude, spatial variation and optical characteristics of carbonaceous aerosol pollution. The observed BC and OC peak concentrations at the site in Suixi, Anhui province, during the 2013 wheat burning season reached 55.3 µg m−3 and 157.9 µg m−3. WRF-Chem simulations reproduced these trends with a correlation coefficient of 0.74, estimating that crop residue burning contributed 86 and 90 % of peak BC and OC, respectively. The simulated hourly DRE from crop residue burning at the top of atmosphere (TOA) reached a maximum of +22.66 W m−2 at the Suixi site. On average, the simulations showed that the crop residue burning introduced a net positive DRE of +0.14 W m−2 at TOA throughout East China, with BC from this source as the main heating contributor (+0.79 W m−2). The OA DRE from crop burning (−0.22 W m−2) was a combined effect of the positive DRE of absorption (+0.21 W m−2) and a stronger negative DRE of scattering (−0.43 W m−2). Sensitivity tests showed that the DRE of OA absorption strongly depended on the imaginary part of the OA refractive index, the BC-to-OA emission ratio from crop residue burning and the assumed mixing state of the aerosol, whereby the volume mixing treatment resulted in a higher positive DRE compared to the core–shell treatment. The BC mixing state and associated absorption enhancement during BC aging processes will be investigated in detail in future research.

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.

The North China Plain (NCP) has been experiencing severe air pollution problems with rapid economic growth and urbanisation. Many field and model studies have examined the distribution of air pollutants in the NCP, but convincing results have not been achieved, mainly due to a lack of direct measurements of pollutants over large areas. Here, we employed a mobile laboratory to observe the main air pollutants in a large part of the NCP from 11 June to 15 July 2013. High median concentrations of sulfur dioxide (SO2) (12 ppb), nitrogen oxides (NOx) (NO + NO2; 452 ppb), carbon monoxide (CO) (956 ppb), black carbon (BC; 5.5 µg m−3) and ultrafine particles (28 350 cm−3) were measured. Most of the high values, i.e. 95 percentile concentrations, were distributed near large cities, suggesting the influence of local emissions. In addition, we analysed the regional transport of SO2 and CO, relatively long-lived pollutants, based on our mobile observations together with wind field and satellite data analyses. Our results suggested that, for border areas of the NCP, wind from outside this area would have a diluting effect on pollutants, while south winds would bring in pollutants that have accumulated during transport through other parts of the NCP. For the central NCP, the concentrations of pollutants were likely to remain at high levels, partly due to the influence of regional transport by prevalent south–north winds over the NCP and partly by local emissions.

The ability of seven state-of-the-art chemistry–aerosol models to reproduce distributions of tropospheric ozone and its precursors, as well as aerosols over eastern Asia in summer 2008, is evaluated. The study focuses on the performance of models used to assess impacts of pollutants on climate and air quality as part of the EU ECLIPSE project. Models, run using the same ECLIPSE emissions, are compared over different spatial scales to in situ surface, vertical profiles and satellite data. Several rather clear biases are found between model results and observations, including overestimation of ozone at rural locations downwind of the main emission regions in China, as well as downwind over the Pacific. Several models produce too much ozone over polluted regions, which is then transported downwind. Analysis points to different factors related to the ability of models to simulate VOC-limited regimes over polluted regions and NOx limited regimes downwind. This may also be linked to biases compared to satellite NO2, indicating overestimation of NO2 over and to the north of the northern China Plain emission region. On the other hand, model NO2 is too low to the south and west of this region and over South Korea/Japan. Overestimation of ozone is linked to systematic underestimation of CO particularly at rural sites and downwind of the main Chinese emission regions. This is likely to be due to enhanced destruction of CO by OH. Overestimation of Asian ozone and its transport downwind implies that radiative forcing from this source may be overestimated. Model-observation discrepancies over Beijing do not appear to be due to emission controls linked to the Olympic Games in summer 2008.With regard to aerosols, most models reproduce the satellite-derived AOD patterns over eastern China. Our study nevertheless reveals an overestimation of ECLIPSE model mean surface BC and sulphate aerosols in urban China in summer 2008. The effect of the short-term emission mitigation in Beijing is too weak to explain the differences between the models. Our results rather point to an overestimation of SO2 emissions, in particular, close to the surface in Chinese urban areas. However, we also identify a clear underestimation of aerosol concentrations over northern India, suggesting that the rapid recent growth of emissions in India, as well as their spatial extension, is underestimated in emission inventories. Model deficiencies in the representation of pollution accumulation due to the Indian monsoon may also be playing a role. Comparison with vertical aerosol lidar measurements highlights a general underestimation of scattering aerosols in the boundary layer associated with overestimation in the free troposphere pointing to modelled aerosol lifetimes that are too long. This is likely linked to too strong vertical transport and/or insufficient deposition efficiency during transport or export from the boundary layer, rather than chemical processing (in the case of sulphate aerosols). Underestimation of sulphate in the boundary layer implies potentially large errors in simulated aerosol–cloud interactions, via impacts on boundary-layer clouds.This evaluation has important implications for accurate assessment of air pollutants on regional air quality and global climate based on global model calculations. Ideally, models should be run at higher resolution over source regions to better simulate urban–rural pollutant gradients and/or chemical regimes, and also to better resolve pollutant processing and loss by wet deposition as well as vertical transport. Discrepancies in vertical distributions require further quantification and improvement since these are a key factor in the determination of radiative forcing from short-lived pollutants.

The morphology and density of black carbon (BC) cores in internally mixed BC (In-BC) particles affect their mixing state and absorption enhancement. In this work, we developed a new method to measure the morphology and effective density of the BC cores of ambient In-BC particles using a single-particle soot photometer (SP2) and a volatility tandem differential mobility analyzer (VTDMA) during the CAREBeijing-2013 campaign from 8 to 27 July 2013 at Xianghe Observatory. This new measurement system can select size-resolved ambient In-BC particles and measure the mobility diameter and mass of the In-BC cores. The morphology and effective density of the ambient In-BC cores are then calculated. For the In-BC cores in the atmosphere, changes in their dynamic shape factor (χ) and effective density (ρeff) can be characterized as a function of the aging process (Dp∕Dc) measured by SP2 and VTDMA. During an intensive field study, the ambient In-BC cores had an average shape factor χ of ∼ 1.2 and an average density of ∼ 1.2 g cm−3, indicating that ambient In-BC cores have a near-spherical shape with an internal void of ∼ 30 %. From the measured morphology and density, the average shell ∕ core ratio and absorption enhancement (Eab) of ambient BC were estimated to be 2.1–2.7 and 1.6–1.9, respectively, for In-BC particles with sizes of 200–350 nm. When the In-BC cores were assumed to have a void-free BC sphere with a density of 1.8 g cm−3, the shell ∕ core ratio and Eab were overestimated by ∼ 13 and ∼ 17 %, respectively. The new approach developed in this work improves the calculations of the mixing state and optical properties of ambient In-BC particles by quantifying the changes in the morphology and density of ambient In-BC cores during aging.

Ammonia (NH3) can interact in the atmosphere with other trace chemical species, which can lead to detrimental environmental consequences, such as the formation of fine particulates and ultimately global climate change. China is a major agricultural country, and livestock numbers and nitrogen fertilizer use have increased drastically since 1978, following the rapid economic and industrial development experienced by the country. In this study, comprehensive NH3 emissions inventories were compiled for China for 1980–2012. In a previous study, we parameterized emissions factors (EFs) considering ambient temperature, soil acidity, and the method and rate of fertilizer application. In this study, we refined these EFs by adding the effects of wind speed and new data from field experiments of NH3 flux in cropland in northern China. We found that total NH3 emissions in China increased from 5.9 to 11.1 Tg from 1980 to 1996, and then decreased to 9.7 Tg in 2012. The two major contributors were livestock manure and synthetic fertilizer application, which contributed 80–90 % of the total emissions. Emissions from livestock manure rose from 2.86 Tg (1980) to 6.16 Tg (2005), and then decreased to 5.0 Tg (2012); beef cattle were the largest source followed by laying hens and pigs. The remarkable downward trend in livestock emissions that occurred in 2007 was attributed to a decrease in the numbers of various livestock animals, including beef cattle, goats, and sheep. Meanwhile, emissions from synthetic fertilizer ranged from 2.1 Tg (1980) to 4.7 Tg (1996), and then declined to 2.8 Tg (2012). Urea and ammonium bicarbonate (ABC) dominated this category of emissions, and a decline in ABC application led to the decrease in emissions that took place from the mid-1990s onwards. High emissions were concentrated in eastern and southwestern China. Seasonally, peak NH3 emissions occurred in spring and summer. The inventories had a monthly temporal resolution and a spatial resolution of 1000 m, and thus are suitable for global and regional air-quality modeling.

Current-induced magnetization switching (CIMS) via the spin-orbit torque is technologically important for applications of spintronic devices. Existing experimental studies are focused on 5d heavy metals with large spin-orbit coupling but theoretical studies indicate that 3d or 4d light metals with weak spin-orbit coupling may also generate sizable torque through the strong orbital Hall effect. However, CIMS has seldom been experimentally demonstrated using 3d or 4d light metals. Here, we report sizable current-induced torque and a robust CIMS in weakly spin-orbit coupled Zr based perpendicular magnetized multilayers. Current-induced effective torque field changes its sign as the Zr layer thickness varies, indicating the competition of multiple effects. Possible roles of the orbital Hall effect in the competition are discussed. Our findings widen the material scope of the CIMS and imply possible applications of the orbital Hall effect.

This paper presents a summary of the work done within the European Union's Seventh Framework Programme project ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants). ECLIPSE had a unique systematic concept for designing a realistic and effective mitigation scenario for short-lived climate pollutants (SLCPs; methane, aerosols and ozone, and their precursor species) and quantifying its climate and air quality impacts, and this paper presents the results in the context of this overarching strategy. The first step in ECLIPSE was to create a new emission inventory based on current legislation (CLE) for the recent past and until 2050. Substantial progress compared to previous work was made by including previously unaccounted types of sources such as flaring of gas associated with oil production, and wick lamps. These emission data were used for present-day reference simulations with four advanced Earth system models (ESMs) and six chemistry transport models (CTMs). The model simulations were compared with a variety of ground-based and satellite observational data sets from Asia, Europe and the Arctic. It was found that the models still underestimate the measured seasonality of aerosols in the Arctic but to a lesser extent than in previous studies. Problems likely related to the emissions were identified for northern Russia and India, in particular. To estimate the climate impacts of SLCPs, ECLIPSE followed two paths of research: the first path calculated radiative forcing (RF) values for a large matrix of SLCP species emissions, for different seasons and regions independently. Based on these RF calculations, the Global Temperature change Potential metric for a time horizon of 20 years (GTP20) was calculated for each SLCP emission type. This climate metric was then used in an integrated assessment model to identify all emission mitigation measures with a beneficial air quality and short-term (20-year) climate impact. These measures together defined a SLCP mitigation (MIT) scenario. Compared to CLE, the MIT scenario would reduce global methane (CH4) and black carbon (BC) emissions by about 50 and 80 %, respectively. For CH4, measures on shale gas production, waste management and coal mines were most important. For non-CH4 SLCPs, elimination of high-emitting vehicles and wick lamps, as well as reducing emissions from gas flaring, coal and biomass stoves, agricultural waste, solvents and diesel engines were most important. These measures lead to large reductions in calculated surface concentrations of ozone and particulate matter. We estimate that in the EU, the loss of statistical life expectancy due to air pollution was 7.5 months in 2010, which will be reduced to 5.2 months by 2030 in the CLE scenario. The MIT scenario would reduce this value by another 0.9 to 4.3 months. Substantially larger reductions due to the mitigation are found for China (1.8 months) and India (11–12 months). The climate metrics cannot fully quantify the climate response. Therefore, a second research path was taken. Transient climate ensemble simulations with the four ESMs were run for the CLE and MIT scenarios, to determine the climate impacts of the mitigation. In these simulations, the CLE scenario resulted in a surface temperature increase of 0.70 ± 0.14 K between the years 2006 and 2050. For the decade 2041–2050, the warming was reduced by 0.22 ± 0.07 K in the MIT scenario, and this result was in almost exact agreement with the response calculated based on the emission metrics (reduced warming of 0.22 ± 0.09 K). The metrics calculations suggest that non-CH4 SLCPs contribute ~ 22 % to this response and CH4 78 %. This could not be fully confirmed by the transient simulations, which attributed about 90 % of the temperature response to CH4 reductions. Attribution of the observed temperature response to non-CH4 SLCP emission reductions and BC specifically is hampered in the transient simulations by small forcing and co-emitted species of the emission basket chosen. Nevertheless, an important conclusion is that our mitigation basket as a whole would lead to clear benefits for both air quality and climate. The climate response from BC reductions in our study is smaller than reported previously, possibly because our study is one of the first to use fully coupled climate models, where unforced variability and sea ice responses cause relatively strong temperature fluctuations that may counteract (and, thus, mask) the impacts of small emission reductions. The temperature responses to the mitigation were generally stronger over the continents than over the oceans, and with a warming reduction of 0.44 K (0.39–0.49) K the largest over the Arctic. Our calculations suggest particularly beneficial climate responses in southern Europe, where surface warming was reduced by about 0.3 K and precipitation rates were increased by about 15 (6–21) mm yr−1 (more than 4 % of total precipitation) from spring to autumn. Thus, the mitigation could help to alleviate expected future drought and water shortages in the Mediterranean area. We also report other important results of the ECLIPSE project.

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.

Oxygenated volatile organic compounds (OVOCs) are important products of the photo-oxidation of hydrocarbons. They influence the oxidizing capacity and the ozone-forming potential of the atmosphere. In the summer of 2008, 2 months of emission restrictions were enforced in Beijing to improve air quality during the Olympic Games. Observational evidence reported in related studies that these control measures were efficient in reducing the concentrations of primary anthropogenic pollutants (CO, NOx and non-methane hydrocarbons, i.e., NMHCs) by 30–40%. In this study, the influence of the emission restrictions on ambient levels of OVOCs was explored using a neural network analysis with consideration of meteorological conditions. Statistically significant reductions in formaldehyde (HCHO), acetaldehyde (CH3CHO), methyl ethyl ketone (MEK) and methanol were found to be 12.9, 15.8, 17.1 and 19.6%, respectively, when the restrictions were in place. The effect of emission controls on acetone was not detected in neural network simulations, probably due to pollution transport from surrounding areas outside Beijing. Although the ambient levels of most NMHCs were reduced by ~35% during the full control period, the emission ratios of reactive alkenes and aromatics closely related to automobile sources did not present much difference (< 30%). A zero-dimensional box model based on the Master Chemical Mechanism version 3.2 (MCM3.2) was applied to evaluate how OVOC production responds to the reduced precursors during the emissions control period. On average, secondary HCHO was produced from the oxidation of anthropogenic alkenes (54%), isoprene (30%) and aromatics (15%). The importance of biogenic sources for the total HCHO formation was almost on par with that of anthropogenic alkenes during the daytime. Anthropogenic alkenes and alkanes dominated the photochemical production of other OVOCs such as acetaldehyde, acetone and MEK. The relative changes of modeled HCHO, CH3CHO, methyl vinyl ketone and methacrolein (MVK + MACR) before and during the pollution controlled period were comparable to the estimated reductions in the neural network, reflecting that current mechanisms can largely explain secondary production of those species under urban conditions. However, it is worth noting that the box model overestimated the measured concentrations of aldehydes by a factor of 1.4–1.7 without consideration of loss of aldehydes on aerosols, and simulated MEK was in good agreement with the measurements when primary sources were taken into consideration. These results suggest that the understanding of the OVOCs budget in the box model remains incomplete, and that there is still considerable uncertainty in particular missing sinks (unknown chemical and physical processes) for aldehydes and absence of direct emissions for ketones.

To investigate the air quality during 2010 World Expo, continuous measurements of particle number size distributions and optical parameters were performed at urban Shanghai from April to June 2010. Total particle number and volume concentrations in the size range 16–600 nm were 12 700±6200 cm−3 and 16±8 µm3/cm3, respectively. Meanwhile, the optical parameters, particle light-scattering coefficient b sp,532nm and absorption coefficient b ap,532nm were 210±140 Mm−1 and 26±20 Mm−1, respectively. Strong correlation (R=0.69) was observed between b sp,532nm and the number concentration of accumulation mode particles, especially in the specific size range 300–500 nm (R=0.87). Cluster analysis on air mass history was performed to explore the relationship between air mass origins and the optical as well as microphysical parameters. Back trajectories were classified into four major clusters. Air masses came from the west direction, in which continental aerosols were predominant, associating with the polluted cases during the summertime in Shanghai. In addition, the northern air mass showed the lower values of aerosol single scattering albedo ω 0,532nm, indicating the presence of smaller light-absorbing particles originated from the North China Plain.

Nighttime HOx chemistry was investigated in two ground-based field campaigns (PRIDE-PRD2006 and CAREBEIJING2006) in summer 2006 in China by comparison of measured and modeled concentration data of OH and HO2. The measurement sites were located in a rural environment in the Pearl River Delta (PRD) under urban influence and in a suburban area close to Beijing, respectively. In both locations, significant nighttime concentrations of radicals were observed under conditions with high total OH reactivities of about 40–50 s−1 in PRD and 25 s−1 near Beijing. For OH, the nocturnal concentrations were within the range of (0.5–3) × 106 cm−3, implying a significant nighttime oxidation rate of pollutants on the order of several ppb per hour. The measured nighttime concentration of HO2 was about (0.2–5) × 108 cm−3, containing a significant, model-estimated contribution from RO2 as an interference. A chemical box model based on an established chemical mechanism is capable of reproducing the measured nighttime values of the measured peroxy radicals and $k_{\text{OH}}$, but underestimates in both field campaigns the observed OH by about 1 order of magnitude. Sensitivity studies with the box model demonstrate that the OH discrepancy between measured and modeled nighttime OH can be resolved, if an additional ROx production process (about 1 ppb h−1) and additional recycling (RO2 → HO2 → OH) with an efficiency equivalent to 1 ppb NO is assumed. The additional recycling mechanism was also needed to reproduce the OH observations at the same locations during daytime for conditions with NO mixing ratios below 1 ppb. This could be an indication that the same missing process operates at day and night. In principle, the required primary ROx source can be explained by ozonolysis of terpenoids, which react faster with ozone than with OH in the nighttime atmosphere. However, the amount of these highly reactive biogenic volatile organic compounds (VOCs) would require a strong local source, for which there is no direct evidence. A more likely explanation for an additional ROx source is the vertical downward transport of radical reservoir species in the stable nocturnal boundary layer. Using a simplified one-dimensional two-box model, it can be shown that ground-based NO emissions could generate a large vertical gradient causing a downward flux of peroxy acetic nitrate (PAN) and peroxymethacryloyl nitrate (MPAN). The downward transport and the following thermal decomposition of these compounds can produce up to 0.3 ppb h−1 radicals in the atmospheric layer near the ground. Although this rate is not sufficient to explain the complete OH discrepancy, it indicates the potentially important role of vertical transport in the lower nighttime atmosphere.

When simulating social action in modeling efforts, as in socio-hydrology, an issue of obvious importance is how to ensure that social action by human agents is well-represented in the analysis and the model. Generally, human decision-making is either modeled on a yearly basis or lumped together as collective social structures. Both responses are problematic, as human decision-making is more complex and organizations are the result of human agency and cannot be used as explanatory forces. A way out of the dilemma of how to include human agency is to go to the largest societal and environmental clustering possible: society itself and climate, with time steps of years or decades. In the paper, another way out is developed: to face human agency squarely, and direct the modeling approach to the agency of individuals and couple this with the lowest appropriate hydrological level and time step. This approach is supported theoretically by the work of Bruno Latour, the French sociologist and philosopher. We discuss irrigation archaeology, as it is in this discipline that the issues of scale and explanatory force are well discussed. The issue is not just what scale to use: it is what scale matters. We argue that understanding the arrangements that permitted the management of irrigation over centuries requires modeling and understanding the small-scale, day-to-day operations and personal interactions upon which they were built. This effort, however, must be informed by the longer-term dynamics, as these provide the context within which human agency is acted out.

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.

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.

We analyze summertime photochemistry near the surface in Beijing, China, using a 1-D photochemical model (Regional chEmical and trAnsport Model, REAM-1D) constrained by in situ observations, focusing on the budgets of ROx (OH + HO2 + RO2) radicals and O3 formation. While the modeling analysis focuses on near-surface photochemical budgets, the implications for the budget of O3 in the planetary boundary layer are also discussed. In terms of daytime average, the total ROx primary production rate near the surface in Beijing is 6.6 ppbv per hour (ppbv h−1, among the highest found in urban atmospheres. The largest primary ROx source in Beijing is photolysis of oxygenated volatile organic compounds (OVOCs), which produces HO2 and RO2 at 2.5 ppbv h−1 and 1.7 ppbv h−1, respectively. Photolysis of excess HONO from an unknown heterogeneous source is the predominant primary OH source at 2.2 ppbv h−1, much larger than that of O1D+H2O (0.4 ppbv h−1). The largest ROx sink is via OH + NO2 reaction (1.6 ppbv h−1), followed by formation of RO2NO2 (1.0 ppbv h−1) and RONO2 (0.7 ppbv h−1). Due to the large aerosol surface area, aerosol uptake of HO2 appears to be another important radical sink, although the estimate of its magnitude is highly variable depending on the uptake coefficient value used. The daytime average O3 production and loss rates near the surface are 32 ppbv h−1 and 6.2 ppbv h−1, respectively. Assuming NO2 to be the source of excess HONO, the NO2 to HONO transformation leads to considerable O3 loss and reduction of its lifetime. Our observation-constrained modeling analysis suggests that oxidation of VOCs (especially aromatics) and heterogeneous reactions (e.g. HONO formation and aerosol uptake HO2) play potentially critical roles in the primary radical budget and O3 formation in Beijing. One important ramification is that O3 production is neither NOx nor VOC limited, but in a transition regime where reduction of either NOx or VOCs could result in reduction of O3 production. The transition regime implies more flexibility in the O3 control strategies than a binary system of either NOx or VOC limited regime. The co-benefit of concurrent reduction of both NOx and VOCs in reducing column O3 production integrated in the planetary boundary layer is significant. Further research on the spatial extent of the transition regime over the polluted eastern China is critically important for controlling regional O3 pollution.

This study investigated the air pollution characteristics of synoptic-scale circulation in the Beijing megacity, and provided quantitative evaluation of the impacts of circulation patterns on air quality during the 2008 Beijing Summer Olympics. Nine weather circulation types (CTs) were objectively identified over the North China region during 2000–2009, using obliquely rotated T-mode principal component analysis (PCA). The resulting CTs were examined in relation to the local meteorology, regional transport pathways, and air quality parameters, respectively. The FLEXPART-WRF model was used to calculate 48-h backward plume trajectories for each CT. Each CT was characterized with distinct local meteorology and air mass origin. CT 1 (high pressure to the west with a strong pressure gradient) was characterized by a northwestern air mass origin, with the smallest local and southeasterly air mass sources, and CT 6 (high pressure to the northwest) had air mass sources mostly from the north and east. On the contrary, CTs 5, 8, and 9 (weak pressure field, high pressure to the east, and low pressure to the northwest, respectively) were characterized by southern and southeastern trajectories, which indicated a greater influence of high pollutant emission sources. In turn, poor air quality in Beijing (high loadings of PM10, BC, SO2, NO2, NOx, O3, AOD, and low visibility) was associated with these CTs. Good air quality in Beijing was associated with CTs 1 and 6. The average visibilities (with ±1σ) in Beijing for CTs 1 and 6 during 2000–2009 were 18.5 ± 8.3 km and 14.3 ± 8.5 km, respectively. In contrast, low visibility values of 6.0 ± 3.5 km, 6.6 ± 3.7 km, and 6.7 ± 3.6 km were found in CTs 5, 8, and 9, respectively. The mean concentrations of PM10 for CTs 1, 6, 5, 8, and 9 during 2005–2009 were 90.3 ± 76.3 μg m−3, 111.7 ± 89.6 μg m−3, 173.4 ± 105.8 μg m−3, 158.4 ± 90.0 μg m−3, and 151.2 ± 93.1 μg m−3, respectively. Analysis of the relationship between circulation pattern and air quality during the emission control period suggests that CTs are the primary drivers of day-to-day variations in pollutant concentrations over Beijing and its vicinity. During the Olympics period, the frequency of CT 6 was twice that of the mean in August from 2000 to 2009. This CT had northerly transport pathways and favorable meteorological conditions (e.g. frequent precipitation) for clean air during the Olympics. Assuming that relationships between CTs and air quality parameters in the same season are fixed in different years, the relative contributions of synoptic circulation to decreases in PM10, BC, SO2, NO2, NOx, CO, and horizontal light extinction during the Olympics were estimated as 19 ± 14%, 18 ± 13%, 41 ± 36%, 12 ± 7%, 10 ± 5%, 19 ± 11%, and 54 ± 25%, respectively.

Shanghai, with a population of over 20 million, is the largest mega-city in China. Rapidly increasing industrial and metropolitan emissions have deteriorated its air quality in the past decades, with fine particle pollution as one of the major issues. However, systematic characterization of atmospheric fine particles with advanced measurement techniques has been very scarce in Shanghai. During 2010 Shanghai World Expo, we deployed a high-resolution time-of-flight aerosol mass spectrometer (HR-ToF-AMS) and a single particle soot photometer (SP2) in urban Shanghai between 15 May and 10 June 2010 to measure fine particles with a high time resolution. The 4-min resolution PM1 mass concentration ranged from 5.5 to 155 μg m−3, with an average of 29.2 μg m−3. On average, sulfate and organic matter (OM) were the most abundant PM1 components, accounting for 33.3 and 28.7% of the total mass, respectively, while the fraction of nitrate showed an increasing trend with the increasing PM1 loading, indicating the photochemical nature of high fine particle pollution in Shanghai. Taking advantage of HR-ToF-AMS and SP2, OM was found to have an average OM/OC ratio (organic matter mass/organic carbon mass) of 1.55 and black carbon (BC) had an average number fraction of internally mixed BC of 41.2%. Positive matrix factorization (PMF) analysis on the high resolution organic mass spectral dataset identified a hydrocarbon-like (HOA), a semi-volatile oxygenated (SV-OOA), and a low-volatility oxygenated (LV-OOA) organic aerosol component, which on average accounted for 24.0, 46.8, and 29.2% of the total organic mass, respectively. The diurnal patterns of them with interesting time delay possibly implied a photochemical oxidizing process from HOA (and/or its concurrently emitted gaseous organic pollutants) to SV-OOA to LV-OOA. Back trajectory analysis indicated that the northwesterly continental air mass represented the most severe pollutant regional transport condition with the highest nitrate and SV-OOA fractions. In addition, the results in Shanghai were compared with similar measurements performed recently in other mega-cities in the world.

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 = a + 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.

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.

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 outflow ((2.5–9.9) × 103 cm−3 vs. (0.4–8.3) × 103 cm−3 for S=0.07–0.86%) although the total aerosol particle number concentration was lower (1.2 × 104 cm−3 vs. 2.3 × 104 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.

Megacities are places with intensive human activity and energy consumption. To reduce air pollution, many megacities have relocated energy supplies and polluted industries to their outer regions. However, regional transport then becomes an important source of air pollution in megacities. To improve air quality before and during the 2008 Beijing Olympics, a wide range of control strategies were implemented, including the relocation of polluting industries. High sulfur dioxide (SO2) concentrations were occasionally observed during this period. Potential sources from southern regions of Beijing were indicated by backward trajectories model and urban/rural stationary measurements, but direct evidence was lacking. Here we used a mobile laboratory to characterize the spatial distribution and regional transport of SO2 to Beijing during the Campaign for Air Quality Research in Beijing and the Surrounding Region (CAREBEIJING)-2008. Among the five days chosen for the case studies during the Olympic air pollution control period, four had high SO2 concentrations (6, 20 August and 3, 4 September 2008) while one had low SO2 concentration (11 September 2008). The average values of SO2 during the low SO2 concentration day were 3.9 ppb, much lower than during the high concentration days (7.8 ppb). This result implied an impact by regional transport from outside Beijing. During these days, we captured transport events of SO2 from areas south of Beijing, with a clear decrease in SO2 concentrations southeast of the 6th to 4th Ring Roads around Beijing and along the 140 km highway from Tianjin to Beijing. The influx of SO2 through the 4th to 6th Ring Roads ranged from 2.1 to 4.6 kg s−1 on 4 September and 0.2 to 1.6 kg s−1 on 20 August 2008. The differences of influx in days were due to the variations of emission changes, transport directions and dilutions. Locally emitted SO2 from a source located along Jingshi Highway outside the southwest section of the 5th Ring Road of Beijing was identified using wind field data generated by the Weather Research and Forecasting model and the measured particle size distribution, with an estimated flux of 0.1 kg s−1 to Beijing. Estimated uncertainties for SO2 influx were approximately 31%.

As a part of the CAREBeijing-2008 campaign, observations of O3, oxides of nitrogen (NOx and NOy), CO, and hydrocarbons (NMHCs) were carried out at the air quality observatory of the Peking University in Beijing, China during August 2008, including the period of the 29th Summer Olympic Games. The measurements were compared with those of the CAREBeijing-2006 campaign to evaluate the effectiveness of the air pollution control measures, which were conducted for improving the air quality in Beijing during the Olympics. The results indicate that significant reduction in the emissions of primary air pollutants had been achieved; the monthly averaged mixing ratios of NOx, NOy, CO, and NMHCs decreased by 42.2, 56.5, 27.8, and 49.7 %, respectively. In contrast to the primary pollutants, the averaged mixing ratio of O3 increased by 42.2 %. Nevertheless, it was revealed that the ambient levels of total oxidant (Ox = O3+NO2+1.5 NOz) and NOz were reduced by 21.3 and 77.4 %, respectively. The contradictions between O3 and Ox were further examined in two case studies. Ozone production rates of 30–70 ppbv h−1 and OPEx of ~8 mole mole−1 were observed on a clear-sky day in spite of the reduced levels of precursors. In that case, it was found that the mixing ratio of O3 increased with the increasing NO2/NO ratio, whereas the NOz mixing ratio leveled off when NO2/NO>8. Consequently, the ratio of O3 to NOz increased to above 10, indicating the shift from VOC-sensitive regime to NOx-sensitive regime. However, in the other case, it was found that the O3 production was inhibited significantly due to substantial reduction in the NMHCs. According to the observations, it was suggested that the O3 and/or Ox production rates in Beijing should have been reduced as a result of the reduction in the emissions of precursors during the Olympic period. However, the nighttime O3 levels increased due to a decline in the NO-O3 titration, and the midday O3 peak levels were elevated because of the shift in the photochemical regime and the inhibition of NOz formation.

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.

The atmospheric concentrations of gaseous ammonia have been measured during two field campaigns in the winter and in the summer of 2007 at Beijing (China). These measurements were carried out by means of diffusion annular denuders coated with phosphorous acid. The results were discussed from the standpoint of temporal and diurnal variations and meteorological effects. The daily average NH3 concentrations were in the range of 0.20–44.38 μg/m3 and showed regular temporal variations with higher concentrations during summer and with lower during winter. The temporal trends seemed to be largely affected by air temperature because of agricultural sources. No diurnal variability was observed for gaseous NH3 levels in both winter and summer seasons. The highest ammonia value of 105.67 μg/m3 was measured in the early morning during the summer period when stable atmospheric conditions occurred. The diurnal winter and summer trends of ammonia showed a weak dependence on the air temperature and they were affected nearly by wind direction suggesting regional and local source influences. Ammonia was also correlated with the atmospheric mixing in the boundary layer, and, with NOx, CO and PM2.5 air concentrations supporting the hypothesis that the traffic may be also an important source of ammonia in Beijing.

Atmospheric mineral aerosols contain CaCO3 as a reactive component. A novel method to produce CaCO3 aerosol was developed by spraying Ca(HCO3)2 solution, which was generated from a CaCO3 suspension and CO2. By aerosol mass spectrometry the freshly sprayed and dried aerosol was characterized to consist of pure Ca(HCO3)2 which under annealing in a tube furnace transformed into CaCO3. Transmission Electron Microscopy demonstrated that the particles produced were spherical. The method was able to generate aerosol of sufficient concentration and proper size for the study of physiochemical properties and investigations of heterogeneous reactions of mineral aerosol. The dried Ca(HCO3)2 particles were somewhat more hygroscopic than CaCO3 particles. However, during humidification a restructuring took place and ∼2/3 of the Ca(HCO3)2 was transformed to CaCO3. The mixed Ca(HCO3)2/CaCO3(s) particles were insoluble with a growth factor of 1.03 at 95% (hygroscopicity parameter κ=0.011±0.007) relative humidity. This compares to a corresponding growth factor of 1.01 for CaCO3(s) (κ=0.0016±0.0004). Mass spectrometric composition analysis, restructuring, and insolubility of the mixed particles suggested that solid Ca(HCO3)2(s) was observed. This would be in contrast to the current belief that Ca(HCO3)2(s) is thermodynamically instable. The CCN activity of Ca(HCO3)2(s) aerosol (κ≈0.15) is remarkably higher than that of CaCO3 aerosol (κ=0.0019±0.0007) and less than that of Ca(NO3)2. The noticeable but limited solubility of Ca(HCO3)2 of ≈0.01 mol/l explains limited hygroscopic growth and good CCN activity. Experiments in the Large Jülich Aerosol Chamber indicated that Ca(HCO3)2(s) could exist for several hours under dry atmospheric conditions. However, it was likely buried in a protective layer of CaCO3(s). We conclude that Ca(HCO3)2 may be formed in the atmosphere in cloud droplets of activated mineral dust by reaction of CaCO3 with CO2 and H2O. The presence of Ca(HCO3)2 and as a consequence an enhanced CCN activity may alter the influence of mineral aerosol on global climate.

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.

Simultaneous measurements of gaseous sulfuric acid and particle number size distributions were performed to investigate aerosol nucleation and growth during CAREBeijing-2008. The analysis of the measured aerosols and sulfuric acid with an aerosol dynamic model shows the dominant role of sulfuric acid in new particle formation (NPF) process but also in the subsequent growth in Beijing. Based on the data of twelve NPF events, the average formation rates (2–13 cm−3 s−1) show a linear correlation with the sulfuric acid concentrations (R2=0.85). Coagulation seems to play a significant role in reducing the number concentration of nucleation mode particles with the ratio of the coagulation loss to formation rate being 0.41±0.16. The apparent growth rates vary from 3 to 11 nm h−1. Condensation of sulfuric acid and its subsequent neutralization by ammonia and coagulation contribute to the apparent particle growth on average 45±18% and 34±17%, respectively. The 30% higher concentration of sulfate than organic compounds in particles during the seven sulfur-rich NPF events but 20% lower concentration of sulfate during the five sulfur-poor type suggest that organic compounds are an important contributor to the growth of the freshly nucleated particles, especially during the sulfur-poor cases.

With increasing NO2 concentration in the troposphere, the importance of NO2 reaction with mineral dust in the atmosphere needs to be evaluated. Until now, little is known about the reaction of NO2 with CaCO3. In this study, the heterogeneous reaction of NO2 on the surface of CaCO3 particles was investigated at 296 K and NO2 concentrations between 4.58×1015 molecules cm−3 to 1.68×1016 molecules cm−3, using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS) combined with X-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM), under wet and dry conditions. Nitrate formation was observed under both conditions, while nitrite was observed under wet conditions, indicating the reaction of NO2 on the CaCO3 surface produced nitrate and probably nitrous acid (HONO). Relative humidity (RH) influences both the initial uptake coefficient and the reaction mechanism. At low RH, surface −OH is formed through dissociation of the surface adsorbed water via oxygen vacancy, thus determining the reaction order. As RH increases, water starts to condense on the surface and the gas-liquid reaction of NO2 with the condensed water begins. With high enough RH (>52% in our experiment), the gas-liquid reaction of NO2 with condensed water becomes dominant, forming HNO3 and HONO. The initial uptake coefficient γ0 was determined to be (4.25±1.18)×10−9 under dry conditions and up to (6.56±0.34)×10−8 under wet conditions. These results suggest that the reaction of NO2 on CaCO3 particle is unable to compete with that of HNO3 in the atmosphere. Further studies at lower NO2 concentrations and with a more accurate assessment of the surface area for calculating the uptake coefficient of the reaction of NO2 on CaCO3 particle and to examine its importance as a source of HONO in the atmosphere are needed.

China implemented systematic air pollution control measures during the 2008 Beijing Summer Olympics and Paralympics to improve air quality. This study used a versatile mobile laboratory to conduct in situ monitoring of on-road air pollutants along Beijing's Fourth Ring Road on 31 selected days before, during, and after the Olympics air pollution control period. A suite of instruments with response times of less than 30 s was used to measure temporal and spatial variations in traffic-related air pollutants, including NOx, CO, PM1.0 surface area (S(PM1)), black carbon (BC), and benzene, toluene, the sum of ethylbenzene, and m-, p-, and o-xylene (BTEX). During the Olympics (8–23 August, 2008), on-road air pollutant concentrations decreased significantly, by up to 54% for CO, 41% for NOx, 70% for SO2, 66% for BTEX, 12% for BC, and 18% for SPM1, compared with the pre-control period (before 20 July). Concentrations increased again after the control period ended (after 20 September), with average increases of 33% for CO, 42% for NOx, 60% for SO2, 40% for BTEX, 26% for BC, and 37% for S(PM1), relative to the control period. Variations in pollutants concentrations were correlated with changes in traffic speed and the number and types of vehicles on the road. Throughout the measurement periods, the concentrations of NOx, CO, and BTEX varied markedly with the numbers of light- and medium-duty vehicles (LDVs and MDVs, respectively) on the road. Only after 8 August was a noticeable relationship found between BC and S(PM1) and the number of heavy-duty vehicles (HDVs). Additionally, BC and S(PM1) showed a strong correlation with SO2 before the Olympics, indicating possible industrial sources from local emissions as well as regional transport activities in the Beijing area. Such factors were identified in measurements conducted on 6 August in an area southwest of Beijing. The ratio of benzene to toluene, a good indicator of traffic emissions, shifted suddenly from about 0.26 before the Olympics to approximately 0.48 after the Olympics began. This finding suggests that regulations on traffic volume and restrictions on the use of painting solvents were effective after the Olympics began. This study demonstrated the effectiveness of air pollution control measures and identified local and regional pollution sources within and surrounding the city of Beijing. The findings will be invaluable for emission inventory evaluations and model verifications.

To understand and predict the role of mineral aerosol particles processed by reactive nitrogen species in the atmosphere, the hygroscopic properties of both Ca(NO3)2 and Ca(NO3)2-containing mineral particles must be well understood. Using a micro-Raman system, the hygroscopic behaviors of micro-sized individual Ca(NO3)2 and internally mixed Ca(NO3)2/CaCO3 particles in both dehumidifying and humidifying processes were investigated systematically. In addition to accurate quantification of the dependence of water content on relative humidity (RH), significant new spectroscopic evidence related to chemical structure was also obtained to confirm the occurrence of amorphous solid state and to better understand the phase transition process. The Ca(NO3)2 particles exhibit reversible behavior in the dehumidifying and humidifying processes; they are in the state of solution droplets above 10% RH and amorphous hydrates below 7% RH, and phase transition occurs at 7–10% RH. The hygroscopic behavior of Ca(NO3)2/CaCO3 particles is identical to that of pure Ca(NO3)2 particles, suggesting a negligible effect of the slightly soluble CaCO3 inclusion on the hygroscopic behavior of a(NO3)2/CaCO3 particles.

It has been shown that sunlit snow and ice plays an important role in processing atmospheric species. Photochemical production of a variety of chemicals has recently been reported to occur in snow/ice and the release of these photochemically generated species may significantly impact the chemistry of the overlying atmosphere. Nitrogen oxide and oxidant precursor fluxes have been measured in a number of snow covered environments, where in some cases the emissions significantly impact the overlying boundary layer. For example, photochemical ozone production (such as that occurring in polluted mid-latitudes) of 3–4 ppbv/day has been observed at South Pole, due to high OH and NO levels present in a relatively shallow boundary layer. Field and laboratory experiments have determined that the origin of the observed NOx flux is the photochemistry of nitrate within the snowpack, however some details of the mechanism have not yet been elucidated. A variety of low molecular weight organic compounds have been shown to be emitted from sunlit snowpacks, the source of which has been proposed to be either direct or indirect photo-oxidation of natural organic materials present in the snow. Although myriad studies have observed active processing of species within irradiated snowpacks, the fundamental chemistry occurring remains poorly understood. Here we consider the nature of snow at a fundamental, physical level; photochemical processes within snow and the caveats needed for comparison to atmospheric photochemistry; our current understanding of nitrogen, oxidant, halogen and organic photochemistry within snow; the current limitations faced by the field and implications for the future.

The concentrations of fine particulate matter (PM) and ozone in Beijing often exceed healthful levels in recent years, therefore China is to taking steps to improve Beijing's air quality for the 2008 Olympic Games. In this paper, the Models-3 Community Multiscale Air Quality (CMAQ) Modeling System was used to investigate a heavy air pollution episode in Beijing during 3–7 April 2005 to obtain the basic information of how heavy air pollution formed and the contributions of local sources and surround emissions. The modeling domain covered from East Asia with four nested grids with 81 to 3 km horizontal resolution focusing on urban Beijing. This was coupled with a regional emissions inventory with a 10 km resolution and a local 1 km Beijing emissions database. The trend of predicted concentrations of various pollutants agreed reasonably well with the observations and captured the main features of this heavy pollution episode. The simulated column concentration distribution of PM was correlated well with the MODIS remote sensing products. Control runs with and without Beijing emissions were conducted to quantify the contributions of non-Beijing sources (NBS) to the Beijing local air pollution. The contributions of NBS to each species differed spatially and temporally with the order of PM2.5>PM10>SO2> soil for this episode. The percentage contribution of NBS to fine particle (PM2.5) in Beijing was averaged about 39%, up to 53% at the northwest of urban Beijing and only 15% at southwest. The spatial distribution of NBS contributions for PM10 was similar to that for PM2.5, with a slightly less average percentage of about 30%. The average NBS contributions for SO2 and soil (diameter between 2.5 μm and 10 μm) were 18% and 10%. In addition, the pollutant transport flux was calculated and compared at different levels to investigate transport pathway and magnitude. It was found that the NBS contribution correlated with the transport flux, contributing 60% of PM10 concentration in Beijing at the time of transport flux peak during a strong episode with a transport path from southwest to northeast.

This paper investigates low temperature ohmic contact formation of Au/Sb to n-type Si substrates through AuSb/NiCr/Au metal stacks. Liquid epitaxy growth is utilized to incorporate Sb dopants into Si substrate in AuSi melt. The best specific contact resistivity achieved is 0.003 Ω ⋅ cm2 at 425 oC. Scanning electron microscopy (SEM) reveals inverted pyramidal crater regions at the metal/semiconductor interface, indicating that AuSi alloying efficiently occurs at such sites. Secondary ion mass spectroscopy (SIMS) shows that Sb atoms are successfully incorporated into Si as doping impurities during the anneal process, and the Sb doping concentration at the contact interface is found to be higher than the solid solubility limit in a Si crystal. This ohmic contacts formation method is suitable for semiconductor fabrication processes with limited thermal budget, such as post CMOS integration of MEMS.

Sulfate particles play a key role in the air quality and the global climate, but the heterogeneous formation mechanism of sulfates on surfaces of atmospheric particles is not well established. Carbonates, which act as a reactive component in mineral dust due to their special chemical properties, may contribute significantly to the sulfate formation by heterogeneous processes. This paper presents a study on the oxidation of SO2 by O3 on CaCO3 particles. Using Diffuse Reflectance Infrared Fourier Transform Spectroscopy (DRIFTS), the formation of sulfite and sulfate on the surface was identified, and the roles of O3 and water in oxidation processes were determined. The results showed that in the presence of O3, SO2can be oxidized to sulfate on the surface of CaCO3 particles. The reaction is first order in SO2 and zero order in O3. The reactive uptake coefficient for SO2 [(0.6–9.8)×1014 molecule cm-3] oxidation by O3 [(1.2–12)×1014 molecule cm-3] was determined to be (1.4±0.3)×10-7 using the BET area as the reactive area and (7.7±1.6)×10-4 using the geometric area. A two-stage mechanism that involves adsorption of SO2 followed by O3 oxidation is proposed and the adsorption of SO2 on the CaCO3 surface is the rate-determining step. The proposed mechanism can well explain the experiment results. The atmospheric implications were explored based on a box model calculation. It was found that the heterogeneous reaction might be an important pathway for sulfate formation in the atmosphere.

Non-polar (11-20) InGaN quantum dots (QDs) were grown by metal organic vapour phase epitaxy. An InGaN epilayer was grown and subjected to a temperature ramp in a nitrogen and ammonia environment before the growth of the GaN capping layer. Uncapped structures with and without the temperature ramp were grown for reference and imaged by atomic force microscopy. Micro-photoluminescence studies reveal the presence of resolution limited peaks with a linewidth of less than ∼500 μeV at 4.2 K. This linewidth is significantly narrower than that of non-polar InGaN quantum dots grown by alternate methods and may be indicative of reduced spectral diffusion. Time resolved photoluminescence studies reveal a mono-exponential exciton decay with a lifetime of 533 ps at 2.70 eV. The excitonic lifetime is more than an order of magnitude shorter than that for previously studied polar quantum dots and suggests the suppression of the internal electric field. Cathodoluminescence studies show the spatial distribution of the quantum dots and resolution limited spectral peaks at 18 K.

Capabilities for uncertainty quantification (UQ) with respect to nuclear data have been developed at PSI in the recent years and applied to the UAM benchmark. The guiding principle for the PSI UQ development has been to implement nonintrusive “black box” UQ techniques in state-of-the-art, production-quality codes used already for routine analyses. Two complimentary UQ techniques have been developed thus far: (i) direct perturbation (DP) and (ii) stochastic sampling (SS). The DP technique is, first and foremost, a robust and versatile sensitivity coefficient calculation, applicable to all types of input and output. Using standard uncertainty propagation, the sensitivity coefficients are folded with variance/covariance matrices (VCMs) leading to a local first-order UQ method. The complementary SS technique samples uncertain inputs according to their joint probability distributions and provides a global, all-order UQ method. This paper describes both DP and SS implemented in the lattice physics code CASMO-5MX (a special PSI-modified version of CASMO-5M) and a preliminary SS technique implemented in MCNPX, routinely used in criticality safety and fluence analyses. Results are presented for the UAM benchmark exercises I-1 (cell) and I-2 (assembly).