The 50 most-cited articles in Atmospheric chemistry and physics, 2017

Abstract. An anthropogenic emission inventory for Asia is developed for the years 2008 and 2010 to support the Model Inter-Comparison Study for Asia (MICS-Asia) and the Task Force on Hemispheric Transport of Air Pollution (TF HTAP) projects by a mosaic of up-to-date regional emission inventories. Emissions are estimated for all major anthropogenic sources in 30 countries and regions in Asia. We conducted detailed comparisons of different regional emission inventories and incorporated the best-available ones for each region into the mosaic inventory at a uniform spatial and temporal resolution. We estimate the total Asian emissions of ten species in 2010 as follows: 51.3 Tg SO2, 52.1 Tg NOx, 336.6 Tg CO, 67.0 Tg NMVOC (non-methane volatile organic compounds), 28.8 Tg NH3, 31.7 Tg PM10, 22.7 Tg PM2.5, 3.5 Tg BC, 8.3 Tg OC and 17.3 Pg CO2. Emissions from China and India dominate the emissions of Asia for most of the species. We also estimated Asian emissions in 2006 using the same methodology of MIX. The relative change rates of Asian emissions for the period of 2006–2010 are estimated…

Abstract. This paper presents the first comprehensive assessment of historical (1990–2010) global anthropogenic particulate matter (PM) emissions including consistent and harmonized calculation of mass-based size distribution (PM1, PM2.5, PM10) as well as primary carbonaceous aerosols including black carbon (BC) and organic carbon (OC). The estimates were developed with the integrated assessment model GAINS, where source- and region-specific technology characteristics are explicitly included. This assessment includes a number of previously unaccounted or often misallocated emission sources, i.e., kerosene lamps, gas flaring, diesel generators, trash burning; some of them were reported in the past for selected regions or in the context of a particular pollutant or sector but not included as part of a total estimate. Spatially, emissions were calculated for 170 source regions (as well as international shipping), presented for 25 global regions, and allocated to 0.5° x 0.5° longitude-latitude grids. No independent estimates of emissions from forest fires and savannah burning are…

Abstract. Oxidation of biogenic volatile organic compounds (BVOC) by the nitrate radical (NO3) represents one of the important interactions between anthropogenic emissions related to combustion and natural emissions from the biosphere. This interaction has been recognized for more than 3 decades, during which time a large body of research has emerged from laboratory, field, and modeling studies. NO3-BVOC reactions influence air quality, climate and visibility through regional and global budgets for reactive nitrogen (particularly organic nitrates), ozone, and organic aerosol. Despite its long history of research and the significance of this topic in atmospheric chemistry, a number of important uncertainties remain. These include an incomplete understanding of the rates, mechanisms, and organic aerosol yields for NO3-BVOC reactions, lack of constraints on the role of heterogeneous oxidative processes associated with the NO3 radical, the difficulty of characterizing the spatial distributions of BVOC and NO3 within the poorly mixed nocturnal atmosphere, and the challenge of…

Abstract. Mercury (Hg) is emitted to the atmosphere mainly as volatile elemental Hg0. Oxidation to water-soluble HgII controls Hg deposition to ecosystems. Here we implement a new mechanism for atmospheric Hg0 / HgII redox chemistry in the GEOS-Chem global model and examine the implications for the global atmospheric Hg budget and deposition patterns. Our simulation includes a new coupling of GEOS-Chem to an ocean general circulation model (MITgcm), enabling a global 3-D representation of atmosphere-ocean Hg0 / HgII cycling. We find that atomic bromine (Br) of marine organobromine origin is the main atmospheric Hg0 oxidant, and that second-stage HgBr oxidation is mainly by the NO2 and HO2 radicals. The resulting lifetime of tropospheric Hg0 against oxidation is 2.7 months, shorter than in previous models. Fast HgII atmospheric reduction must occur in order to match the ~ 6-month lifetime of Hg against deposition implied by the observed atmospheric variability of total gaseous mercury (TGM ≡ Hg0 + HgII(g)). We implement this reduction in GEOS-Chem as photolysis of aqueous-phase…

Abstract. A comprehensive field campaign was carried out in summer 2014 in Wangdu, located in the North China Plain. A month of continuous OH, HO2 and RO2 measurements was achieved. Observations of radicals by the laser-induced fluorescence (LIF) technique revealed daily maximum concentrations between (5–15) × 106 cm−3, (3–14) × 108 cm−3 and (3–15) × 108 cm−3 for OH, HO2 and RO2, respectively. Measured OH reactivities (inverse OH lifetime) were 10 to 20 s−1 during daytime. The chemical box model RACM 2, including the Leuven isoprene mechanism (LIM), was used to interpret the observed radical concentrations. As in previous field campaigns in China, modeled and measured OH concentrations agree for NO mixing ratios higher than 1 ppbv, but systematic discrepancies are observed in the afternoon for NO mixing ratios of less than 300 pptv (the model–measurement ratio is between 1.4 and 2 in this case). If additional OH recycling equivalent to 100 pptv NO is assumed, the model is capable of reproducing the observed OH, HO2 and RO2 concentrations for conditions of high volatile organic…

Abstract. Black carbon (BC) measured by a multi-wavelength Aethalometer can be apportioned to traffic and wood burning. The method is based on the differences in the dependence of aerosol absorption on the wavelength of light used to investigate the sample, parameterized by the source-specific Ångström absorption exponent (α). While the spectral dependence (defined as α values) of the traffic-related BC light absorption is low, wood smoke particles feature enhanced light absorption in the blue and near ultraviolet. Source apportionment results using this methodology are hence strongly dependent on the α values assumed for both types of emissions: traffic αTR, and wood burning αWB. Most studies use a single αTR and αWB pair in the Aethalometer model, derived from previous work. However, an accurate determination of the source specific α values is currently lacking and in some recent publications the applicability of the Aethalometer model was questioned. Here we present an indirect methodology for the determination of WB and αTR by comparing the source apportionment of BC using the…

Abstract. To obtain a thorough knowledge of PM2.5 chemical composition and its impact on aerosol optical properties across China, existing field studies conducted after the year of 2000 are reviewed and summarized in terms of geographical, inter-annual, and seasonal distributions. Annual PM2.5 was up to six times of the national air quality standard in some megacities in northern China. Annual PM2.5 was higher in northern than southern cities, and higher in inland than coastal cities. In a few cities with data longer than a decade, PM2.5 showed a slight decrease only in the second half of the past decade, while carbonaceous aerosols decreased, sulfate (SO42−) and ammonium (NH4+) remained at high levels, and nitrate (NO3−) increased. The highest seasonal averages of PM2.5 and its major chemical components were mostly observed in the cold seasons. Annual average contributions of secondary inorganic aerosols to PM2.5 ranged from 25 % to 48 %, and those of carbonaceous aerosols ranged from 23 % to 47 %, both with higher values in southern regions due to the frequent dust events in…

Abstract. The climate research community uses atmospheric reanalysis data sets to understand a wide range of processes and variability in the atmosphere, yet different reanalyses may give very different results for the same diagnostics. The Stratosphere–troposphere Processes And their Role in Climate (SPARC) Reanalysis Intercomparison Project (S-RIP) is a coordinated activity to compare reanalysis data sets using a variety of key diagnostics. The objectives of this project are to identify differences among reanalyses and understand their underlying causes, to provide guidance on appropriate usage of various reanalysis products in scientific studies, particularly those of relevance to SPARC, and to contribute to future improvements in the reanalysis products by establishing collaborative links between reanalysis centres and data users. The project focuses predominantly on differences among reanalyses, although studies that include operational analyses and studies comparing reanalyses with observations are also included when appropriate. The emphasis is on diagnostics of the upper…

Abstract. Global surface emissions of nitrogen oxides (NOx) over a 10-year period (2005–2014) are estimated from an assimilation of multiple satellite data sets: tropospheric NO2 columns from Ozone Monitoring Instrument (OMI), Global Ozone Monitoring Experiment-2 (GOME-2), and Scanning Imaging Absorption Spectrometer for Atmospheric Chartography (SCIAMACHY), O3 profiles from Tropospheric Emission Spectrometer (TES), CO profiles from Measurement of Pollution in the Troposphere (MOPITT), and O3 and HNO3 profiles from Microwave Limb Sounder (MLS) using an ensemble Kalman filter technique. Chemical concentrations of various species and emission sources of several precursors are simultaneously optimized. This is expected to improve the emission inversion because the emission estimates are influenced by biases in the modelled tropospheric chemistry, which can be partly corrected by also optimizing the concentrations. We present detailed distributions of the estimated emission distributions for all major regions, the diurnal and seasonal variability, and the evolution of these emissions…

Abstract. Air quality observations by satellite instruments are global and have a regular temporal resolution, which makes them very useful in studying long-term trends in atmospheric species. To monitor air quality trends in China for the period 2005–2015, we derive SO2 columns and NOx emissions on a provincial level with improved accuracy. To put these trends into perspective they are compared with public data on energy consumption and the environmental policies of China. We distinguish the effect of air quality regulations from economic growth by comparing them relatively to fossil fuel consumption. Pollutant levels, per unit of fossil fuel, are used to assess the effectiveness of air quality regulations. We note that the desulfurization regulations enforced in 2005–2006 only had a significant effect in the years 2008–2009, when a much stricter control of the actual use of the installations began. For national NOx emissions a distinct decreasing trend is only visible from 2012 onwards, but the emission peak year differs from province to province. Unlike SO2, emissions of NOx are…

Abstract. Biomass burning injects many different gases and aerosols into the atmosphere that could have a harmful effect on air quality, climate, and human health. In this study, a comprehensive biomass burning emission inventory including domestic and in-field straw burning, firewood burning, livestock excrement burning, and forest and grassland fires is presented, which was developed for mainland China in 2012 based on county-level activity data, satellite data, and updated source-specific emission factors (EFs). The emission inventory within a 1 × 1 km2 grid was generated using geographical information system (GIS) technology according to source-based spatial surrogates. A range of key information related to emission estimation (e.g. province-specific proportion of domestic and in-field straw burning, detailed firewood burning quantities, uneven temporal distribution coefficient) was obtained from field investigation, systematic combing of the latest research, and regression analysis of statistical data. The established emission inventory includes the major precursors of complex…

Abstract. Surface ozone (O3) responds to varying global-to-regional precursor emissions, climate, and extreme weather, with implications for designing effective air quality control policies. We examine these conjoined processes with observations and global chemistry-climate model (GFDL-AM3) hindcasts over 1980–2014. The model captures the salient features of observed trends in daily maximum 8-hour average O3; (1) increases over East Asia (up to 2 ppb yr−1), (2) springtime increases at western US (WUS) rural sites (0.2–0.5 ppb yr−1) with a ‘baseline’ sampling approach, (3) summertime decreases, largest at the 95th percentile, and wintertime increases in the 50th to 5th percentiles over the eastern US (EUS). Asian NOx emissions tripled since 1990, contributing as much as 65 % to modeled springtime background O3 increases (0.3–0.5 ppb yr−1) over the WUS, outpacing O3 decreases attained via US domestic emission controls. Methane increases over this period raise WUS background O3 by 15 %. During summer, increasing Asian emissions approximately offset the effects of US emission…

Abstract. Organic compounds and liquid water are major aerosol constituents in the southeast United States (SE US). Water associated with inorganic constituents (inorganic water) can contribute to the partitioning medium for organic aerosol when relative humidities or organic matter to organic carbon (OM/OC) ratios are high such that separation relative humidities (SRH) are below the ambient relative humidity (RH). As OM/OC ratios in the SE US are often between 1.8 and 2.2, organic aerosol experiences both mixing with inorganic water and separation from it. Regional chemical transport model simulations including inorganic water (but excluding water uptake by organic compounds) in the partitioning medium for secondary organic aerosol (SOA) when RH > SRH led to increased SOA concentrations, particularly at night. Water uptake to the organic phase resulted in even greater SOA concentrations as a result of a positive feedback in which water uptake increased SOA, which further increased aerosol water and organic aerosol. Aerosol properties, such as the OM/OC and hygroscopicity parameter…

Abstract. In this work, we presented the characteristics of PM2. 5 chemical composition over China for the period of 2005–2012 by synthesis of in situ measurement data collected from literatures and satellite-based estimates using aerosol optical depth (AOD) data and the GEOS-Chem chemical transport model. We revealed the spatiotemporal variations in PM2. 5 composition during 2005–2012 and investigated the driving forces behind the variations by examining the changes in precursor emissions using a bottom-up emission inventory. Both in situ observations and satellite-based estimates identified that secondary inorganic aerosols (i.e., sulfate, nitrate, and ammonium; SNA) ranked as the highest fraction of dust-free PM2. 5 concentrations, followed by organic matter (OM) and black carbon (BC). For instance, satellite-based estimates found that SNA, OM, and BC contributed to 59, 33, and 8 %, respectively, of national population-weighted mean dust-free PM2. 5 concentrations during 2005–2012. National population-weighted mean PM2. 5 concentration increased from 63.9 µg m−3 in 2005 to 75.2…

Abstract. The second edition of the satellite-derived climate data record CLARA ("The CM SAF cLoud, Albedo and surface RAdiation dataset from AVHRR data" – second edition denoted CLARA-A2) is described. The data record covers the 34-year period from 1982 until 2015 and consists of cloud, surface albedo and surface radiation budget products derived from the AVHRR (Advanced Very High Resolution Radiometer) sensor carried by polar-orbiting, operational meteorological satellites. The data record is produced by the EUMETSAT Climate Monitoring Satellite Application Facility (CM SAF) project as part of the operational ground segment. Its upgraded content and methodology improvements since edition 1 are described in detail as well as some major validation results. Some of the main improvements of the data record come from a major effort in cleaning and homogenising the basic AVHRR level 1 radiance record and a systematic use of CALIPSO-CALIOP cloud information for development and validation purposes. Examples of applications studying decadal changes in Polar Summer surface albedo and cloud…

Abstract. Meteorological conditions within the planetary boundary layer (PBL) are closely governed by large-scale synoptic patterns and play important roles in air quality by directly and indirectly affecting the emission, transport, formation, and deposition of air pollutants. Partly due to the lack of long-term fine-resolution observations of the PBL, the relationships between synoptic patterns, PBL structure, and aerosol pollution in Beijing have not been well understood. This study applied the obliquely rotated principal component analysis in T-mode to classify the summertime synoptic conditions over Beijing using the National Centers for Environmental Prediction reanalysis from 2011 to 2014, and investigated their relationships with PBL structure and aerosol pollution by combining measurements of surface meteorological variables, fine-resolution soundings, the concentration of particles with diameters less than or equal to 2.5 μm, total cloud cover (CLD), and reanalysis data. Among the seven identified synoptic patterns, three types accounted for 67 % of the total number of…

Abstract. pH is a fundamental aerosol property that affects ambient particle concentration and composition, linking pH to all aerosol environmental impacts. Here, PM1 and PM2.5 pH are calculated based on data from measurements during the California Research at the Nexus of Air Quality and Climate Change (CalNex) study from 15 May to 15 June 2010 in Pasadena CA. Particle pH and water were predicted with the ISORROPIA-II thermodynamic model and validated by comparing predicted to measured gas-particle partitioning of inorganic nitrate, ammonium and chloride. The study mean ± standard deviation PM1 pH was 1.9 ± 0.5 for the SO42−-NO3−-NH4+-HNO3-NH3 system. For PM2.5, internal mixing of sea salt components (SO42−-NO3−-NH4+-Na+-Cl−-K+-HNO3-NH3-HCl system) raised the bulk pH to 2.7 ± 0.3 and improved predicted nitric acid partitioning with PM2.5 components. The results show little effect of sea salt on PM1 pH, but significant effects on PM2.5 pH. A mean PM1 pH of 1.9 at Pasadena was approximately one unit higher than what we have reported in the southeastern US, despite similar…

Abstract. The North China Plain (NCP) frequently experiences heavy haze pollution, particularly during wintertime. In winter 2015–2016, the NCP region suffered several extremely severe haze episodes with air pollution red alerts issued in many cities. We have investigated the sources and aerosol evolution processes of the severe pollution episodes in Handan, a typical industrialized city in the NCP region, using real-time measurements from an intensive field campaign during the winter of 2015–2016. The average (±1σ) concentration of submicron aerosol (PM1) during 3 December 2015–5 February 2016 was 187.6 (±137.5) µg m−3, with the hourly maximum reaching 700.8 µg m−3. Organic was the most abundant component, on average accounting for 45 % of total PM1 mass, followed by sulfate (15 %), nitrate (14 %), ammonium (12 %), chloride (9 %) and black carbon (BC, 5 %). Positive matrix factorization (PMF) with the multilinear engine (ME-2) algorithm identified four major organic aerosol (OA) sources, including traffic emissions represented by a hydrocarbon-like OA (HOA, 7 % of total OA),…

Abstract. High frequencies of haze in China, especially in the Beijing–Tianjin–Hebei region, have received widespread attention in recent years. In this study, samples of filtered atmospheric fine particulate matter (PM2.5) were collected synchronously at three urban sites (Beijing, Tianjin, and Shijiazhuang) and at a regional background site (Xinglong) for one month during each season from June 2014 to April 2015. Chemical composition determination/analysis, chemical mass closure, positive matrix factorization (PMF) and backward trajectory clustering were employed to investigate the chemical speciation, haze formation mechanism, emission sources, and influences of regional transport in North China. Our results reported that the aerosol chemical compositions were very similar at the urban sites and the background site and mainly comprised organic matter (16.0 %–25.0 %), sulfate (14.4 %–20.5 %), nitrate (15.1 %–19.5 %), ammonium (11.6 %–13.1 %) and mineral dust (14.7 %–20.8 %). Sources apportionment of PM2.5 by PMF model revealed that secondary aerosols (background) and secondary…

Abstract. Atmospheric pollutants have both beneficial and detrimental effects on carbon uptake by land ecosystems. Surface ozone 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 ozone and aerosol pollution on net primary productivity (NPP) in China. In the present day, air pollution reduces annual NPP by 0.4 Pg C (9 %), resulting from a decrease of 0.6 Pg C (14 %) by ozone damage, and an increase of 0.2 Pg C (5 %) by aerosol direct effects. The enhancement by aerosols is a combination of diffuse radiation fertilization, reduced…

Abstract. A new global reanalysis data set of atmospheric composition (AC) for the period 2003–2015 has been produced by the Copernicus Atmosphere Monitoring Service (CAMS). Satellite observations of total column (TC) carbon monoxide (CO) and aerosol optical depth (AOD) as well as several TC and profile observation of ozone have been assimilated with the Integrated Forecasting System for Composition (C-IFS) of the European Centre for Medium-Range Weather Forecasting. Compared to the previous MACC reanalysis (MACCRA), the new CAMS interim reanalysis (CAMSiRA) is of a coarser horizontal resolution of about 110 km compared to 80 km but covers a longer period with the intent to be continued to present day. This paper compares CAMSiRA against MACCRA and a control experiment (CR) without assimilation of AC retrievals. CAMSiRA has smaller biases than CR with respect to independent observations of CO, AOD and stratospheric ozone. However, ozone at the surface could not be improved by the assimilation. The assimilation of AOD led to a global reduction of sea salt and desert dust as well as…

Abstract. Ice nucleating particles (INP) are known to affect the amount of ice in mixed-phase clouds, thereby influencing many of their properties. The atmospheric INP concentration changes by orders of magnitude from terrestrial to marine environments, which typically contain much lower concentrations. Many modelling studies use parameterizations for heterogeneous ice nucleation and cloud ice processes that do not account for this difference because they were developed based on measurements predominantly from terrestrial environments. Errors in the assumed INP concentration will influence the simulated amount of ice in mixed-phase clouds, leading to errors in top-of-atmosphere radiative flux and ultimately the climate sensitivity of climate models. Here we develop a global model of INP concentrations relevant for mixed-phase clouds based on laboratory and field measurements of ice nucleation by K-feldspar (an ice-active component of desert dust) and marine organic aerosols (from sea spray). The simulated global distribution of INP concentrations based on these two-species agrees…

Abstract. Non-methane volatile organic compounds (NMVOC) include a large number of chemical species which differ significantly in their chemical characteristics and thus in their impacts on ozone and secondary organic aerosols formation. It is important that chemical transport models (CTMs) simulate the chemical transformation of the different NMVOC species in the troposphere consistently. In most emission inventories, however, only total NMVOC emissions are reported, which need to be decomposed into classes to fit the requirements of CTMs. For instance, the Emissions Database for Global Atmospheric Research (EDGAR) provides spatially resolved global anthropogenic emissions of total NMVOC. In this study the EDGAR NMVOC inventory was revised and extended in time and in sectors. Moreover the new version of NMVOC emission data in the EDGAR database were disaggregated on a high sector resolution to individual species or species groups, thus enhancing the usability of the NMVOC emission data by the modelling community. Region- and source-specific speciation profiles of NMVOC species or…

Abstract. A global chemistry-climate model has been used to study the impacts of pollutants released by agriculture on fine-particulate matter (PM2.5), with a focus on Europe, North America, East and South Asia. Simulations reveal that a relatively strong reduction in PM2.5 levels can be achieved by decreasing agricultural emissions, notably of ammonia (NH3) released from fertilizer use and animal husbandry. The absolute impact on PM2.5 reduction is strongest in East Asia, even for small emission decreases. Conversely, over Europe and North America, aerosol formation is not immediately limited by the availability of ammonia. Nevertheless, reduction of NH3 can also substantially decrease PM2.5 concentrations over the latter regions, especially when emissions are abated systematically. Our results document how reduction of agricultural emissions decreases aerosol pH due to the depletion of aerosol ammonium, which affects particle liquid phase and heterogeneous chemistry. Further, it is shown that a 50 % reduction of agricultural emissions could prevent the mortality attributable to…

Abstract. Aerosol direct effects (ADE), i.e., scattering and absorption of incoming solar radiation, reduce radiation reaching the ground and the resultant photolysis attenuation can decrease ozone (O3) formation in polluted areas. One the other hand, evidence also suggests that ADE associated cooling suppresses atmospheric ventilation thereby enhancing surface-level O3. Assessment of ADE impacts is thus important for understanding emission reduction strategies that seek co-benefits associated with reductions in both particulate matter and O3 levels. This study quantifies the impacts of ADE on tropospheric ozone by using a two-way online coupled meteorology and atmospheric chemistry model, WRF-CMAQ, instrumented with process analysis methodology. Two manifestations of ADE impacts on O3 including changes in atmospheric dynamics (ΔDynamics) and changes in photolysis rates (ΔPhotolysis) were assessed separately through multiple scenario simulations for January and July of 2013 over China. Results suggest that ADE reduced surface daily maxima 1 h O3 (DM1O3) in China by up to 39 μg m-3…

Abstract. The impact of ground-level ozone (O3) on vegetation is largely under-investigated at global scale despite worldwide large areas are exposed to high surface O3 levels and concentrations are expected to increase in the next future. To explore future potential impacts of O3 on vegetation, we compared historical and projected O3 concentrations simulated by six global atmospheric chemistry transport models on the basis of three representative concentration pathways emission scenarios (i.e. RCP2.6, 4.5, 8.5). To assess changes in the potential O3 threat to vegetation, we used the AOT40 metric. Results point out a significant overrun of AOT40 in comparison with the recommendations of UNECE for the protection of vegetation. In fact, many areas of the northern hemisphere show that AOT40-based critical levels will be exceeded by a factor of at least 10 under RCP8.5. Changes in surface O3 by 2100 range from about +4–5 ppb worldwide in RCP8.5 scenario to reductions of about 2–10 ppb in the RCP2.6 scenario. The risk of O3 injury for vegetation decreased by 61 % and 47 % under RCP2.6…

Abstract. Rapid industrialization and urbanization have caused frequent occurrence of haze in China during wintertime in recent years. The sulfate aerosol is one of the most important components of fine particles (PM2.5) in the atmosphere, contributing significantly to the haze formation. However, the heterogeneous formation mechanism of sulfate remains poorly characterized. Observed filter measurements of PM2.5, sulfate, and iron, and relative humidity in Xi'an, China have been employed to evaluate the mechanism and to develop a parameterization of the sulfate heterogeneous formation involving aerosol water for incorporation into atmospheric chemical transport models. Model simulations with the proposed parameterization can successfully reproduce the observed sulfate rapid growth and diurnal variations in Xi'an and Beijing, China. Reasonable representation of sulfate heterogeneous formation in chemical transport models considerably improves the PM2.5 simulations, providing the underlying basis for better understanding the haze formation and supporting the design and implementation…

Abstract. The relative contributions of eight nitrated aromatic compounds (NACs: nitrophenols and nitrated salicylic acids) to the light absorption of aqueous particle extracts and particulate brown carbon were determined from aerosol particle samples collected in Germany and China.High-volume filter samples were collected during six campaigns, performed at five locations in two seasons: (I) two campaigns with strong influence of biomass-burning (BB) aerosol at the TROPOS institute (winter, 2014, urban background, Leipzig, Germany) and the Melpitz research site (winter, 2014, rural background); (II) two campaigns with strong influence from biogenic emissions at Melpitz (summer, 2014) and the forest site Waldstein (summer, 2014, Fichtelgebirge, Germany); and (III) two CAREBeijing-NCP campaigns at Xianghe (summer, 2013, anthropogenic polluted background) and Wangdu (summer, 2014, anthropogenic polluted background with a distinct BB episode), both in the North China Plain. The filter samples were analyzed for NAC concentrations and the light absorption of aqueous filter extracts was…

Abstract. The WRF-Chem model coupled with a single-layer Urban Canopy Model (UCM) is integrated for 5 years at convection-permitting scale to investigate the individual and combined impacts of urbanization-induced changes in land cover and pollutants emission on regional climate in the Yangtze River Delta (YRD) region in eastern China. Simulations with the urbanization effects reasonably reproduced the observed features of temperature and precipitation in the YRD region. Urbanization over the YRD induces an Urban Heat Island (UHI) effect, which increases the surface temperature by 0.53 °C in summer and increases the annual heat wave days at a rate of 3.7 d/yr in the major megacities in the YRD, accompanied by intensified heat stress. In winter, the near-surface air temperature increases by approximately 0.7 °C over commercial areas in the cities but decreases in the surrounding areas. Radiative effects of aerosols tend to cool the surface air by reducing net shortwave radiation at the surface. Compared to the more localized UHI effect, aerosol effects on solar radiation and…

Abstract. Projections of the response to anthropogenic emission scenarios, evaluation of some greenhouse gas metrics and estimates of the social cost of carbon, often require a simple model that links emissions of carbon dioxide CO2 to atmospheric concentrations and global temperature changes. An essential requirement of such a model is to reproduce the behaviour of more complex models as well as an ability to sample their range of response in a transparent, accessible and reproducible form. Here we adapt the simple model of the Intergovernmental Panel on Climate Change 5th Assessment Report (IPCC-AR5) to explicitly represent the state-dependence of the CO2 airborne fraction and reproduce several idealised experiments performed with more complex models. We find that a simple linear increase in 100-year integrated airborne fraction with cumulative carbon uptake and global temperature change is both necessary and sufficient to represent the response of the climate system to CO2 on a range of timescales and under a range of experimental designs. Quantified ranges of uncertainty…

Abstract. Satellite NO2 observations have been widely used to evaluate emission changes. To determine trends in NOx emission over China, we used a method independent of chemical transport models to quantify the NOx emissions from 48 cities and 7 power plants over China, on the basis of Ozone Monitoring Instrument (OMI) NO2 observations during 2005 to 2015. We found that NOx emissions over 48 Chinese cities increased by 52 % from 2005 to 2011 and decreased by 21 % from 2011 to 2015. The decrease since 2011 could be mainly attributed to emission control measures in power sector; while cities with different dominant emission sources (i.e. power, industrial and transportation sectors) showed variable emission decline timelines that corresponded to the schedules for emission control in different sectors. The time series of the derived NOx emissions was consistent with the bottom-up emission inventories for all power plants (r = 0.8 on average), but not for some cities (r = 0.4 on average). The lack of consistency observed for cities was most probably due to the high uncertainty of…

Abstract. A revised Community Multi-scale Air Quality (CMAQ) model with updated secondary organic aerosol (SOA) yields and a more detailed description of SOA formation from isoprene oxidation was applied to study the spatial and temporal distribution of SOA in China in the entire year of 2013. Predicted organic carbon (OC), elemental carbon and volatile organic compounds agreed favorably with observations at several urban areas, although the high OC concentrations in wintertime in Beijing were under-predicted. Predicted summer SOA was generally higher (10–15 µg m−3) due to large contributions of isoprene (country average, 61 %), although the relative importance varies in different regions. Winter SOA was slightly lower and was mostly due to emissions of alkane and aromatic compounds (51 %). Contributions of monoterpene SOA was relatively constant (8–10 %). Overall, biogenic SOA accounted for approximately 75 % of total SOA in summer, 50–60 % in autumn and spring, and 24 % in winter. The Sichuan Basin had the highest predicted SOA concentrations in the country in all seasons, with…

Abstract. Relationship between aerosol optical depth (AOD) and PM2.5 is often investigated in order to obtain surface PM2.5 from satellite observation of AOD with a broad area coverage. However, various factors could affect the AOD-PM2.5 regressions. Using both ground and satellite observations in Beijing from 2011 to 2015, this study analyzes the influential factors including the aerosol type, relative humidity (RH), atmospheric boundary layer height (PBLH), wind speed and direction, and the vertical structure of aerosol distribution. The ratio of PM2.5 to AOD, which is defined as η, and the square of their correlation coefficient (R2) have been examined. It shows that η varies from 54.32 to 183.14, 87.32 to 104.79, 95.13 to 163.52 and 1.23 to 235.08 μg/m3 with aerosol type in four seasons respectively. η is smaller for scattering-dominant aerosols than for absorbing-dominant aerosols, and smaller for coarse mode aerosols than for fine mode aerosols. Both RH and PBLH affect the η value significantly. The higher the RH, the larger the η, and the higher the PBLH, the smaller the η.…

Abstract. Multiple trace-gas instruments were deployed during the fourth Fire Lab at Missoula Experiment (FLAME-4), including the first application of proton-transfer-reaction time-of-flight mass spectrometry (PTR-TOFMS) and comprehensive two-dimensional gas chromatography-time-of-flight mass spectrometry (GC×GC-TOFMS) for laboratory biomass burning (BB) measurements. Open-path Fourier-transform infrared spectroscopy (OP-FTIR) was also deployed, as well as whole air sampling (WAS) with one-dimensional gas chromatography-mass spectrometry (GC-MS) analysis. This combination of instruments provided an unprecedented level of detection and chemical speciation. The chemical composition and emission factors (EFs) determined by these four analytical techniques were compared for four representative fuels. The results demonstrate that the instruments are highly complementary, with each covering some unique and important ranges of compositional space, thus demonstrating the need for multi-instrument approaches to adequately characterize BB smoke emissions. Emission factors for overlapping…

Abstract. Particulate matter (PM), of which a significant fraction is comprised of secondary organic aerosols (SOA), has received considerable attention due to their health implications. In this study, the water-soluble oxidative potential (OPWS) of SOA generated from the photooxidation of biogenic and anthropogenic hydrocarbon precursors (isoprene, α-pinene, β-caryophyllene, pentadecane, m-xylene, and naphthalene) under different reaction conditions (RO2 + HO2/RO2 + NO dominant, dry/humid) was characterized using dithiothreitol (DTT) consumption. The measured intrinsic OPWS-DTT ranged from 9–205 pmol min−1 µg−1 and were highly dependent on the specific hydrocarbon precursor, with naphthalene and isoprene SOA generating the highest and lowest OPWS-DTT, respectively. Humidity and RO2 fate affected OPWS-DTT in a hydrocarbon-specific manner, with naphthalene SOA exhibiting the most pronounced effects, likely due to the formation of nitroaromatics. Together, these results suggest that precursor identity may be more influential than reaction condition in determining SOA health effects,…

Abstract. A severe regional haze problem in the megacity Beijing and surrounding areas, caused by fast formation and growth of fine particles, has attracted much attention in recent years. In order to investigate the secondary formation and aging process of urban aerosols, four intensive campaigns were conducted in four seasons between March 2012 and March 2013 at an urban site in Beijing (116.31° E, 37.99° N). An Aerodyne high-resolution time-of-flight aerosol mass spectrometry (HR-ToF-AMS) was deployed to measure non-refractory chemical components of submicron particulate matter (NR-PM1). The average mass concentrations of PM1 (NR-PM1+black carbon) were 45.1 ± 45.8, 37.5 ± 31.0, 41.3 ± 42.7, and 81.7 ± 72.4 µg m−3 in spring, summer, autumn, and winter, respectively. Organic aerosol (OA) was the most abundant component in PM1, accounting for 31, 33, 44, and 36 % seasonally, and secondary inorganic aerosol (SNA, sum of sulfate, nitrate, and ammonium) accounted for 59, 57, 43, and 55 % of PM1 correspondingly. Based on the application of positive matrix factorization (PMF), the…

Abstract. Modeling the interaction of dust with long-wave (LW) radiation is still a challenge because of the scarcity of information on the complex refractive index of dust from different source regions. In particular, little is known about the variability of the refractive index as a function of the dust mineralogical composition, which depends on the specific emission source, and its size distribution, which is modified during transport. As a consequence, to date, climate models and remote sensing retrievals generally use a spatially invariant and time-constant value for the dust LW refractive index. In this paper, the variability of the mineral dust LW refractive index as a function of its mineralogical composition and size distribution is explored by in situ measurements in a large smog chamber. Mineral dust aerosols were generated from 19 natural soils from 8 regions: northern Africa, the Sahel, eastern Africa and the Middle East, eastern Asia, North and South America, southern Africa, and Australia. Soil samples were selected from a total of 137 available samples in order to…

Abstract. The impact of regional emissions (e.g., domestic and international) on surface particulate matter (PM) concentrations in the Seoul Metropolitan Area (SMA), South Korea and its sensitivities to meteorology and emissions inventories are quantitatively estimated for 2014 using regional air quality modeling systems. Located on the downwind side of strong sources of anthropogenic emissions, South Korea bears the full impact of the regional transport of pollutants and their precursors. However, the impact of foreign emission sources have not yet been fully documented. We utilized two regional air quality simulation systems: (1) a Weather Research and Forecasting and Community Multi-Scale Air Quality (CMAQ) system; and (2) a United Kingdom Met Office Unified Model and CMAQ system. The following combinations of emission inventories are used: the Intercontinental Chemical Transport Experiment-Phase B, Inter-comparison Study for Asia 2010, and the National Institute of Environment Research Clean Air Policy Support System. Partial contributions of domestic and foreign emissions are…

Abstract. An assessment of global nitrate and ammonium aerosol based on simulations from nine models participating in the AeroCom Phase III study is presented. A budget analyses was conducted to understand the typical magnitude, distribution, and diversity of the aerosols and their precursors among the models. To gain confidence on model performance, the model results were evaluated with various observations globally, including ground station measurements over North America, Europe, and East Asia for tracer concentrations and dry and wet depositions, as well as with aircraft measurements in the Northern Hemisphere mid-high latitudes for tracer vertical distributions. Given the unique chemical and physical features of the nitrate occurrence, we further investigated the similarity and differentiation among the models by examining: (1) the pH-dependent NH3 wet deposition; (2) the nitrate formation via heterogeneous chemistry on the surface of dust and sea-salt particles; and (3) the nitrate coarse mode fraction (i.e., coarse/total). It is found that HNO3, which is simulated explicitly…

Abstract. Ozone profile trends over the period 2000 to 2016 from several merged satellite ozone data sets and from ground-based data measured by four techniques at stations of the Network for the Detection of Atmospheric Composition Change indicate significant ozone increases in the upper stratosphere, between 35 and 48 km altitude (5 and 1 hPa). Near 2 hPa (42 km), ozone has been increasing by about 1.5 % per decade in the tropics (20° S to 20° N), and by 2 to 2.5 % per decade in the 35 to 60° latitude bands of both hemispheres. At levels below 35 km (5 hPa), 2000 to 2016 ozone trends are smaller and not statistically significant. The observed trend profiles are consistent with expectations from chemistry climate model simulations. This study confirms positive trends of upper stratospheric ozone already reported, e.g., in the WMO/UNEP Ozone Assessment 2014 or by Harris et al. (2015). Compared to those studies, three to four additional years of observations, updated and improved data sets with reduced drift, and the fact that nearly all individual data sets indicate ozone increase…

Abstract. In this study we utilize a new dust product developed using CALIPSO observations and EARLINET measurements and methods to provide a 3D multiyear analysis on the evolution of Saharan dust over North Africa and Europe. The product utilizes CALIPSO L2 backscatter product corrected with a depolarization-based method to separate pure dust in external aerosol mixtures and an adjusted Saharan dust lidar ratio based on long-term EARLINET measurements. The methodology is applied on a nine-year CALIPSO dataset (2007–2015) and the results are analysed here to reveal for the first time the 3D dust evolution and the seasonal patterns of dust over its transportation paths from the Sahara towards the Mediterranean and Continental Europe. During spring, dust is uniformly distributed in the horizontal over the Sahara desert. The dust transport over the Mediterranean Sea results on mean Dust Optical Depth (DOD) values of 0.1. During summer, the dust activity is mostly shifted to the western part of the desert where mean DOD near the source is up to 0.6. Elevated dust plumes with mean…

Abstract. Heterogeneous reactions of mineral dust aerosol with trace gases in the atmosphere could directly and indirectly affect tropospheric oxidation capacity, in addition to aerosol composition and physicochemical properties. In this article we provide a comprehensive and critical review of laboratory studies of heterogeneous uptake of OH, NO3, O3, and their directly related species as well (including HO2, H2O2, HCHO, HONO, and N2O5) by mineral dust particles. Atmospheric importance of heterogeneous uptake as sinks for these species are assessed (i) by comparing their lifetimes with respect to heterogeneous reactions with mineral dust to lifetimes with respect to other major loss processes and (ii) by discussing relevant field and modelling studies. We have also outlined major open questions and challenges in laboratory studies of heterogeneous uptake by mineral dust and discussed research strategies to address them in order to better understand the effects of heterogeneous reactions with mineral dust on tropospheric oxidation capacity.

Abstract. Ground based Multi-Axis Differential Optical Absorption Spectroscopy (MAX-DOAS) and lidar measurements were performed in Shanghai, China during May 2016 to investigate the summertime atmospheric pollutants vertical distribution. In this study, vertical profiles of aerosol extinction coefficient, nitrogen dioxide (NO2) and formaldehyde (HCHO) concentrations were retrieved from MAX-DOAS measurement using the Heidelberg Profile (HeiPro) algorithm, while vertical distribution of ozone (O3) was obtained from an ozone lidar. Sensitivity study of the MAX-DOAS aerosol profile retrieval shows that the a priori aerosol profile shape has significant influences on the aerosol profile retrieval. Aerosol profiles retrieved from MAX-DOAS measurements with Gaussian a priori demonstrate the best agreements with simultaneous lidar measurements and vehicle-based tethered-balloon observations among all a priori aerosol profiles. MAX-DOAS measured tropospheric NO2Vertical Column Densities (VCDs) show a good agreement with OMI satellite observations with Pearson correlation coefficient (R) of…

Abstract. The weather research and forecasting model with chemistry (WRF-Chem) was used to investigate a typical dust storm event that occurred from 18th to 23rd March 2010 and swept across almost all of China, Japan, and Korea. WRF-Chem captured the spatial and temporal variations in dust aerosols and the meteorological conditions over East Asia well, and the results were used to further investigate details of processes related to dust emission, long-range transport, and radiative effects of dust aerosols over the Taklimakan desert (TD) and Gobi desert (GD). Results showed that the differences of weather conditions and topography and surface types in dust source regions may lead to the differences of dust emission, uplift height and transport. The typical dust event over East Asia was classified into two main stages. In the first stage (18th–20th March), the GD was located in the warm zone in advance of a cold front. The enhanced convection increased momentum transfer in the middle and lower troposphere because of the instability in the atmosphere. Moreover, the GD is located in…

Abstract. Mounting evidence from field and laboratory observations coupled with atmospheric model analyses show that primary combustion emissions of organic compounds dynamically partition between the vapor and particulate phases, especially as near-source emissions dilute and cool to ambient conditions. The most recent version of the Community Multiscale Air Quality (CMAQ) Model v5.2 accounts for the semivolatile partitioning and gas-phase aging of these primary organic aerosol (POA) compounds consistent with experimentally derived parameterizations. We also include a new surrogate species, potential secondary organic aerosol from combustion emissions (pcSOA), which provides a representation of the SOA from anthropogenic combustion sources that could be missing from current chemical transport model predictions. The reasons for this missing mass likely include the following: 1) unspeciated semivolatile and intermediate volatility organic compound (SVOC and IVOC, respectively) emissions missing from current inventories, 2) multigenerational aging of organic vapor products from known…

Abstract. Triple-wavelength polarization lidar measurements in Saharan dust layers were performed at Barbados (13.1° N, 59.6° W), 5000–8000 km west of the Saharan dust sources, in the framework of the Saharan Aerosol Long-range Transport and Aerosol-Cloud-Interaction Experiment (SALTRACE-1, June–July 2013, SALTRACE-3, June–July 2014). Three case studies are discussed. High quality was achieved by comparing the dust linear depolarization ratio profiles measured at 355, 532, and 1064 nm with respective dual-wavelength (355, 532 nm) depolarization ratio profiles measured with a reference lidar. A unique case of long-range transported dust over more than 12 000 km is presented. Saharan dust plumes crossing Barbados were measured with an airborne triple-wavelength polarization lidar over Missouri in the midwestern United States 7 days later. Similar dust optical properties and depolarization features were observed over both sites indicating almost unchanged dust properties within this 1 week of travel from the Caribbean to the United States. The main results of the triple-wavelength…

Abstract. Currently, the emission inventory of vehicular volatile organic compounds (VOCs) is one of those with the largest errors and uncertainties due to the imperfection of estimation methods and the lack of first-hand basic data. In this study, an updated speciated emission inventory of VOCs and an estimation of intermediate-volatility organic compounds (IVOCs) from vehicles in China at the provincial level, with a target year of 2015, were developed based on a set of state-of-the-art methods and a mass of local measurement data. The activity data for light-duty vehicles were derived from trajectories of more than 70 thousand cars for one year. The annual mileages of trucks were calculated from reported data by more than 2 million trucks in China. The emission profiles were updated using measurement data. Not only vehicular tailpipe emissions (VTEs) but also four kinds of vehicular evaporation emissions (VEEs), including refuelling, hot soak, diurnal and running loss, were taken into account. The results showed that the total vehicular VOCs emissions in China were 4.21 Tg and…

Abstract. We report continuous surface observations of carbon dioxide (CO2) and methane (CH4) from the Los Angeles (LA) Megacity Carbon Project during 2015. We devised a calibration strategy, methods for selection of background air masses, calculation of urban enhancements, and a detailed algorithm for estimating uncertainties in urban-scale CO2 and CH4 measurements. These methods are essential for understanding carbon fluxes from the LA megacity and other complex urban environments globally. We estimate background mole fractions entering LA using observations from four extra-urban sites including two marine sites located south of LA in La Jolla (LJO) and offshore on San Clemente Island (SCI), one continental site located in Victorville (VIC), in the high desert northeast of LA, and one continental/mid-troposphere site located on Mount Wilson (MWO) in the San Gabriel Mountains. We find that a local marine background can be established to within ∼ 1 ppm CO2 and ∼ 10 ppb CH4 using these local measurement sites. Overall, atmospheric carbon dioxide and methane levels are highly variable…

Abstract. New particle formation (NPF) events have been observed all around the world and are known to be a major source of atmospheric aerosol particles. Here we combine 20 years of observations in a boreal forest at the SMEAR II station (Station for Measuring Ecosystem-Atmosphere Relations) in Hyytiälä, Finland, by utilizing previously accumulated knowledge, and by focusing on clear-sky (non-cloudy) conditions. We first investigated the effect of cloudiness on NPF and then compared the NPF event and non-event days during clear-sky conditions. In this comparison we considered, for example, the effects of calculated particle formation rates, condensation sink, trace gas concentrations and various meteorological quantities. The formation rate of 1.5 nm particles was calculated by using proxies for gaseous sulfuric acid and oxidized products of low volatile organic compounds. As expected, our results indicate an increase in the frequency of NPF events under clear-sky conditions. Also, focusing on clearsky conditions enabled us to find a clear separation of many variables related to…

Abstract. Hydroxyl radical (OH) oxidation of toluene produces ring-retaining products: cresol and benzaldehyde, and ring-opening products: bicyclic intermediate compounds and epoxides. Here, first- and later-generation OH oxidation products from cresol and benzaldehyde are identified in laboratory chamber experiments. For benzaldehyde, first-generation ring-retaining products are identified, but later-generation products are not detected. For cresol, low-volatility (saturation mass concentration, C* ∼ 3.5 × 104 − 7.7 × 10−3 µg m−3), first- and later-generation ring-retaining products are identified. Subsequent OH addition to the aromatic ring of o-cresol leads to compounds such as hydroxy, dihydroxy, and trihydroxy methyl benzoquinones and dihydroxy, trihydroxy, tetrahydroxy, and pentahydroxy toluenes. These products are detected in the gas phase by chemical ionization mass spectrometry (CIMS) and in the particle phase using offline direct analysis in real-time mass spectrometry (DART-MS). Our data suggest that the yield of trihydroxy toluene from dihydroxy toluene is substantial.…