ALBERT

Description: This paper describes ESM-SnowMIP, an international coordinated modelling effort to evaluate current snow schemes, including snow schemes that are included in Earth system models, in a wide variety of settings against local and global observations. The project aims to identify crucial processes and characteristics that need to be improved in snow models in the context of local- and global-scale modelling. A further objective of ESM-SnowMIP is to better quantify snow-related feedbacks in the Earth system. Although it is not part of the sixth phase of the Coupled Model Intercomparison Project (CMIP6), ESM-SnowMIP is tightly linked to the CMIP6-endorsed Land Surface, Snow and Soil Moisture Model Intercomparison (LS3MIP).

Description: ClNO2 and Cl2 can affect atmospheric oxidation and thereby the formation of ozone and secondary aerosols, yet their sources and production mechanisms are not well understood or quantified. In this study we present field observations of ClNO2 and Cl2 at a suburban site in eastern China during April 2018. Persistent high levels of ClNO2 (maximum: ∼3.7 ppbv; 1 min average) were frequently observed at night, due to the high ClNO2 yield (φ (ClNO2), 0.56±0.20) inferred from the measurements. The φ (ClNO2) value showed a positive correlation with the [Cl−] / [H2O] ratio, and its parameterization was improved at low to median yields (0–0.75) by the incorporation of [Cl−] / [H2O] and the suppression effect of aerosol organics. ClNO2 and Cl2 showed a significant correlation on most nights. We show that the Cl2 at our site was more likely a co-product with ClNO2 from N2O5 uptake on acidic aerosols that contain chloride than being produced by ClNO2 uptake as previously suggested. We propose a mechanism in which NO2+ can react with Cl− to produce Cl2 and ClNO2 simultaneously. Under a new framework which regards Cl2, ClNO2, and nitrate as products of N2O5 uptake, the Cl2 yield (φ (Cl2)) was derived using ambient data. φ (Cl2) exhibited significant correlations with [Cl−] and [H+], based on which a parameterization of φ (Cl2) was developed. The derived parameterizations of φ (ClNO2) and φ (Cl2) can be used in models to evaluate the nighttime production of ClNO2 and Cl2 and their impact on the next day's photochemistry.

Description: Heterogeneous reactivity of N2O5 on aerosols is a critical parameter in assessing NOx fate, nitrate production, and particulate chloride activation. Accurate measurement of its uptake coefficient (γN2O5) and representation in air quality models are challenging, especially in the polluted environment. With an in situ aerosol flow-tube system, the γN2O5 was directly measured on ambient aerosols at two rural sites in northern and southern China. The results were analyzed together with the γN2O5 derived from previous field studies in China to obtain a holistic picture of N2O5 uptake and the influencing factors under various climatic and chemical conditions. The field-derived or measured γN2O5 was generally promoted by the aerosol water content and suppressed by particle nitrate. Significant discrepancies were found between the measured γN2O5 and that estimated from laboratory-determined parameterizations. An observation-based empirical parameterization was derived in the present work, which better reproduced the mean value and variability of the observed γN2O5. Incorporating this new parameterization into a regional air quality model (WRF-CMAQ) has improved the simulation of N2O5, nitrogen oxides, and secondary nitrate in the polluted regions of China.

Description: China has suffered from increasing levels of ozone pollution in urban areas despite the implementation of various stringent emission reduction measures since 2013. In this study, we conducted numerical experiments with an up-to-date regional chemical transport model to assess the contribution of the changes in meteorological conditions and anthropogenic emissions to the summer ozone level from 2013 to 2017 in various regions of China. The model can faithfully reproduce the observed meteorological parameters and air pollutant concentrations and capture the increasing trend in the surface maximum daily 8 h average (MDA8) ozone (O3) from 2013 to 2017. The emission-control measures implemented by the government induced a decrease in MDA8 O3 levels in rural areas but an increase in urban areas. The meteorological influence on the ozone trend varied by region and by year and could be comparable to or even more significant than the impact of changes in anthropogenic emissions. Meteorological conditions can modulate the ozone concentration via direct (e.g., increasing reaction rates at higher temperatures) and indirect (e.g., increasing biogenic emissions at higher temperatures) effects. As an essential source of volatile organic compounds that contributes to ozone formation, the variation in biogenic emissions during summer varied across regions and was mainly affected by temperature. China's midlatitude areas (25 to 40∘ N) experienced a significant decrease in MDA8 O3 due to a decline in biogenic emissions, especially for the Yangtze River Delta and Sichuan Basin regions in 2014 and 2015. In contrast, in northern (north of 40∘ N) and southern (south of 25∘ N) China, higher temperatures after 2013 led to an increase in MDA8 O3 via an increase in biogenic emissions. We also assessed the individual effects of changes in temperature, specific humidity, wind field, planetary boundary layer height, clouds, and precipitation on ozone levels from 2013 to 2017. The results show that the wind field change made a significant contribution to the increase in surface ozone over many parts of China. The long-range transport of ozone and its precursors from outside the modeling domain also contributed to the increase in MDA8 O3 in China, especially on the Qinghai–Tibetan Plateau (an increase of 1 to 4 ppbv). Our study represents the most comprehensive and up-to-date analysis of the impact of changes in meteorology on ozone across China and highlights the importance of considering meteorological variations when assessing the effectiveness of emission control on changes in the ozone levels in recent years.

Description: The Chinese government launched the Air Pollution Prevention and Control Action Plan in 2013, and various stringent measures have since been implemented, which have resulted in significant decreases in emissions and ambient concentrations of primary pollutants such as SO2, NOx, and particulate matter (PM). However, surface ozone (O3) concentrations have still been increasing in urban areas across the country. In a previous analysis, we examined in detail the roles of meteorological variation during 2013–2017 in the summertime surface O3 trend in various regions of China. In this study, we evaluated the effect of changes in multi-pollutant emissions from anthropogenic activities on O3 levels during the same period by using an up-to-date regional chemical transport model (WRF-CMAQ) driven by an interannual anthropogenic emission inventory. The Community Multiscale Air Quality (CMAQ) model was improved with regard to heterogeneous reactions of reactive gases on aerosol surfaces, which led to better model performance in reproducing the ambient concentrations of those gases. The model simulations showed that the maximum daily 8 h average (MDA8) O3 mixing ratio in urban areas increased by 0.46 ppbv per year (ppbv a−1) (p=0.001) from 2013 to 2017. In contrast, a slight decrease in MDA8 O3 by 0.17 ppbv a−1 (p=0.005) in rural areas was predicted, mainly attributable to the NOx emission reduction. The effects of changes in individual pollutant emissions on O3 were also simulated. The reduction of NOx emission increased the O3 levels in urban areas due to the nonlinear NOx and volatile organic compound (VOC) chemistry and decreasing aerosol effects; the slight increase in VOC emissions enhanced the O3 levels; the reduction of PM emissions increased the O3 levels by enhancing the photolysis rates and reducing the loss of reactive gases on aerosol surfaces; and the reduction of SO2 emissions resulted in a drastic decrease in sulfate concentrations, which increased O3 through aerosol effects. In contrast to the unfavorable effect of the above changes in pollutant emissions on efforts to reduce surface O3, the reduction of CO emissions did help to decrease the O3 level in recent years. The dominant cause of increasing O3 due to changes in anthropogenic emissions varied geographically. In Beijing, NOx and PM emission reductions were the two largest causes of the O3 increase; in Shanghai, the reduction of NOx and increase in VOC emissions were the two major causes; in Guangzhou, NOx reduction was the primary cause; in Chengdu, the PM and SO2 emission decreases contributed most to the O3 increase. Regarding the effects of decreasing concentrations of aerosols, the drop in heterogeneous uptake of reactive gases – mainly HO2 and O3 – was found to be more important than the increase in photolysis rates. The adverse effect of the reductions of NOx, SO2, and PM emissions on O3 abatement in Beijing, Shanghai, Guangzhou, and Chengdu would have been avoided if the anthropogenic VOCs emission had been reduced by 24 %, 23 %, 20 %, and 16 %, respectively, from 2013 to 2017. Our analysis revealed that the NOx reduction in recent years has helped to contain the total O3 production in China. However, to reduce O3 levels in major urban and industrial areas, VOC emission controls should be added to the current NOx-SO2-PM policy.

Description: Nadir-viewing satellite observations of tropospheric ozone in the UV have been shown to have some sensitivity to boundary layer ozone pollution episodes, but so far they have not yet been compared to surface ozone observations collected by large-scale monitoring networks. Here we use 2013–2017 surface ozone data from China's new Ministry of Ecology and Environment (MEE) network of ∼ 1000 sites, together with vertical profiles from ozonesondes and aircraft, to quantify the ability of tropospheric ozone retrievals from the Ozone Monitoring Instrument (OMI) and to detect boundary layer ozone pollution in China. We focus on summer when ozone pollution in China is most severe and when OMI has the strongest sensitivity. After subtracting the Pacific background, we find that the 2013–2017 mean OMI ozone enhancements over eastern China have strong spatial correlation with the corresponding multiyear means in the surface afternoon observations (R=0.73), and that OMI can estimate these multiyear means in summer afternoon surface ozone with a precision of 8 ppb. The OMI data show significantly higher values on observed surface ozone episode days (〉82 ppb) than on non-episode days. Day-to-day correlations with surface ozone are much weaker due to OMI noise and are stronger for sites in southern China (

Description: Nitrous acid (HONO) can strongly affect atmospheric photochemistry in polluted regions through the production of hydroxyl radicals (OHs). In January 2017, a severe pollution episode occurred in the Pearl River Delta (PRD) of China, with maximum hourly PM2.5, ozone, and HONO levels reaching 400 µg m−3, 150 ppb, and 8 ppb, respectively, at a suburban site. The present study investigated the sources and processes generating such high HONO concentrations and the role of HONO chemistry in this severe winter episode. Four recently reported HONO sources were added to the Community Multiscale Air Quality (CMAQ) model, including RH-dependent (relative humidity) and light-enhancing effects on heterogeneous reactions, photolysis of particulate nitrate in the atmosphere, and photolysis of HNO3 and nitrate on surfaces. The revised model reproduced the observed HONO and significantly improved its performance for O3 and PM2.5. The model simulations showed that the heterogeneous generation on surfaces (with RH and light effects) was the largest contributor (72 %) to the predicted HONO concentrations, with the RH-enhancing effects more significant at nighttime and the light-enhancing effects more important in the daytime. The photolysis of total nitrate in the atmosphere and deposited on surfaces was the dominant HONO source during noon and afternoon, contributing above 50 % of the simulated HONO. The HONO photolysis was the dominant contributor to HOx production in this episode. With all HONO sources, the daytime average O3 at the Heshan site was increased by 24 ppb (or 70 %), compared to the simulation results without any HONO sources. Moreover, the simulated mean concentrations of TNO3 (HNO3+ fine particle NO3-) at the Heshan site, which was the key species for this haze formation, increased by about 17 µg m−3 (67 %) due to the HONO chemistry, and the peak enhancement reached 55 µg m−3. This study highlights the key role of HONO chemistry in the formation of winter haze in a subtropical environment.

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

Description: Nitrate aerosol makes up a significant fraction of fine particles and plays a key role in regional air quality and climate. The North China Plain (NCP) is one of the most industrialized and polluted regions in China. To obtain a holistic understanding of the nitrate pollution and its formation mechanisms over the NCP region, intensive field observations were conducted at three sites during summertime in 2014–2015. The measurement sites include an urban site in downtown Jinan – the capital city of Shandong Province –, a rural site downwind of Jinan city, and a remote mountain site at Mt. Tai (1534 m a.s.l.). Elevated nitrate concentrations were observed at all three sites despite distinct temporal and spatial variations. Using historical observations, the nitrate ∕ PM2.5 and nitrate ∕ sulfate ratios have statistically significantly increased in Jinan (2005–2015) and at Mt. Tai (from 2007 to 2014), indicating the worsening situation of regional nitrate pollution. A multiphase chemical box model (RACM–CAPRAM) was deployed and constrained by observations to elucidate the nitrate formation mechanisms. The principal formation route is the partitioning of gaseous HNO3 to the aerosol phase during the day, whilst the nocturnal nitrate formation is dominated by the heterogeneous hydrolysis of N2O5. The daytime nitrate production in the NCP region is mainly limited by the availability of NO2 and to a lesser extent by O3 and NH3. In comparison, the nighttime formation is controlled by both NO2 and O3. The presence of NH3 contributes to the formation of nitrate aerosol during the day, while there is slightly decreasing nitrate formation at night. Our analyses suggest that controlling NOx and O3 is an efficient way, at the moment, to mitigate nitrate pollution in the NCP region, where NH3 is usually in excess in summer. This study provides observational evidence of a rising trend of nitrate aerosol as well as scientific support for formulating effective control strategies for regional haze in China.

Description: Nitryl chloride (ClNO2) accumulation at night acts as a significant reservoir for active chlorine and impacts the following day's photochemistry when the chlorine atom is liberated at sunrise. Here, we report simultaneous measurements of N2O5 and a suite of inorganic halogens including ClNO2 and reactions of chloride with volatile organic compounds (Cl–VOCs) in the gas and particle phases utilising the Filter Inlet for Gas and AEROsols time-of-flight chemical ionisation mass spectrometer (FIGAERO-ToF-CIMS) during an intensive measurement campaign 40 km northwest of Beijing in May and June 2016. A maximum mixing ratio of 2900 ppt of ClNO2 was observed with a mean campaign nighttime mixing ratio of 487 ppt, appearing to have an anthropogenic source supported by correlation with SO2, CO and benzene, which often persisted at high levels after sunrise until midday. This was attributed to such high mixing ratios persisting after numerous e-folding times of the photolytic lifetime enabling the chlorine atom production to reach 2.3  ×  105 molecules cm−3 from ClNO2 alone, peaking at 09:30 LT and up to 8.4  ×  105 molecules cm−3 when including the supporting inorganic halogen measurements.Cl–VOCs were observed in the particle and gas phases for the first time at high time resolution and illustrate how the iodide ToF-CIMS can detect unique markers of chlorine atom chemistry in ambient air from both biogenic and anthropogenic sources. Their presence and abundance can be explained via time series of their measured and steady-state calculated precursors, enabling the assessment of competing OH and chlorine atom oxidation via measurements of products from both of these mechanisms and their relative contribution to secondary organic aerosol (SOA) formation.