The 50 most-cited articles in Atmospheric chemistry and physics, 2019

Abstract. The Copernicus Atmosphere Monitoring Service (CAMS) reanalysis is the latest global reanalysis data set of atmospheric composition produced by the European Centre for Medium-Range Weather Forecasts (ECMWF), consisting of 3-dimensional time-consistent atmospheric composition fields, including aerosols and chemical species. The dataset currently covers the period 2003–2016 and will be extended in the future by adding one year each year. A reanalysis for greenhouse gases is being produced separately. The CAMS reanalysis builds on the experience gained during the production of the earlier Monitoring Atmospheric Composition and Climate (MACC) reanalysis and CAMS interim reanalysis. Satellite retrievals of total column CO, tropospheric column NO2, aerosol optical depth and total column, partial column and profile ozone retrievals were assimilated for the CAMS reanalysis with ECMWF’s Integrated Forecasting System. The new reanalysis has an increased horizontal resolution of about 80 km and provides more chemical species at a better temporal resolution (3-hourly analysis fields,…

Abstract. Since the publication of the compilation of biomass burning emission factors by Andreae and Merlet (2001), a large number of studies has greatly expanded the amount of available data on emissions from various types of biomass burning. Using essentially the same methodology as Andreae and Merlet (2001), this paper presents an updated compilation of emission factors. The data from over 350 published studies were critically evaluated and integrated into a consistent format. Several new categories of biomass burning have been added, and the number of species for which emission data are presented has been increased from 93 to 121. Where field data are still insufficient, estimates based on appropriate extrapolation techniques are proposed. Based on these emission factors and published global activity estimates, I have derived estimates of pyrogenic emissions for important species emitted by the various types of biomass burning.

Abstract. Fine particulate matter (PM2.5) is a severe air pollution problem in China. Observations of PM2.5 have been available since 2013 from a large network operated by the China National Environmental Monitoring Center (CNEMC). The data show a general 30–50 % decrease of annual mean PM2.5 across China over the 2013–2018 period, averaging 5.2 μg m−3 a−1. Trends in the five megacity cluster regions targeted by the government for air quality control are 9.3 ± 1.8 μg m−3 a−1 (±95 % confidence interval) for Beijing-Tianjin-Hebei, 6.1 ± 1.1 μg m−3 a−1 for Yangtze River Delta, 2.7 ± 0.8 μg m−3 a−1 for Pearl River Delta, 6.7 ± 1.3 μg m−3 a−1 for Sichuan Basin, and 6.5 ± 2.5 μg m−3 a−1 for Fenwei Plain (Xi'an). Concurrent 2013–2018 observations of sulfur dioxide (SO2) and CO show that the declines in PM2.5 are qualitatively consistent with drastic controls of emissions from coal combustion. However, there is also a large meteorologically driven interannual variability of PM2.5 that complicates trend attribution. We used a stepwise multiple linear regression (MLR) model to quantify this…

Abstract. The European Centre for Medium-Range Weather Forecasts' (ECMWF's) next-generation reanalysis ERA5 provides many improvements, but it also confronts the community with a big data challenge. Data storage requirements for ERA5 increase by a factor of ~ 80 compared with the ERA-Interim reanalysis, introduced a decade ago. Considering the significant increase in resources required for working with the new ERA5 data set, it is important to assess its impact on Lagrangian transport simulations. To quantify the differences between transport simulations using ERA5 and ERA-Interim data, we analyzed comprehensive global sets of 10-day forward trajectories for the free troposphere and the stratosphere for the year 2017. The new ERA5 data have considerable impact on the simulations. Spatial transport deviations between ERA5 and ERA-Interim trajectories are up to an order of magnitude larger than those caused by diffusion and subgrid-scale wind fluctuations after 1 day and still up to a factor of 2–3 larger after 10 days. Depending on the height range, the spatial differences between…

Abstract. Non-methane volatile organic compounds (NMVOC) are important ozone and secondary organic aerosol precursors and play important roles in tropospheric chemistry. In this work, we estimated the total and speciated NMVOC emissions from China’s anthropogenic sources during 1990–2017 by using a bottom-up emission inventory framework, and investigated the main drivers behind the trends. We found that, anthropogenic NMVOC emissions in China have been increased continuously since 1990 due to the dramatic growth in activity rates and absence of effective control measures. We estimated that, anthropogenic NMVOC emissions in China increased from 9.76 Tg in 1990 to 28.5 Tg in 2017, mainly driven by persistent growth from the industry sector and solvent use. In the meanwhile, emissions from the residential and transportation sectors declined after 2005, partly offset the total emission increase. During 1990–2017, mass-based emissions of alkanes, alkenes, alkynes, aromatics, oxygenated VOCs (OVOC) and other species increased by 274 %, 88 %, 4 %, 387 %, 91 %, and 231 % respectively.…

Abstract. Severe surface ozone pollution over major Chinese cities has become an emerging air quality concern, raising a new challenge for emission control measures in China. In this study, we explore the source contributions to surface daily maximum 8-h average (MDA8) ozone over China in 2016 and 2017, the two years with the highest surface ozone averaged over Chinese cities in record. We estimate the contributions of anthropogenic, background, and individual natural sources to surface ozone over China, using the GEOS-Chem chemical transport model at 0.25° × 0.3125° horizontal resolution with the most up-to-date Chinese anthropogenic emission inventory. Model results are evaluated with concurrent surface ozone measurements at 169 cities over China and show general good agreement. We find that background ozone (defined as ozone that would be presented in the absence of all Chinese anthropogenic emissions) accounts for 90 % (49.4 ppbv) of the national March–April mean surface MDA8 ozone over China and 80 % (44.5 ppbv) for May–August. It includes large contributions from natural…

Abstract. In 2013, China's government published the Air Pollution Prevention and Control Action Plan (APPCAP) with a specific target for Beijing, which aims to reduce annual mean PM2.5 concentrations in Beijing to 60 m−3 in 2017. During 2013–2017, the air quality in Beijing was significantly improved following the implementation of various emission control measures locally and regionally, with the annual mean PM2.5 concentration decreasing from 89.5 m−3 in 2013 to 58 m−3 in 2017. As meteorological conditions were more favourable to the reduction of air pollution in 2017 than in 2013 and 2016, the real effectiveness of emission control measures on the improvement of air quality in Beijing has frequently been questioned. In this work, by combining a detailed bottom-up emission inventory over Beijing, the MEIC regional emission inventory, and the WRF-CMAQ model, we attribute the improvement in Beijing's PM2.5 air quality in 2017 (compared to 2013 and 2016) to the following factors: changes in meteorological conditions, reduction of emissions from surrounding regions, and seven specific…

A 5-year Clean Air Action Plan was implemented in 2013 to reduce air pollutant emissions and improve ambient air quality in Beijing. Assessment of this action plan is an essential part of the decision-making process to review its efficacy and to develop new policies. Both statistical and chemical transport modelling have been previously applied to assess the efficacy of this action plan. However, inherent uncertainties in these methods mean that new and independent methods are required to support the assessment process. Here, we applied a machine-learning-based random forest technique to quantify the effectiveness of Beijing's action plan by decoupling the impact of meteorology on ambient air quality. Our results demonstrate that meteorological conditions have an important impact on the year-to-year variations in ambient air quality. Further analyses show that the PM 2.5 mass concentration would have broken the target of the plan (2017 annual PM 2.5 <60 µg m −3 ) were it not for the meteorological conditions in winter 2017 favouring the dispersion of air pollutants. However, over…

Abstract. We present a comprehensive simulation of tropospheric chlorine within the GEOS-Chem global 3-D model of oxidant-aerosol-halogen atmospheric chemistry. The simulation includes explicit accounting of chloride mobilization from sea-salt aerosol by acid displacement of HCl and by other heterogeneous processes. Additional sources of tropospheric chlorine (combustion, organochlorines, transport from stratosphere) are small in comparison. Reactive gas-phase chlorine Cl*, including Cl, ClO, Cl2, BrCl, ICl, HOCl, ClNO3, ClNO2, and minor species, is produced by the HCl + OH reaction and by heterogeneous conversion of sea-salt aerosol chloride to BrCl, ClNO2, Cl2, and ICl. The model simulates successfully the observed mixing ratios of HCl in marine air (highest at northern mid-latitudes) and the associated HNO3 decrease from acid displacement. It captures the high ClNO2 mixing ratios observed in continental surface air at night with chlorine of sea salt origin transported inland as HCl and fine aerosol. It simulates successfully the vertical profiles of HCl measured from aircraft,…

Atmospheric oxidation capacity is the basis for converting freshly emitted substances into secondary products and is dominated by reactions involving hydroxyl radicals (OH) during daytime. In this study, we present in situ measurements of RO x radical (hydroxy OH, hydroperoxy HO 2 , and organic peroxy RO 2 ) precursors and products; the measurements are carried out in four Chinese megacities (Beijing, Shanghai, Guangzhou, and Chongqing) during photochemically polluted seasons. The atmospheric oxidation capacity is evaluated using an observation-based model and radical chemistry precursor measurements as input. The radical budget analysis illustrates the importance of HONO and HCHO photolysis, which account for ∼50 % of the total primary radical sources. The radical propagation is efficient due to abundant NO in urban environments. Hence, the production rate of secondary pollutants, that is, ozone (and fine-particle precursors (H 2 SO 4 , HNO 3 , and extremely low volatility organic compounds, ELVOCs) is rapid, resulting in secondary air pollution. The ozone budget demonstrates its…

Abstract. The optical properties of airborne mineral dust depend on its mineralogy, size distribution, shape, and might vary between different source regions. To date, large differences in refractive index values found in the literature have not been fully explained. In this paper we present a new dataset of complex refractive indices (m=n‒ik) and single scattering albedos (SSA) for 19 mineral dust aerosols over the 370–950 nm range in dry conditions. Dust aerosols were generated from natural parent soils from eight source regions (Northern Africa, Sahel, Middle East, Eastern Asia, North and South America, Southern Africa, and Australia). These were selected to represent the global scale variability of the dust mineralogy. Dust was re‒suspended into a 4.2 m3 smog chamber where its spectral shortwave scattering (βsca) and absorption (βabs) coefficients, number size distribution, and bulk composition were measured. The complex refractive index was estimated by Mie calculations combining optical and size data, while the spectral SSA was directly retrieved from βsca and βabs…

Abstract. Volatile organic compounds (VOCs) are key precursors of photochemical smog. Quantitatively evaluating the contributions of VOCs sources to ozone (O3) formation could provide valuable information for emissions control and photochemical pollution abatement. This study analysed the continuously measured VOCs during the photochemical season in 2014 at a receptor site (Heshan site, HS) in the Pearl River Delta (PRD) region, where photochemical pollution has been a long-standing issue. The averaged mixing ratio of measure VOCs was 34 ± 3 ppbv, with the largest contribution from alkanes (17 ± 2 ppbv, 49 %), followed by aromatics, alkenes, and acetylene. The positive matrix factorization (PMF) model was applied to resolve the anthropogenic sources of VOCs, coupled with a photochemical-aged-based parameterization that better considers the photochemical processing effects. Four anthropogenic emission sources were identified and quantified, with gasoline vehicular emission as the most significant contributor to the observed VOCs, followed by diesel vehicular emissions, biomass…

Abstract. The clean air actions implemented by the Chinese government in 2013 have led to significantly improved air quality in Beijing. In this work, we combined the in-situ measurements of the chemical components of submicron particles (PM1) in Beijing during the winters of 2014 and 2017 and a regional chemical transport model to investigate the impact of clean air actions on aerosol chemistry and quantify the relative contributions of anthropogenic emissions, meteorological conditions, and regional transport to the changes in aerosol chemical composition from 2014 to 2017. We found that the average PM1 concentration in winter in Beijing decreased by 49.5 % from 2014 to 2017 (from 66.2 μg m−3 to 33.4 μg m−3). Sulfate exhibited a much larger decline than nitrate and ammonium, which led to a rapid transition from sulfate-driven to nitrate-driven aerosol pollution during the wintertime. Organic aerosol (OA), especially coal combustion OA, and black carbon also showed large decreasing rates, indicating the effective emission control of coal combustion and biomass burning. The…

Abstract. We use 2010–2015 observations of atmospheric methane columns from the GOSAT satellite instrument in a global inverse analysis to improve estimates of methane emissions and their trends over the period, as well as the global concentration of tropospheric OH (the hydroxyl radical, methane's main sink) and its trend. Our inversion solves the Bayesian optimization problem analytically including closed-form characterization of errors. This allows us to (1) quantify the information content from the inversion towards optimizing methane emissions and its trends, (2) diagnose error correlations between constraints on emissions and OH concentrations, and (3) generate a large ensemble of solutions testing different assumptions in the inversion. We show how the analytical approach can be used even when prior error standard deviation distributions are log-normal. Inversion results show large overestimates of Chinese coal emissions and Middle East oil/gas emissions in the EDGAR v4.3.2 inventory, but little error in the US where we use a new gridded version of the EPA national greenhouse…

Abstract. The impact of aerosols on cloud properties is one of the largest uncertainties in the anthropogenic radiative forcing of the climate. In recent years, significant progress has been made in constraining this forcing using observations, but uncertainty still remains, particularly in the adjustments of cloud properties to aerosol perturbations. Cloud liquid water path (LWP) is the leading control on liquid-cloud albedo, making it important to observationally constrain the aerosol impact LWP. Previous modelling and observational studies have shown that multiple processes play a role in determining the LWP response to aerosol perturbations, but that the aerosol effect can be difficult to isolate. Following previous studies using mediating variables, this work investigates use of the relationship between cloud droplet number concentration (Nd) and LWP for constraining the role of aerosols. Using joint probability histograms to account for the non-linear relationship, this work finds a relationship that is broadly consistent with previous studies. There is significant…

Abstract. Aerosol optical depth (AOD) has become a crucial metric for assessing global climate change. Although global and regional AOD trends have been studied extensively, it remains unclear what factors are driving the inter-decadal variations in regional AOD and how to quantify the relative contribution of each dominant factor. This study used a long-term (1980–2016) aerosol dataset from the Modern-Era Retrospective Analysis for Research and Applications, version 2 (MERRA-2) reanalysis, along with two satellite-based AOD datasets (MODIS/Terra and MISR) from 2001 to 2016, to investigate the long-term trends in global and regional aerosol loading. Statistical models based on emission factors and meteorological parameters were developed to identify the main factors driving the inter-decadal changes of regional AOD and to quantify their contribution. Evaluation of the MERRA-2 AOD with the combined in-situ measurements of AERONET and the China Aerosol Remote Sensing Network indicated significant spatial agreement on the global scale (r = 0.84, RMSE = 0.14, and MAE = 0.07). In…

Abstract. The Orbiting Carbon Observatory-2 has been on orbit since 2014, and its global coverage holds the potential to reveal new information about the carbon cycle through the use of top-down atmospheric inversion methods combined with column average CO2 retrievals. We employ a large ensemble of atmospheric inversions utilizing different transport models, data assimilation techniques and prior flux distributions in order to quantify the satellite-informed fluxes from OCO-2 Version 7r land observations and their uncertainties at continental scales. Additionally, we use in situ measurements to provide a baseline against which to compare the satellite-constrained results. We find that within ensemble spread, in situ observations and satellite retrievals constrain a similar global total carbon sink of 3.7 ± 0.5 PgC, and 1.5 ± 0.6 PgC per year for global land, for the 2015–2016 annual mean. This agreement breaks down on smaller regions, and we discuss the differences between the experiments. Of particular interest is the difference between the different assimilation constraints in the…

Abstract. Atmospheric oxidation of isoprene, the most abundantly emitted non-methane hydrocarbon, affects the abundances of ozone, the hydroxyl radical (OH), nitrogen oxide radicals (NOx), carbon monoxide (CO), oxygenated and nitrated organic compounds, and secondary organic aerosol (SOA). We analyze these effects in box models and in the global GEOS-Chem chemical transport model using the new Reduced Caltech Isoprene Mechanism (RCIM) condensed from a recently developed explicit isoprene oxidation mechanism. We find many similarities with previous global models of isoprene chemistry along with a number of important differences. Proper accounting of the isomer distribution of peroxy radicals following the addition of OH and O2 to isoprene influences the subsequent distribution of products, decreasing in particular the yield of methacrolein, and increasing the capacity of intramolecular hydrogen shifts to promptly regenerate OH. Hydrogen shift reactions throughout the mechanism lead to increased OH recycling, resulting in less depletion of OH under low-NO conditions than in previous…

Abstract. Acidity (pH) plays a key role in the physical and chemical behavior of aerosol and cannot be measured directly. In this work, aerosol liquid water content (ALWC) and size-resolved pH are predicted by thermodynamic model (ISORROPIA-II) in 2017 of Beijing. The mean aerosol pH over four seasons is 4.3±1.6 (spring), 4.5±1.1 (winter), 3.9±1.3 (summer), 4.1±1.0 (autumn), respectively, showing the moderate aerosol acidity. The aerosol pH in fine mode is in the range of 1.8 ~ 3.9, 2.4 ~ 6.3 and 3.5 ~ 6.5 for summer, autumn and winter, respectively. And coarse particles are generally neutral or alkaline. Diurnal variation of aerosol pH follows both aerosol components (especially the sulfate) and ALWC. For spring, summer and autumn, the averaged nighttime pH is 0.3~0.4 unit higher than that on daytime. Whereas in winter, the aerosol pH is relatively low at night and higher at sunset. SO42− and RH are two crucial factors affecting aerosol pH. For spring, winter and autumn, the effect of SO42− on aerosol pH is greater than RH, and it is comparable with RH in summer. The aerosol pH…

Abstract. Haze pollution caused by PM2.5 is the largest air quality concern in China in recent years. Long-term measurements of PM2.5 and the precursors and chemical speciation is crucially important for evaluating the efficiency of emission control, understanding formation and transport of PM2.5 associated with the change of meteorology and for accessing the impact of human activities to regional climate change. Here we reported long-term continuous measurements of PM2.5, chemical components, and their precursors at a regional background station, the Station for Observing Regional Processes of the Earth System (SORPES), in Nanjing eastern China since 2011. We found that PM2.5 at the station has experienced a substantial decrease (−9.1 %/yr), accompanied with even much significant reduction of SO2 (−16.7 %/yr), since the national "Ten measures" for air took action in 2013. Control of open biomass burning and fossil-fuel combustion are the two dominant factors that influence the PM2.5 reduction in early summer and winter, respectively. In cold season (November–January), increased…

Abstract. Delhi, India routinely experiences some of the world's highest urban particulate matter concentrations. We established the Delhi Aerosol Supersite campaign to provide long-term characterization of the ambient submicron aerosol composition in Delhi. Here we report on 1.25 years of highly time resolved speciated submicron particulate matter (PM1) data, including black carbon (BC) and non-refractory PM1 (NR-PM1), which we combine to develop a composition-based estimate of PM1 (“C-PM1” = BC + NR-PM1) concentrations. We observed marked seasonal and diurnal variability in the concentration and composition of PM1 owing to the interactions of sources and atmospheric processes. Winter was the most polluted period of the year with average C-PM1 mass concentrations of ~210 μg m−3. Monsoon was hot and rainy, consequently making it the least polluted (C-PM1 ~50 μg m−3) period. Organics constituted more than half of the C-PM1 for all seasons and times of day. While ammonium, chloride and nitrate each were ~10% of the C-PM1 for the cooler months, BC and sulfate contributed ~5% each. For…

Abstract. Motivated by the need to predict how the Arctic atmosphere will change in a warming world, this article summarizes recent advances made by the research consortium NETCARE (Network on Climate and Aerosols: Addressing Key Uncertainties in Remote Canadian Environments) that contribute to our fundamental understanding of Arctic aerosol particles as they relate to climate forcing. The overall goal of NETCARE research has been to use an interdisciplinary approach encompassing extensive field observations and a range of chemical transport, earth system, and biogeochemical models. Several major findings and advances have emerged from NETCARE since its formation in 2013 . (1) Unexpectedly high summertime dimethyl sulfide (DMS) levels were identified in ocean water and the overlying atmosphere in the Canadian Arctic Archipelago (CAA). Furthermore, melt ponds, which are widely prevalent, were identified as an important DMS source. (2) Evidence was found of widespread particle nucleation and growth in the marine boundary layer in the CAA in the summertime. DMS-oxidation-driven…

Abstract. Despite its key role for climate change, large uncertainties persist in our knowledge of the anthropogenic emissions of carbon dioxide (CO2) and no global observing system exists allowing to monitor emissions from localized CO2 sources with sufficient accuracy. The Orbiting Carbon Observatory-2 (OCO-2) satellite can retrieve the column-average dry-air mole fractions of CO2 (XCO2). However, regional column-average enhancements of individual point sources are usually small compared to the background concentration and its natural variability. This makes the unambiguous identification and quantification of anthropogenic emission plume signals challenging. NO2 is co-emitted with CO2 when fossil fuels are combusted at high temperatures. It has a short lifetime of the order of hours so that NO2 columns often exceed background levels by orders of magnitude near sources making it a suitable tracer of recently emitted CO2. Based on six case studies (Moscow, Russia; Lipetsk, Russia; Baghdad, Iraq; Medupi and Matimba power plants, South Africa; Australian wildfires; and Nanjing,…

Abstract. Nitrous acid (HONO) can strongly affect atmospheric photochemistry in polluted regions through the production of hydroxyl radical (OH). 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/m3, 150 ppb, and 8 ppb, respectively, at a suburban site. The present study investigated the sources/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 Multi-scale Air Quality (CMAQ) model, including RH-dependent 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…

Abstract. Past studies have suggested that ozone in the troposphere has increased globally throughout much of the 20th century due to increases in anthropogenic emissions and transport. We show by combining satellite measurements with a chemical transport model that during the last four decades tropospheric ozone does indeed indicate increases that are global in nature, yet still highly regional. Satellite ozone measurements from Nimbus-7 and Earth Probe Total Ozone Mapping Spectrometer (TOMS) are merged with ozone measurements from Aura Ozone Monitoring Instrument/Microwave Limb Sounder (OMI/MLS) to determine trends in tropospheric ozone for 1979–2016. Both TOMS (1979–2005) and OMI/MLS (2005–2016) depict large increases in tropospheric ozone from the Near East to India/East Asia and further eastward over the Pacific Ocean. The 38-year merged satellite record shows total net change over this region of about +6 to +7 Dobson Units (DU) (i.e., ~ 15–20 % of average background ozone), with the largest increase (~ 4 DU) occurring during the 2005–2016 Aura period. The Global Modeling…

Abstract. Nitro-aromatic compounds (NACs), as important contributors to the light absorption by brown carbon, have been widely observed in various ambient atmospheres; however, their formation in the urban atmosphere was little studied. In this work, we report an intensive field study of NACs in summer 2016 at an urban Beijing site, characterized by both high-NOx and anthropogenic VOC dominated conditions. We investigated the factors that influence NAC formation (e.g., NO2, VOC precursors, RH and photolysis) through quantification of eight NACs, along with major components in fine particulate matter, selected volatile organic compounds, and gases. The average total concentration of the quantified NACs was 6.63 ng m−3, higher than those reported in other summertime studies (0.14–6.44 ng m−3). 4-Nitrophenol (4NP, 32.4 %) and 4-nitrocatechol (4NC, 28.5 %) were the top two most abundant NACs, followed by methyl-nitrocatechol (MNC), methyl-nitrophenol (MNP), and dimethyl-nitrophenol (DMNP). The oxidation of toluene and benzene in the presence of NOx was found to be a more dominant source…

Abstract. Air quality models have not been able to reproduce the magnitude of the observed concentrations of fine particulate matter (PM2.5) during wintertime Chinese haze events. The discrepancy has been at least partly attributed to low biases in modeled sulfate production rates due to the lack of heterogeneous sulfate production on aerosols in the models. In this study, we explicitly implement four heterogeneous sulfate formation mechanisms into a regional chemical transport model, in addition to gas-phase and in-cloud sulfate production. We compare the model results with observations of sulfate concentrations and oxygen isotopes (Δ17O(SO42−)) in the winter of 2014–2015, the latter of which is highly sensitive to the relative importance of different sulfate production mechanisms. Model results suggest that heterogeneous sulfate production on aerosols accounts for about 20 % of sulfate production in clean and polluted conditions, partially reducing the modeled low bias in sulfate concentrations. Model sensitivity studies in comparison with the Δ17O(SO42−) observations suggest that…

Abstract. Understanding the effectiveness of air pollution control policies is important for future policy making. China implemented strict air pollution control polices since 11th Five Year Plan (FYP). There is still a lack of overall evaluation of the effects of air pollution control policies on PM2.5 pollution improvement in China since FYP. In this study, we aimed to assess the effects of air pollution control policies from 2005 to 2017 on PM2.5 from the view of satellite remote sensing. We used the satellite derived PM2.5 of 2005–2013 from one of our previous studies. For the data of 2014–2017, we developed a two-stage statistical model to retrieve satellite PM2.5 data. Results show that the Energy Conservation and Emissions Reduction (ECER) policy, implemented in 11th FYP period and focused on SO2 emissions control, had co-benefits on PM2.5 reductions. The increasing trends of PM2.5 pollutions was suppressed after 2007, and the PM2.5 in Central and South China showed significant decreasing trends. The ECER policy during 12th FYP period were basically the extension of 11th FYP…

Abstract. Hydroxyl (OH) and peroxy radicals (HO2, RO2) were measured in the Pearl River Delta which is one of the most polluted areas in China, in autumn 2014. The radical observations were complemented by measurements of OH reactivity (inverse OH lifetime) and a comprehensive set of trace gases including CO, NOx and VOCs. OH reactivity was in the range between 15 s−1 and 80 s−1, of which about 50 % was unexplained by the measured OH reactants. In the three weeks of the campaign, maximum median radical concentrations were 4.5 × 106 cm−3 for OH at noon, and 3 × 108 cm−3 and 2.0 × 108 cm−3 for HO2 and RO2, respectively, in the early afternoon. The completeness of the daytime radical measurements made it possible to carry out experimental budget analyses for all radicals (OH, HO2, and RO2) and their sum (ROx). The maximum loss rates for OH, HO2, and RO2 reached values between 10 ppbv/h and 15 ppbv/h during daytime. The largest fraction of this can be attributed to radical interconveresio reactions while the real loss rate of ROx remained below 3 ppbv/h. Within experimental…

Abstract. In the summer of 2017, heavy ozone pollution swamped most of the North China Plain (NCP), with the maximum regional average of daily maximum 8-h ozone concentration (MDA8) reaching almost 120 ppbv. In light of the continuing reduction of anthropogenic emissions in China, the underlying mechanisms for the occurrences of these regional extreme ozone episodes are elucidated from two perspectives: meteorology and biogenic emissions. The significant positive correlation between MDA8 and temperature, which is amplified during heat waves concomitant with stagnant air and no precipitation, supports the crucial role of meteorology in driving high ozone concentrations. We also find that biogenic emissions are enhanced due to factors previously not considered. During the heavy ozone pollution episodes in June 2017, biogenic emissions driven by high vapor pressure deficit (VPD), land cover change and urban landscape yield an extra mean MDA8 ozone of 3.08, 2.79 and 4.74 ppbv, respectively over the NCP, which together contribute as much to MDA8 ozone as biogenic emissions simulated…

Abstract. Biomass burning is a major source of atmospheric brown carbon (BrC) and through its absorption of UV/VIS radiation, it can play an important role on the planetary radiative balance and atmospheric photochemistry. The considerable uncertainty of BrC impacts is associated with its poorly constrained sources, transformations and atmospheric lifetime. Here we report laboratory experiments that examined changes in the optical properties of the water-soluble BrC fraction of biomass burning particles. Effects of direct UVB photolysis and OH oxidation in the aqueous phase on molecular weight-separated BrC were studied. Results indicated that low molecular weight (MW) BrC ( 10 hours) biomass burning emissions, poor linear correlations were found between light absorptivity and levoglucosan, consistent with other studies suggesting a short atmospheric lifetime for levoglucosan. However, a much stronger correlation between light absorptivity and total hydrous sugars was observed, suggesting that they may serve as more robust tracers for aged biomass burning emissions. Overall, the…

Abstract. This study presents a novel methodology for remote monitoring of aerosol composition over large spatial and temporal domains. The concept is realized within the GRASP (Generalized Retrieval of Aerosol and Surface Properties) algorithm to directly infer aerosol composition from the measured radiances. This approach is different from the conventional methods that use post-processing of the retrieved aerosol optical properties for aerosol typing. The proposed method assumes observed aerosols as mixtures of particles composed of black carbon, brown carbon, absorbing insoluble, non-absorbing insoluble embedded in a soluble host. The algorithm then derives size distribution and the fractions of these components. The complex refractive index of each component is fixed a priori and the complex refractive index of mixture is computed using mixing rules. The approach is first tested with synthetic data and the uncertainties are estimated. Then, it is applied to the real ground-based AERONET and space-borne POLDER/PARASOL observations, known to be sensitive to aerosol complex…

Abstract. Organic peroxy radicals (RO2), formed from the degradation of hydrocarbons and other volatile organic compounds (VOCs), play a key role in tropospheric oxidation mechanisms. Several competing reactions may be available for a given RO2 radical, the relative rates of which depend on both the structure of RO2 and the ambient conditions. Published kinetics and branching ratio data are reviewed for the bimolecular reactions of RO2 with NO, NO2, NO3, OH and HO2; and for their self-reactions and cross-reactions with other RO2 radicals. This information is used to define generic rate coefficients and structure-activity relationship (SAR) methods that can be applied to the bimolecular reactions of a series of important classes of hydrocarbon and oxygenated RO2 radical. Information for selected unimolecular isomerization reactions (i.e. H-atom shift and ring-closure reactions) is also summarised and discussed. The methods presented here are intended to guide the representation of RO2 radical chemistry in the next generation of explicit detailed chemical mechanisms.

Abstract. Mineral dust is an important component of the climate system, interacting with radiation, clouds and biogeochemical systems, and impacting atmospheric circulation, air quality, aviation and solar energy generation. These impacts are sensitive to dust particle size distribution (PSD), yet models struggle or even fail to represent coarse (diameter (d) > 2.5 µm) and giant (d>20 µm) dust particles and the evolution of the PSD with transport. Here we examine three state-of-the-art airborne observational datasets, all of which measured the full size range of dust (d = 0.1 to > 100 µm) at different stages during transport, with consistent instrumentation. We quantify the presence and evolution of coarse and giant particles and their contribution to optical properties. Observations are taken from the Fennec fieldwork over the Sahara and in the Saharan Air Layer (SAL) near the Canary Islands, and from the AER-D fieldwork in the vicinity of the Cape Verde Islands in the SAL. Observations show significantly more abundant coarse and giant dust particles over the Sahara compared to the…

Abstract. Ground-level observations, reanalyzed meteorological fields and a 3-D global chemical and transport model (GEOS-Chem) were applied in this study to investigate ozone (O3) pollution events (OPEs) in North China (36.5° N–40.5° N, 114.5° E–119.5° E) during 2014–2017. Ozone pollution days (OPDs) were defined as days with maximum daily averaged 8-h (MDA8) concentrations over North China larger than 160 μg m−3, and OPEs were defined as periods with 3 or more consecutive OPDs. Observations showed that there were 167 OPDs and 27 OPEs in North China during 2014–2017, in which 123 OPDs and 21 OPEs occurred in May–July. We found that OPEs in North China occurred under a typical weather pattern with high daily maximum temperature (Tmax), low relative humidity (RH), anomalous southerlies and divergence in the lower troposphere, an anomalous high-pressure system at 500 hPa and an anomalous downward air flow from 500 hPa to the surface. Under such a weather pattern, chemical production of O3 was high between 800 and 900 hPa, which was then transported downward to enhance O3 pollution at…

Abstract. Ammonia (NH3) is an essential reactive nitrogen species in the biosphere and through its use in agriculture in the form of fertilizer important for sustaining human kind. The current emission levels however, are up to four times higher than in the previous century and continue to grow with uncertain consequences to human health and the environment. While NH3 at its current levels is a hazard to the environmental and human health the atmospheric budget is still highly uncertain, which is a product of an overall lack of measurements. The capability to measure NH3 with satellites has opened up new ways to study the atmospheric NH3 budget. In this study we present the first estimates of NH3 emissions, lifetimes, and plume widths from large (> ~ 5 kt/yr) agricultural and industrial point sources from CrIS satellite observations across the globe with a consistent methodology. The same methodology is also applied to the IASI (A and B) satellite observations and we show that the satellites typically provide comparable results that are within the uncertainty of the estimates. The…

Abstract. In order to identify and quantify key-species associated with non-exhaust emissions and exhaust vehicular emissions a large comprehensive dataset of particulate species has been obtained thanks to simultaneous near-road and urban background measurements coupled with detailed traffic counts and chassis dynamometer measurements of exhaust emissions of a few in-use vehicles well-represented in the French fleet. Elemental Carbon, brake-wear metals (Cu, Fe, Sb, Sn, Mn), n-alkanes (C19–C26), light molecular weight PAHs (Pyrene, Fluoranthene, Anthracene) and two hopanes (17α21βNorhopane and 17α21βhopane) are strongly associated with the road traffic. Traffic-fleet emission factors have been determined for all of them and are consistent with most recent published equivalent data. When possible, light-duty and heavy-duty duty traffic emission factors are also determined. Most of the first ones are in good agreement with emissions from chassis dynamometer measurements in absence of significant non-combustion emissions. This study has shown that ratios involving copper (mainly Cu/Fe…

Abstract. New particle formation (NPF) studies in China were summarized comprehensively in this paper. NPF frequency, formation rate and particle growth rate were closely compared among the observations carried out at different types of sites in different regions of China in different seasons, with the aim of exploring the nucleation and particle growth mechanisms. The interactions between air pollution and NPF are discussed, emphasizing on the properties of NPF under heavy pollution conditions. The current understanding of NPF cannot not be fully explain the frequent occurrence of NPF at high aerosol loadings in China, and possible reasons for this phenomenon are proposed. The effects of NPF and some aspects of NPF research requiring further investigations are also summarized in this paper.

A 5-month campaign (from May to September 2017) was conducted to characterize volatile organic compounds (VOCs) for the first time at four sites in Zhengzhou, Henan Province, China, where ground level ozone (O 3 ) concentration has shown an increasing trend in recent years. Canister samples were collected for the measurement of 57 VOCs, which, along with reactive nitrogen oxides (NO x ), are the most important O 3 precursors. During the same period, O 3 and its precursor gases were monitored online simultaneously. The results indicated that the average mixing ratio of total quantified VOCs (ΣVOCs=28.8±22.1 ppbv) in Zhengzhou was lower than that in the other Chinese megacities, while alkyne comprised a higher proportion of Σ VOCs . The abundances, compositions and ratios of typical VOCs showed clear spatial and temporal variations. Cluster analysis indicates that air masses from the south of Zhengzhou were cleaner than from other directions. The molar ratio of VOCs to NO x indicated that, in general, O 3 formation was more sensitive to VOCs than NO x formation in Zhengzhou. The…

Abstract. In this work, a ~ 21-years self-consistent global dataset from four different satellite sensors with a mid-morning overpass (GOME/ERS-2, SCIAMACHY/ENVISAT, GOME-2/Metop-A and GOME-2/Metop-B) is compiled to study the long-term tropospheric NO2 patterns and trends. The GOME and GOME-2 data are corrected relative to the SCIAMACHY data in order to reproduce what SCIAMACHY would measure if it was in orbit for the period 4/1996–9/2017. The highest tropospheric NO2 concentrations are seen over urban, industrialized and highly populated areas and over ship tracks in the oceans. Tropospheric NO2 has generally decreased during the last two decades over the industrialized and highly populated regions of the Western World (e.g. average decrease of the order of ~ 49 % over the U.S., the Netherlands and the U.K., ~ 36 % over Italy and Japan and ~ 32 % over Germany and France) and increased over developing regions (e.g. average increase of ~ 160 % over China and ~ 33 % over India). It is suggested here that linear trends cannot be used efficiently worldwide for such long periods.…

Abstract. Number concentrations of ice nucleating particles (NINP) in the Arctic were derived from ground-based filter samples. Examined samples had been collected in Alert (Nunavut, Northern Canadian Archipelago on Ellesmere Island), Utqiagvik, formerly known as Barrow (Alaska), Ny Ålesund (Svalbard) and at the Villum Research Station (VRS, North Greenland). For the former two stations, examined filters span a full yearly cycle. For VRS, 10 weekly samples, mostly from different month of one year, were included. Samples from Ny Ålesund were collected during the months from March until September of one year. At all four stations, highest concentrations were found in the summer months from roughly June to September. For those stations with sufficient data coverage, an annual cycle can be seen. The spectra of NINP observed at the highest temperatures, i.e., those obtained for summer month, showed the presence of INP that nucleate ice up to − 5 °C. It is know from literature that ice activivity observed at such high temperatures indicates the presence of ice active material of biogenic…

Abstract. The National Emission Inventory (NEI) of the US Environmental Protection Agency (EPA) reports a steady decrease of US NOx emissions over the 2005–2017 period at a rate of 0.1 Mt a−1 (53 % decrease over the period), reflecting sustained efforts to improve air quality. Tropospheric NO2 columns observed by the satellite-based Ozone Monitoring Instrument (OMI) over the US show a steady decrease until 2009 but a flattening afterward, which has been attributed to a flattening of NOx emissions in contradiction with the NEI. We show here that the steady 2005–2017 decrease of NOx emissions reported by the NEI is in fact consistent with observed network trends of surface NO2 and ozone concentrations. The OMI NO2 trend is instead similar to that observed for nitrate wet deposition fluxes, where post-2009 flattening is due to an increasing relative contribution of non-anthropogenic background (mainly lightning and soils) and not to a flattening of anthropogenic emissions. This is confirmed by contrasting OMI NO2 trends in urban winter, where the background is low and OMI NO2 shows a…

Abstract. Long-range transported smoke aerosols in the UTLS (Upper Troposphere/Lower Stratosphere) over Europe were detected in Summer 2017. The measurements of ground-based instruments and satellite sensors indicate that the UTLS aerosol layers were originated from Canadian wildfires and were transported to Europe by UTLS advection. In this study, the observations of two multi-wavelength Raman Lidar systems in northern France (Lille and Palaiseau) are used to derive aerosol properties, such as optical depth of the UTLS layer, Lidar ratios at 355 and 532 nm and particle linear depolarization ratios at 355, 532 and 1064 nm. The optical depth of the UTLS layers at 532 nm varies from 0.05 to above 0.20, with very weak spectral dependence between 355 and 532 nm. Lidar ratios at 355 nm are in 31 ± 15 sr to 45 ± 9 sr range and at 532 nm, the Lidar ratios are in the range of 54 ± 12 sr to 58 ± 9 sr. Such spectral dependence of Lidar ratio is known to be a characteristic feature of aged smoke. The typical particle depolarization ratios in the UTLS smoke layer are 25 ± 4 % at 355 nm, 19 ± 3…

Abstract. Atmospheric marine aerosol particles impact Earth's albedo and climate. These particles can be primary or secondary and come from a variety of sources, including sea salt, dissolved organic matter, volatile organic compounds, and sulfur-containing compounds. Dimethylsulfide (DMS) marine emissions contribute greatly to the global biogenic sulfur budget, and its oxidation products can contribute to aerosol mass, specifically as sulfuric acid and methanesulfonic acid (MSA). Further, sulfuric acid is a known nucleating compound, and MSA may be able to participate in nucleation when bases are available. As DMS emissions, and thus MSA and sulfuric acid from DMS oxidation, may have changed since pre-industrial times and may change in a warming climate, it is important to characterize and constrain the climate impacts of both species. Currently, global models that simulate aerosol size distributions include contributions of sulfate and sulfuric acid from DMS oxidation, but to our knowledge, global models typically neglect the impact of MSA on size distributions. In this study, we…

Abstract. The Himalaya is very sensitive to climatic variations because of its fragile environmental and climatic settings. There are clear and strong indicators of climate change reported for the Himalaya, particularly the Jammu and Kashmir region in the western Himalayas. In this study, the detailed characteristics of long and short term as well as localized variations of temperature and precipitation are analysed for six meteorological stations (Gulmarg, Pahalgam, Kokarnag, Quazigund, Kupwara and Srinagar) over Jammu and Kashmir, India for a period of 37 years during 1980–2016 by making use of observed stations data, WRF model downscaled monthly-averaged surface temperature and precipitation and ERA-interim (ERA-I) reanalysis data. The annual and seasonal temperature and precipitation changes were analysed by carrying out the Student's t-test, Mann–Kendall, Spearman Rho and Cumulative deviation statistical tests. The results show an increase of 0.8 °C in average annual temperature over thirty years during 1980–2016 with higher increase in maximum temperature (0.97 °C) compared to…

Abstract. Six months of stratospheric aerosol observations with the European Aerosol Research Lidar Network (EARLINET) from August 2017 to January 2018 are presented. The decay phase of an unprecedented, record-breaking stratospheric perturbation caused by wild fire smoke is reported and discussed in terms of geometrical, optical, and microphysical aerosol properties. Enormous amounts of smoke (mainly soot particles) were injected into the upper troposphere and lower stratosphere over fire areas in western Canada on 12 August 2017 during strong thunderstorm-pyrocumulonimbus activity. The stratospheric smoke plumes spread over the entire northern hemisphere in the following weeks and months. Twenty-eight European lidar stations from northern Norway to southern Portugal and the Eastern Mediterranean monitored the strong stratospheric perturbation on a continental scale. The main smoke layer (over central, western, southern, and eastern Europe) was found between 15 and 20 km height since September 2017 (about two weeks after entering the stratosphere). Thin layers of smoke were…

Abstract. Chemical mechanisms responsible for rapid sulfate production, an important driver of winter haze formation in northern China, remain unclear. Here, we propose a potentially important heterogeneous hydroxymethanesulfonate (HMS) chemical mechanism. Through analyzing field measurements with aerosol mass spectrometry, we show evidence for a possible significant existence in haze aerosols of organosulfur primarily as HMS, misidentified as sulfate in previous observations. We estimate that HMS can account for up to about one-third of the sulfate concentrations unexplained by current air quality models. In addition, HMS in the presence of hydroxyl radicals can trigger rapid sulfate production in aerosol water. Heterogeneous production of HMS by SO2 and formaldehyde is favored under northern China winter haze conditions due to high aerosol water content, moderately acidic pH values, high gaseous precursor levels, and low temperature. These analyses identify an unappreciated importance of formaldehyde in secondary aerosol formation and calls for more research on sources and on the…

Abstract. Chamber oxidation experiments conducted at the Fire Sciences Laboratory in 2016 are evaluated to identify important chemical processes contributing to the OH chemistry of biomass burning non-methane organic gases (NMOG). Based on the decay of primary carbon measured by proton transfer reaction time-of-flight mass spectrometry (PTR-ToF-MS), it is confirmed that furans and oxygenated aromatics are among the NMOG emitted from western United States fuel types with the highest reactivities towards OH. The oxidation processes and formation of secondary NMOG masses measured by PTR-ToF-MS and iodide clustering time-of-flight chemical ionization mass spectrometry (I-CIMS) is interpreted using a box model employing a modified version of the Master Chemical Mechanism (v. 3.3.1) that includes the OH oxidation of furan, 2-methylfuran, 2,5-dimethylfuran, furfural, 5-methylfurfural, and guaiacol. The model supports the assignment of major PTR-ToF-MS and I-CIMS signals to a series of anhydrides and hydroxy furanones formed primarily through furan chemistry. This mechanism is applied to a…

Abstract. Hygroscopicity is one of the most important physicochemical properties of aerosol particles, and also plays indispensable roles in many other scientific and technical fields. A myriad of experimental techniques, which differ in principles, configurations and cost, are available for investigating aerosol hygroscopicity under subsaturated conditions (i.e., relative humidity below 100 %). A comprehensive review of these techniques is provided in this paper, in which experimental techniques are broadly classified into four categories, according to the way samples under investigation are prepared. For each technique, we describe its operation principle and typical configuration, use representative examples reported in previous work to illustrate how this technique can help better understand aerosol hygroscopicity, and discuss its advantages and disadvantages. In addition, future directions are outlined and discussed for further technical improvement and instrumental development.

Abstract. On-road vehicle emissions are a major contributor to elevated air pollution levels in populous metropolitan areas. We developed a link-level emissions inventory of vehicular pollutants, called EMBEV-Link, based on multiple datasets extracted from the extensive road traffic monitoring network that covers the entire municipality of Beijing, China (16 400 km2). We employed the EMBEV-Link model under various traffic scenarios to capture the significant variability in vehicle emissions, temporally and spatially, due to the real-world traffic dynamics and the traffic restrictions implemented by the local government. The results revealed high carbon monoxide (CO) and total hydrocarbon (THC) emissions in the urban area (i.e., within the Fifth Ring Road) and during rush hours, both associated with the passenger vehicle traffic. By contrast, considerable fractions of nitrogen oxides (NOX), fine particulate matter (PM2.5) and black carbon (BC) emissions were present beyond the urban area, as heavy-duty trucks (HDTs) were not allowed to drive through the urban area during daytime. The…