The 50 most-cited articles in Atmospheric chemistry and physics, 2016

Abstract. The Ozone Monitoring Instrument (OMI) onboard NASA's Aura satellite has been providing global observations of the ozone layer and key atmospheric pollutant gases, such as nitrogen dioxide (NO2) and sulfur dioxide (SO2), since October 2004. The data products from the same instrument provide consistent spatial and temporal coverage and permit the study of anthropogenic and natural emissions on local-to-global scales. In this paper, we examine changes in SO2 and NO2 over some of the world's most polluted industrialized regions during the first decade of OMI observations. In terms of regional pollution changes, we see both upward and downward trends, sometimes in opposite directions for NO2 and SO2, for different study areas. The trends are, for the most part, associated with economic and/or technological changes in energy use, as well as regional regulatory policies. Over the eastern US, both NO2 and SO2 levels decreased dramatically from 2005 to 2015, by more than 40 and 80 %, respectively, as a result of both technological improvements and stricter regulations of emissions.…

Abstract. There is evidence of ice melt, sea level rise to +5–9 m, and extreme storms in the prior interglacial period that was less than 1 °C warmer than today. Human-made climate forcing is stronger and more rapid than paleo forcings, but much can be learned by combining insights from paleoclimate, climate modeling, and on-going observations. We argue that ice sheets in contact with the ocean are vulnerable to non-linear disintegration in response to ocean warming, and we posit that ice sheet mass loss can be approximated by a doubling time up to sea level rise of at least several meters. Doubling times of 10, 20 or 40 years yield sea level rise of several meters in 50, 100 or 200 years. Paleoclimate data reveal that subsurface ocean warming causes ice shelf melt and ice sheet discharge. Our climate model exposes amplifying feedbacks in the Southern Ocean that slow Antarctic bottom water formation and increase ocean temperature near ice shelf grounding lines, while cooling the surface ocean and increasing sea ice cover and water column stability. Ocean surface cooling, in the…

Abstract. The important roles of the planetary boundary layer (PBL) in climate, weather and air quality have long been recognized, but little is known about the PBL climatology in China. Using the fine-resolution sounding observations made across China and reanalysis data, we conducted a comprehensive investigation of the PBL in China from January 2011 to July 2015. The boundary layer height (BLH) is found to be generally higher in spring and summer than that in fall and winter. The comparison of seasonally averaged BLHs derived from observations and reanalysis, on average, shows good agreement, despite the pronounced inconsistence in some regions. The BLH, derived from soundings conducted three or four times daily in summer, tends to peak in the early afternoon, and the diurnal amplitude of BLH is higher in the northern and western subregions of China than other subregions. The meteorological influence on the annual cycle of BLH is investigated as well, showing that BLH at most sounding sites is negatively associated with the surface pressure and lower tropospheric stability, but…

Abstract. The self-cleaning or oxidation capacity of the atmosphere is principally controlled by hydroxyl (OH) radicals in the troposphere. Hydroxyl has primary (P) and secondary (S) sources, the former through the photo-dissociation of ozone, the latter through OH recycling in radical reaction chains. We used the recent Mainz Organics Mechanism (MOM) to advance volatile organic carbon (VOC) chemistry in the general circulation model EMAC, and show that S is larger than previously assumed. MOM calculates substantially higher OH reactivity from VOC oxidation compared to predecessor models. Further, we find that nighttime OH formation may be significant in the polluted subtropical boundary layer in summer. Globally S exceeds P, most distinctively in the free troposphere. As a consequence, OH is buffered and not sensitive to perturbations by natural or anthropogenic emission changes. Complementary OH formation mechanisms in pristine and polluted environments of the continental and marine troposphere, connected through long-range transport of O3, maintain stable global OH levels.

Abstract. Methane is a greenhouse gas emitted by a range of natural and anthropogenic sources. Atmospheric methane has been measured continuously from space since 2003, and new instruments are planned for launch in the near future that will greatly expand the capabilities of space-based observations. We review the value of current, future, and proposed satellite observations to better quantify and understand methane emissions through inverse analyses, down to the scale of point sources and in combination with suborbital (surface and aircraft) data. Current observations from GOSAT are of high quality but have sparse spatial coverage. They provide limited information to quantify methane emissions on a regional (100–1000 km) scale. TROPOMI to be launched in late 2016 is expected to quantify daily emissions on the regional scale and will also effectively detect large point sources. Future satellite instruments with much higher spatial resolution, such as the recently launched GHGSat with 50 × 50 m2 resolution over targeted viewing domains, have the potential to detect a wide range of…

Abstract. Ozone pollution in the Southeast US involves complex chemistry driven by emissions of anthropogenic nitrogen oxide radicals (NOx ≡ NO + NO2) and biogenic isoprene. Model estimates of surface ozone concentrations tend to be biased high in the region and this is of concern for designing effective emission control strategies to meet air quality standards. We use detailed chemical observations from the SEAC4RS aircraft campaign in August and September 2013, interpreted with the GEOS-Chem chemical transport model (CTM) at 0.25°×0.3125° horizontal resolution, to better understand the factors controlling surface ozone in the Southeast US. We find that the National Emission Inventory (NEI) for NOx from the US Environmental Protection Agency (EPA) is too high in the Southeast and nationally by 50 %. This is demonstrated by SEAC4RS observations of NOx and its oxidation products, by surface network observations of nitrate wet deposition fluxes, and by OMI satellite observations of tropospheric NO2 columns. Upper tropospheric NO2 from lightning makes a large contribution to the…

Abstract. Ammonia (NH3) can interact in the atmosphere with other trace chemical species, which can lead to detrimental environmental consequences, such as the formation of fine particulates and ultimately global climate change. China is a major agricultural country, and livestock numbers and nitrogen fertilizer use have increased drastically since 1978, following the rapid economic and industrial development experienced by the country. In this study, comprehensive NH3 emissions inventories were compiled for China for 1980–2012. In a previous study, we parameterized emissions factors (EFs) considering ambient temperature, soil acidity, and the method and rate of fertilizer application. In this study, we refined these EFs by adding the effects of wind speed and new data from field experiments of NH3 flux in cropland in northern China. We found that total NH3 emissions in China increased from 5.9 to 11.2 Tg from 1980 to 1996, and then decreased to 9.5 Tg in 2012. The two major contributors were livestock manure and synthetic fertilizer application, which contributed 80–90 % of the…

Abstract. China has been experiencing severe air pollution in recent decades. Although ambient air quality monitoring network for criteria pollutants has been constructed in over 100 cities since 2013 in China, the temporal and spatial characteristics of some important pollutants, such as particulate matter (PM) components, remain unknown, limiting further studies investigating potential air pollution control strategies to improve air quality and associating human health outcomes with air pollution exposure. In this study, a yearlong (2013) air quality simulation using the Weather Research & Forecasting model (WRF) and the Community Multi-scale Air Quality model (CMAQ) was conducted to provide detailed temporal and spatial information of ozone (O3), PM2.5 total and chemical components. Multi-resolution Emission Inventory for China (MEIC) was used for anthropogenic emissions and observation data obtained from the national air quality monitoring network were collected to validate model performance. The model successfully reproduces the O3 and PM2.5 concentrations at most cities for…

Abstract. The mixing layer is an important meteorological factor that affects atmospheric pollution. A study of atmospheric pollution in the Beijing area was performed from July 2009 to December 2012, using a ceilometer, to observe and study the atmospheric mixing layer height (MLH). Based on a comparison and validation of multiple types of data, we evaluated the quality of the MLH data as observed by the ceilometer and found that the ceilometer underestimates MLH during neutral stratification caused by strong winds, whereas it overestimates MLH during dust crossing. By combining conventional meteorological data and PM2.5 and PM10 observational data, we screened the observational results for the MLH, and the ceilometer observations were fairly consistent with the meteorological radiosonde profile results. The correlation coefficient is more than 0.9, and the effective rate of acquired data is near 80 %. Further analysis of the variation in the MLH indicates that the MLH in the Beijing area exhibits the feature of being low in autumn and winter and being high in spring and summer.…

Abstract. The AIRUSE-LIFE+ project aims at characterising similarities and heterogeneities in PM sources and contributions in urban areas from the Southern Europe. Once the main PMx sources are identified, AIRUSE aims at developing and testing the efficiency of specific and non-specific measures to improve urban air quality. This article reports the results of the source apportionment of PM10 and PM2.5 conducted at three urban background sites (Barcelona, Florence and Milan, BCN-UB, FI-UB, MLN-UB) one sub-urban background site (Athens, ATH-SUB) and one traffic site (Porto, POR-TR). After collecting 1047 PM10 and 1116 PM2.5 24 h samples from January 2013 to February 2014 simultaneously at the 5 cities, these were analysed for the contents of OC, EC, anions, cations, major and trace elements and levoglucosan. The USEPA PMF5 receptor model was applied to these datasets in a harmonised way for each city. The sum of vehicle exhaust and non-exhaust contributes within 3.9–10.8 μg m−3 (16–32 %) to PM10 and 2.3–9.4 μg m−3 (15–36 %) to PM2.5, although a fraction of secondary nitrate is also…

Abstract. Winter has the worst air pollution in a year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge on the sources, formation mechanisms and evolution of aerosol particles is not complete. Here we have a comprehensive characterization of the sources, variations and processes of submicron aerosols that were measured by an Aerodyne high-resolution aerosol mass spectrometer from December 17, 2013 to January 17, 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was overall similar in winter among different years, which was mainly composed of organics (60 %), sulfate (15 %) and nitrate (11 %). Positive matrix factorization of high- and unit-mass resolution spectra identified four primary organic aerosol (POA) factors from traffic, cooking, biomass burning (BBOA) and coal combustion (CCOA) emissions, and two secondary OA (SOA) factors. POA dominated OA, on average accounting for 56% with CCOA being the largest contributor (20 %). Both CCOA and BBOA showed…

Abstract. During winter 2013–2014 aerosol mass spectrometer (AMS) measurements were conducted for the first time with a novel PM2.5 (particulate matter with aerodynamic diameter ≤ 2.5 μm) lens in two major cities of China: Xi'an and Beijing. We denote the periods with visibility below 2 km as extreme haze and refer to the rest as reference periods. During the measurements in Xi'an an extreme haze covered the city for about a week and the total non-refractory (NR)-PM2.5 mass fraction reached peak concentrations of over 1000 μg m-3. During the measurements in Beijing two extreme haze events occurred, but the temporal extent and the total concentrations reached during these events were lower than in Xi'an. Average PM2.5 concentrations of 537 ± 146 μg m-3 and 243 ± 47 μg m-3 (including NR species and equivalent black carbon, eBC) were recorded during the extreme haze events in Xi'an and Beijing, respectively. During the reference periods the measured average concentrations were 140 ± 99 μg m-3 in Xi'an and 75 ± 61 μg m-3 in Beijing. The relative composition of the NR-PM2.5 evolved…

Abstract. The formation and aging of organic aerosols (OA) proceed through multiple steps of chemical reaction and mass transport in the gas and particle phases, which is challenging for the interpretation of field measurements and laboratory experiments as well as accurate representation of OA evolution in atmospheric aerosol models. Based on data from over 30 000 compounds, we show that organic compounds with a wide variety of functional groups fall into molecular corridors, characterized by a tight inverse correlation between molar mass and volatility. We developed parameterizations to predict the volatility of organic compounds containing oxygen, nitrogen and sulfur from the elemental composition that can be measured by soft-ionization high-resolution mass spectrometry. Field measurement data from new particle formation events, biomass burning, cloud/fog processing, and indoor environments were mapped into molecular corridors to characterize the chemical nature of the observed OA components. We found that less oxidized indoor OA are constrained to a corridor of low molar mass…

Abstract. We present a simulation of the global composition of the troposphere which includes the chemistry of halogens (Cl, Br, I). Building on previous work within the GEOS-Chem model we include emissions of inorganic iodine from the oceans, anthropogenic and biogenic sources of halogenated gases, gas phase chemistry, and a parameterised approach to heterogeneous halogen chemistry. Consistent with Schmidt et al. (2016) we do not include sea-salt de-bromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. IO shows both high and low biases in different datasets, BrO concentrations though appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggests the model represents a lower limit on impacts due to likely underestimates in emissions and therefore burdens. Inclusion of Cl, Br, I results in a general improvement in simulation of ozone (O3) concentrations, except in polar regions where the model now underestimates O3 concentrations. Halogen chemistry reduces the global…

Abstract. The ability of certain components of particulate matter to induce oxidative stress through catalytic generation of reactive oxygen species (ROS) in vivo may be one mechanism accounting for observed linkages between ambient aerosols and adverse health outcomes. A variety of assays have been used to measure this so-called aerosol oxidative potential. We developed a semi-automated system to quantify oxidative potential of filter aqueous extracts utilizing the dithiothreitol (DTT) assay and have recently developed a similar semi-automated system using the ascorbic acid (AA) assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed using both assays. We found that water-soluble DTT activity on a per air volume basis was more spatially uniform than water-soluble AA activity. DTT activity was higher in winter than in summer/fall, whereas AA activity was higher in summer/fall compared to winter, with highest levels near highly trafficked highways. DTT activity was correlated with organic and metal species, whereas AA…

Abstract. The EDGAR (Emissions Database for Global Atmospheric Research) v4.3 global anthropogenic emissions inventory of several gaseous (SO2, NOx, CO, non-methane volatile organic compounds (NMVOCs) and NH3) and particulate (PM10, PM2.5, black and organic carbon (BC and OC)) air pollutants for the period 1970–2010 is used to develop retrospective air pollution emission scenarios to quantify the roles and contributions of changes in fuels consumption, technology, end-of-pipe emission reduction measures and their resulting impact on health and crop yields. This database presents changes in activity data, fuels and air pollution abatement technology for the past 4 decades, using international statistics and following guidelines for bottom-up emission inventory at the Tier 1 and Tier 2 levels with region-specific default values. With two further retrospective scenarios we assess (1) the impact of the technology and end-of-pipe (EOP) reduction measures in the European Union (EU) by considering a stagnation of technology with constant emission factors from 1970 and with no further…

Abstract. Recent laboratory studies suggest that secondary organic aerosol (SOA) formation rates are higher than assumed in current models. There is also evidence that SOA removal by dry and wet deposition occurs more efficiently than some current models suggest, and that photolysis and heterogeneous oxidation may be important (but currently ignored) SOA sinks. Here, we have updated the global GEOS-Chem model to include this new information on formation (i.e. wall-corrected yields and emissions of semi-volatile and intermediate volatility organic compounds) and on removal processes (photolysis and heterogeneous oxidation). We compare simulated SOA from various model configurations against ground, aircraft and satellite measurements to assess the extent to which these improved representations of SOA formation and removal processes are consistent with observed characteristics of the SOA distribution. The updated model presents a more dynamic picture of the lifecycle of atmospheric SOA, with production rates 4 times higher and sinks a factor of 3.7 more efficient than in the base…

Abstract. Isoprene emitted by vegetation is an important precursor of secondary organic aerosol (SOA), but the mechanism and yields are uncertain. Aerosol is prevailingly aqueous under the humid conditions typical of isoprene-emitting regions. Here we develop an aqueous-phase mechanism for isoprene SOA formation coupled to a detailed gas-phase isoprene oxidation scheme. The mechanism is based on aerosol reactive uptake probabilities (γ) for water-soluble isoprene oxidation products, including sensitivity to aerosol acidity and nucleophile concentrations. We apply this mechanism to simulation of aircraft (SEAC4RS) and ground-based (SOAS) observations over the Southeast US in summer 2013 using the GEOS-Chem chemical transport model. Emissions of nitrogen oxides (NOx ≡ NO + NO2) over the Southeast US are such that the peroxy radicals produced from isoprene oxidation (ISOPO2) react significantly with both NO (high-NOx pathway) and HO2 (low-NOx pathway), leading to different suites of isoprene SOA precursors. We find a mean SOA mass yield of 3.3 % from isoprene oxidation, consistent with…

Abstract. The Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5) Experiment was carried out in the environs of Manaus, Brazil, in the central region of the Amazon basin during two years from 1 January 2014 through 31 December 2015. The experiment focused on the complex interactions among vegetation, atmospheric chemistry, and aerosol production on the one hand and their connections to aerosols, clouds, and precipitation on the other. The objective was to understand and quantify these linked processes, first under natural conditions to obtain a baseline and second when altered by the effects of human activities. To this end, the pollution plume from the Manaus metropolis, superimposed on the background conditions of the central Amazon basin, served as a natural laboratory. The present paper, as the Introduction to the GoAmazon2014/5 Special Issue, presents the context and motivation of the GoAmazon2014/5 Experiment. The nine research sites, including the characteristics and instrumentation of each site, are presented. The sites range from time point zero (T0) upwind…

Abstract. A global vertically resolved aerosol data set covering more than 10 years of observations at more than 20 measurement sites distributed from 63° N to 52° S and 72° W to 124° E has been achieved within the Raman and polarization lidar network PollyNET. This network consists of portable, remote-controlled multiwavelength-polarization-Raman lidars (Polly) for automated and continuous 24/7 observations of clouds and aerosols. PollyNET is an independent, voluntary, and scientific network. All Polly lidars feature a standardized instrument design and apply unified calibration, quality control, and data analysis. The observations are processed in near-real time without manual intervention, and are presented online at http://polly.tropos.de. The paper gives an overview of the observations on four continents and two research vessels obtained with eight Polly systems. The specific aerosol types at these locations (mineral dust, smoke, dust-smoke and other dusty mixtures, urban haze, and volcanic ash) are identified by their Ångström exponent, lidar ratio, and depolarization ratio.…

Abstract. Ozone pollution has become one of the top environmental concerns in eastern China. Quantifying temporal trend of surface ozone concentrations is very meaningful to assess the impacts of the anthropogenic precursor reductions and the effects of emission control strategies. The level of surface ozone is impacted by both emissions of precursors and meteorological conditions. In order to examine the variation trend of ozone from 2003 to 2015 in Shangdianzi regional atmosphere background station, the modified KZ filter method was performed in this study to remove the influence of meteorological fluctuations on ozone concentrations. Results reveal that the short-term component, seasonal component and long-term component of ozone account for 36.4, 57.6 and 2.2 % of the total variance, respectively. The long-term trend shows that the surface daily maximum 8-h O3 has undergone a significant increase during 2003–2015, with a rate of 1.1 ppb yr−1. We find that the increase was completely resulted from the change of the emissions when the influence of the meteorological factors was…

Long-term monitoring of data of ambient mercury (Hg) on a global scale to assess its emission, transport, atmospheric chemistry, and deposition processes is vital to understanding the impact of Hg pollution on the environment. The Global Mercury Observation System (GMOS) project was funded by the European Commission (http://www.gmos.eu) and started in November 2010 with the overall goal to develop a coordinated global observing system to monitor Hg on a global scale, including a large network of ground-based monitoring stations, ad hoc periodic oceanographic cruises and measurement flights in the lower and upper troposphere as well as in the lower stratosphere. To date, more than 40 ground-based monitoring sites constitute the global network covering many regions where little to no observational data were available before GMOS. This work presents atmospheric Hg concentrations recorded worldwide in the framework of the GMOS project (2010-2015), analyzing Hg measurement results in terms of temporal trends, seasonality and comparability within the network. Major findings highlighted in…

Abstract. The microphysical and radiative properties of cirrus clouds continue to be beyond understanding and thus still represent one of the largest uncertainties in the prediction of the Earth's climate (IPCC, 2013). Our study aims to provide a guide to cirrus microphysics, which is compiled from an extensive set of model simulations, covering the broad range of atmospheric conditions for cirrus formation and evolution. The model results are portrayed in the same parameter space as field measurements, i.e. in the Ice Water Content-Temperature (IWC-T) parameter space. We validate this cirrus analysis approach by evaluating cirrus data sets from seventeen aircraft campaigns, conducted in the last fifteen years, spending about 94 h in cirrus over Europe, Australia, Brazil as well as Southern and Northern America. Altogether, the approach of this study is to track cirrus IWC development with temperature by means of model simulations, compare with observations and then assign, to a certain degree, cirrus microphysics to the observations. Indeed, the field observations show…

Abstract. Recent observations suggest that a certain fraction of organic carbon (OC) aerosol effectively absorbs solar radiation, which is also known as brown carbon (BrC) aerosol. Despite much observational evidence of its presence, very few global modeling studies have been conducted because of poor understanding of global BrC emissions. Here we present an explicit global simulation of BrC in a global 3-D chemical transport model (GEOS-Chem), including global BrC emission estimates from primary (5.7 and 4.3 Tg C yr-1 from biomass burning and biofuel) and secondary (5.7 Tg C yr-1 from aromatic oxidation) sources. We evaluate the model by comparing the results with observed absorption by OC in surface air in the United States, and with single scattering albedo observations at AERONET sites all over the globe. The model successfully reproduces the observed seasonal variations, but underestimates the magnitudes, especially in regions with high secondary source contributions. Our global simulations show that BrC accounts for 24 % of the global mean OC concentration, which is typically…

Abstract. We analyze a multi-day photochemical smog episode to understand the oxidative capacity and radical chemistry of the polluted atmosphere in Hong Kong and the Pearl River Delta (PRD) region. A photochemical box model based on the Master Chemical Mechanism (MCM v3.2) is constrained by an intensive set of field observations to elucidate the budgets of ROX (ROX=OH+HO2+RO2) and NO3 radicals. Highly abundant radical precursors (i.e., O3, HONO and carbonyls), nitrogen oxides (NOX) and volatile organic compounds (VOCs) facilitate strong production and efficient recycling of ROX radicals. The OH reactivity is dominated by oxygenated VOCs (OVOCs), followed by aromatics, alkenes and alkanes. Photolysis of OVOCs (except for formaldehyde) is the dominant primary source of ROX with an average daytime contribution of 47 %. HONO photolysis is the largest contributor to OH and the second most significant source (19 %) of ROX. Other considerable ROX sources include O3 photolysis (11 %), formaldehyde photolysis (10 %), and ozonolysis reactions of unsaturated VOCs (6.2 %). In one case when…

Abstract. Sulfur dioxide (SO2) measurements from the Ozone Monitoring Instrument (OMI) satellite sensor processed with the new principal component analysis (PCA) algorithm were used to detect large point emission sources or clusters of sources. The total of 491 continuously emitting point sources releasing from about 30 kt yr−1 to more than 4000 kt yr−1 of SO2 per year have been identified and grouped by country and by primary source origin: volcanoes (76 sources); power plants (297); smelters (53); and sources related to the oil and gas industry (65). The sources were identified using different methods, including through OMI measurements themselves applied to a new emission detection algorithm, and their evolution during the 2005–2014 period was traced by estimating annual emissions from each source. For volcanic sources, the study focused on continuous degassing, and emissions from explosive eruptions were excluded. Emissions from degassing volcanic sources were measured, many for the first time, and collectively they account for about 30 % of total SO2 emissions estimated from…

Abstract. Formation of organic nitrates (RONO2) during oxidation of biogenic volatile organic compounds (BVOCs: isoprene, monoterpenes) is a significant loss pathway for atmospheric nitrogen oxide radicals (NOx), but the chemistry of RONO2 formation and degradation remains uncertain. Here we implement a new BVOC oxidation mechanism (including updated isoprene chemistry, new monoterpene chemistry, and particle uptake of RONO2) in the GEOS-Chem global chemical transport model with ∼ 25 × 25 km2 resolution over North America. We evaluate the model using aircraft (SEAC4RS) and ground-based (SOAS) observations of NOx, BVOCs, and RONO2 from the Southeast US in summer 2013. The updated simulation successfully reproduces the concentrations of individual gas- and particle-phase RONO2 species measured during the campaigns. Gas-phase isoprene nitrates account for 25–50 % of observed RONO2 in surface air, and we find that another 10 % is contributed by gas-phase monoterpene nitrates. Observations in the free troposphere show an important contribution from long-lived nitrates derived from…

Abstract. We present a new method to quantify NOx emissions and corresponding atmospheric lifetimes from OMI NO2 observations together with ECMWF wind fields without further model input for sources located in a polluted background. NO2 patterns under calm wind conditions are used as proxy for the spatial patterns of NOx emissions, and the effective atmospheric NOx lifetime is determined from the change of spatial patterns measured at larger wind speeds. Emissions are subsequently derived from the NO2 mass above the background, integrated around the source of interest. Lifetimes and emissions are estimated for 17 power plants and 53 cities located in non-mountainous regions across China and the USA. The derived lifetimes for the ozone season (May–September) are 3.8 ± 1.0 h (mean ± standard deviation) with a range of 1.8 to 7.5 h. The derived NOx emissions show generally good agreement with bottom-up inventories for power plants and cities. Regional inventory shows better agreement with top-down estimates for Chinese cities compared to global inventory, most likely due to different…

Abstract. The online coupled Weather Research and Forecasting-Chemistry (WRF-Chem) model was applied to simulate a haze event that happened in January 2010 in the North China Plain (NCP), and was validated against various types of measurements. The evaluations indicate that WRF-Chem provides reliable simulations for the 2010 haze event in the NCP. This haze event is mainly caused by high emissions of air pollutants in the NCP and stable weather conditions in winter. Secondary inorganic aerosols also played an important role and cloud chemistry had important contributions. Air pollutants outside Beijing contributed about 47.8 % to the PM2.5 levels in Beijing during this haze event, and most of them are from south Hebei, Shandong and Henan provinces. In addition, aerosol feedback has important impacts on surface temperature, Relative Humidity (RH) and wind speeds, and these meteorological variables affect aerosol distribution and formation in turn. In Shijiazhuang, Planetary Boundary Layer (PBL) decreased about 300 m and PM2.5 increased more than 20 μg m-3 due to aerosol feedback.…

Abstract. Surface ozone is a secondary air pollutant produced during the atmospheric photochemical degradation of emitted volatile organic compounds (VOCs) in the presence of sunlight and nitrogen oxides (NOx). Temperature directly influences ozone production through speeding up the rates of chemical reactions and increasing the emissions of VOCs, such as isoprene, from vegetation. In this study, we used an idealised box model with different chemical mechanisms (Master Chemical Mechanism, MCMv3.2; Common Representative Intermediates, CRIv2; Model for OZone and Related Chemical Tracers, MOZART-4; Regional Acid Deposition Model, RADM2; Carbon Bond Mechanism, CB05) to examine the non-linear relationship between ozone, NOx and temperature, and we compared this to previous observational studies. Under high-NOx conditions, an increase in ozone from 20 to 40 °C of up to 20 ppbv was due to faster reaction rates, while increased isoprene emissions added up to a further 11 ppbv of ozone. The largest inter-mechanism differences were obtained at high temperatures and high-NOx emissions. CB05…

Abstract. We use the combined Dark Target/Deep Blue aerosol optical depth (AOD) satellite product of the Moderate-resolution Imaging Spectroradiometer (MODIS) collection 6 to study trends over the Middle East between 2000 and 2015. Our analysis corroborates a previously identified positive AOD trend over large parts of the Middle East during the period 2001 to 2012. We relate the annual AOD to precipitation, soil moisture and surface winds to identify regions where these attributes are directly related to the AOD over Saudi Arabia, Iraq and Iran. Regarding precipitation and soil moisture, a relatively small area in and surrounding Iraq turns out to be of prime importance for the AOD over these countries. Regarding surface wind speed, the African Red Sea coastal area is relevant for the Saudi Arabian AOD. Using multiple linear regression we show that AOD trends and interannual variability can be attributed to soil moisture, precipitation and surface winds, being the main factors controlling the dust cycle. Our results confirm the dust driven AOD trends and variability, supported by a…

Abstract. Within the framework of air quality studies at the megacity scale, highly time-resolved volatile organic compound (C2–C8) measurements were performed in downtown Paris (urban background sites) from January to November 2010. This unique dataset included non-methane hydrocarbons (NMHCs) and aromatic/oxygenated species (OVOCs) measured by a GC-FID (gas chromatograph with a flame ionization detector) and a PTR-MS (proton transfer reaction – mass spectrometer), respectively. This study presents the seasonal variability of atmospheric VOCs being monitored in the French megacity and their various associated emission sources. Clear seasonal and diurnal patterns differed from one VOC to another as the result of their different origins and the influence of environmental parameters (solar radiation, temperature). Source apportionment (SA) was comprehensively conducted using a multivariate mathematical receptor modeling. The United States Environmental Protection Agency's positive matrix factorization tool (US EPA, PMF) was used to apportion and quantify ambient VOC concentrations…

Abstract. Soil organic matter (SOM) may be a significant source of atmospheric ice nucleating particles (INPs), especially of those active >-15 °C. However, due to both a lack of investigations and the complexity of the SOM itself, the principal sources of these INPs remain unknown. To more comprehensively characterize organic INPs we tested locally representative soils in Wyoming and Colorado for total organic INPs, INPs in the heat-labile fraction, ice nucleating (IN) bacteria, IN fungi, IN fulvic and humic acids, IN plant tissue, and ice nucleation by monolayers of aliphatic alcohols. All soils contained ≈106 to ≈5 ×107 INPs g-1 dry soil active at -10 °C. Removal of SOM with H2O2 effectively removed all INPs active >-18 °C (the limit of testing), while heating of soil suspensions to 105 °C showed that labile INPs increasingly predominated >-12 °C and comprised ≥90% of INPs active >-9 °C. Papain protease, which inactivates IN proteins produced by the fungus Mortierella alpina, common in the region’s soils, lowered INPs active at ≥-11 °C by ≥75% in two arable soil and sagebrush…

Abstract. Single scattering albedo (SSA) and absorption angstrom exponent (AAE) are two critical parameters in determining the impact of absorbing aerosol on the Earth's radiative balance. Aerosol emitted by biomass burning represent a significant fraction of absorbing aerosol globally, but it remains difficult to accurately predict SSA and AAE for biomass burning aerosol. Black carbon (BC), brown carbon (BrC), and non-absorbing coatings all make significant contributions to the absorption coefficient of biomass burning aerosol. SSA and AAE cannot be directly inferred based on fuel type because they depend strongly on burn conditions. It has been suggested that SSA can be effectively parameterized via the modified combustion efficiency (MCE) of a biomass-burning event and that this would be useful because emission factors for the MCE of a large number of fuels are available. Here we demonstrate, with data from the FLAME-4 experiment, that for a wide variety of globally relevant biomass fuels, over a range of combustion conditions, parameterizations of SSA and AAE based on the…

Abstract. Elemental carbon (EC) has been widely used as a tracer to track the portion of co-emitted primary organic carbon (OC) and, by extension, to estimate secondary OC (SOC) from ambient observations of EC and OC. Key to this EC tracer method is to determine an appropriate OC / EC ratio that represents primary combustion emission sources (i.e., (OC / EC)pri) at the observation site. The conventional approaches include regressing OC against EC within a fixed percentile of the lowest (OC / EC) ratio data (usually 5–20 %) or relying on a subset of sampling days with low photochemical activity and dominated by local emissions. The drawback of these approaches is rooted in its empirical nature, i.e., a lack of clear quantitative criteria in the selection of data subsets for the (OC / EC)pri determination. We examine here a method that derives (OC / EC)pri through calculating a hypothetical set of (OC / EC)pri and SOC followed by seeking the minimum of the coefficient of correlation (R2) between SOC and EC. The hypothetical (OC / EC)pri that generates the minimum R2(SOC,EC) then…

Abstract. Tropospheric ozone (O3) is a trace gas playing important roles in atmospheric chemistry, air quality and climate change. In contrast to North America and Europe, long-term measurements of surface O3 are very limited in China. We compile available O3 observations at Mt. Tai – the highest mountain over the North China Plain – during 2003–2015 and analyze the decadal change of O3 and its sources. A linear regression analysis shows that summertime O3 measured at Mt. Tai has increased significantly by 1.7 ppbv yr−1 for June and 2.1 ppbv yr−1 for the July–August average. The observed increase is supported by a global chemistry-climate model hindcast (GFDL-AM3) with O3 precursor emissions varying from year to year over 1980–2014. Analysis of satellite data indicates that the O3 increase was mainly due to the increased emissions of O3 precursors, in particular volatile organic compounds (VOCs). An important finding is that the emissions of nitrogen oxides (NOx) have diminished since 2011, but the increase of VOCs appears to have enhanced the ozone production efficiency and…

Abstract. Peat fires in Southeast Asia have become a major annual source of trace gases and particles to the regional-global atmosphere. The assessment of their influence on atmospheric chemistry, climate, air quality, and health has been uncertain partly due to a lack of field measurements of the smoke characteristics. During the strong 2015 El Niño event we deployed a mobile smoke sampling team in the Indonesian province of Central Kalimantan on the island of Borneo and made the first, or rare, field measurements of trace gases, aerosol optical properties, and aerosol mass emissions for authentic peat fires burning at various depths in different peat types. This paper reports the trace gas and aerosol measurements obtained by Fourier transform infrared spectroscopy, whole air sampling, photoacoustic extinctiometers (405 and 870 nm), and a small subset of the data from analyses of particulate filters. The trace gas measurements provide emission factors (EFs, g compound per kg biomass burned) for CO2, CO, CH4, non-methane hydrocarbons up to C10, 15 oxygenated organic compounds, NH3,…

Abstract. More size-resolved chemical information is needed before the physicochemical characteristics and sources of airborne particles can be understood, but this information remains unavailable in most regions of China due to a paucity of measurement data. In this study, we report a one-year observation of various chemical species in size-segregated particle samples collected in urban Beijing, a mega city that experiences severe haze episodes. In addition to fine particles, the measured particle size distributions showed high concentrations of coarse particles during the haze periods. The abundance and chemical compositions of the particles in this study were temporally and spatially variable, with major contributions from organic matter and secondary inorganic aerosols. The contribution of the organic matter to the mass decreased from 37.9 to 33.1%, whereas the total contribution of SO42−, NO3− and NH4+ increased from 19.1 to 32.3% on non-haze and haze days, respectively. Due to heterogeneous reactions and hygroscopic growth, the peaks in the size distributions of organic…

Abstract. The chemical link between isoprene and formaldehyde (HCHO) is a strong, non-linear function of NOx (= NO + NO2). This relationship is a linchpin for top-down isoprene emission inventory verification from orbital HCHO column observations. It is also a benchmark for overall mechanism performance with regard to VOC oxidation. Using a comprehensive suite of airborne in situ observations over the Southeast US, we quantify HCHO production across the urban-rural spectrum. Analysis of isoprene and its major first-generation oxidation products allows us to define both a "prompt" yield of HCHO (molecules of HCHO produced per molecule of freshly-emitted isoprene) and the background HCHO mixing ratio (from oxidation of longer-lived hydrocarbons). Over the range of observed NOx values (roughly 0.1–2 ppbv), the prompt yield increases by a factor of 3 (from 0.3 to 0.9 ppbv ppbv−1), while background HCHO increases by more than a factor of 2 (from 1.5 to 3.3 ppbv). We apply the same method to evaluate the performance of both a global chemical transport model (AM3) and a…

Abstract. In this paper, the variation and trend of haze pollution in eastern China for winter of 1960–2012 were analyzed. With the overall increasing number of winter haze days in this period, the 5 decades were divided into three sub-periods based on the changes of winter haze days (WHD) in central North China (30–40° N) and eastern South China (south of 30° N) for east of 109° E mainland China. Results show that WHD kept gradually increasing during 1960–1979, remained stable overall during 1980–1999, and increased fast during 2000–2012. The author identified the major climate forcing factors besides total energy consumption. Among all the possible climate factors, variability of the autumn Arctic sea ice extent, local precipitation and surface wind during winter is most influential to the haze pollution change. The joint effect of fast increase of total energy consumption, rapid decline of Arctic sea ice extent and reduced precipitation and surface winds intensified the haze pollution in central North China after 2000. There is a similar conclusion for haze pollution in eastern…

Abstract. Mineral dust particles from wind-blown soils are known to act as effective ice nucleating particles in the atmosphere and are thought to play an important role in the glaciation of mixed phase clouds. Recent work suggests that feldspars are the most efficient nucleators of the minerals commonly present in atmospheric mineral dust. However, the feldspar group of minerals is complex, encompassing a range of chemical compositions and crystal structures. To further investigate the ice-nucleating properties of the feldspar group we measured the ice nucleation activities of 15 well-characterised feldspar samples. We show that alkali feldspars, in particular the potassium feldspars, generally nucleate ice more efficiently than feldspars containing significant amounts of calcium in the plagioclase series. We also find that there is variability in ice nucleating ability within these groups. While five out of six potassium-rich feldspars have a similar ice nucleating ability, one potassium rich feldspar sample and one sodium-rich feldspar sample were significantly more active. The…

Abstract. The light-absorbing organic aerosol (OA), commonly referred to as "brown carbon (BrC)", has attracted considerable attention in recent years because of its potential to affect atmospheric radiation balance, especially in the ultraviolet region and thus impact photochemical processes. A growing amount of data has indicated that BrC is prevalent in the atmosphere, which has motivated numerous laboratory and field studies; however, our understanding of the relationship between the chemical composition and optical properties of BrC remains limited. We conducted chamber experiments to investigate the effect of various VOC precursors, NOx concentrations, photolysis time and relative humidity (RH) on the light absorption of selected secondary organic aerosols (SOA). Light absorption of chamber generated SOA samples, especially aromatic SOA, was found to increase with NOx concentration, at moderate RH, and for the shortest photolysis aging times. The highest mass absorption coefficients (MAC) value is observed from toluene SOA products formed under high NOx conditions at moderate…

Abstract. Methane (CH4) has a 28-fold greater global warming potential than CO2 over 100 years. Atmospheric CH4 concentration has tripled since 1750. Anthropogenic CH4 emissions from China have been growing rapidly in the past decades and contribute more than 10 % of global anthropogenic CH4 emissions with large uncertainties in existing global inventories, generally limited to country-scale statistics. To date, a long-term CH4 emission inventory including the major sources sectors and based on province-level emission factors is still lacking. In this study, we produced a detailed annual bottom-up inventory of anthropogenic CH4 emissions from the eight major source sectors in China for the period 1980–2010. In the past 3 decades, the total CH4 emissions increased from 24.4 [18.6–30.5] Tg CH4 yr−1 in 1980 (mean [minimum–maximum of 95 % confidence interval]) to 44.9 [36.6–56.4] Tg CH4 yr−1 in 2010. Most of this increase took place in the 2000s decade with averaged yearly emissions of 38.5 [30.6–48.3] Tg CH4 yr−1. This fast increase of the total CH4 emissions after 2000 is mainly…

Abstract. Global climate and chemistry models routinely simulate dust emission, transport, and deposition to provide estimates of the role dust plays in climate and ecosystems. However, differences between these model simulations are substantial, with estimates of global dust aerosol optical depth (AOD) that vary by over a factor of 5. Here we develop an observationally-based estimate of the global dust AOD, using multiple satellite platforms, in-situ AOD observations and four state-of-the-science global models over 2004–2008. We estimate that the global dust AOD at 550 nm is 0.033 ± 0.006 (2σ), higher than the AeroCom model median (0.023) and substantially narrowing the uncertainty. The methodology used provides regional, seasonal dust AOD and the associated statistical uncertainty for key dust regions around the globe with which model dust schemes can be evaluated. Exploring the regional and seasonal differences in dust AOD between our observationally-based estimate and the four models in this study, we find that emissions in Africa are often overrepresented at the expense of…

Abstract. Nitryl chloride (ClNO2) is a dominant source of chlorine radical in polluted environment and can significantly affect the atmospheric oxidative chemistry. However, the abundance of ClNO2 and its exact role are not fully understood under different environmental conditions. During the summer of 2014, we deployed a chemical ionization mass spectrometer to measure ClNO2 and dinitrogen pentoxide (N2O5) at a rural site in the polluted North China Plain. Elevated mixing ratios of ClNO2 (> 350 pptv) were observed at most of the nights with low levels of N2O5 (< 200 pptv). The highest ClNO2 mixing ratio of 2070 pptv (1-min average) was observed in a plume from megacity (Tianjin) and was characterized with faster N2O5 heterogeneous loss rate and ClNO2 production rate compared to average condition. The abundant ClNO2 concentration kept increasing even after sunrise and reached a peak 4 hours later. Such highly sustained ClNO2 peaks after sunrise are discrepant from the previously observed typical diurnal pattern. Meteorological and chemical analysis show that the sustained ClNO2…

Abstract. Agricultural activities are a major source contributing to NH3 emissions in Shanghai and most other regions of China; however, there is a long-standing and ongoing controversy regarding the contributions of vehicle-emitted NH3 to the urban atmosphere. From April 2014 to April 2015, we conducted measurements of a wide range of gases (including NH3) and the chemical properties of PM2.5 at hourly resolution at a Shanghai urban supersite. This large dataset shows NH3 pollution events, lasting several hours with concentrations four times the annual average of 5.3 μg m-3, caused by the burning of crop residues in spring. There are also generally higher NH3 concentrations (mean ± 1σ) in summer (7.3 ± 4.9 μg m-3; n = 2181) because of intensive emissions from temperature-dependent agricultural sources. However, the NH3 concentration in summer was only an average of 2.4 μg m-3 or 41 % higher than the average NH3 concentration of other seasons. Furthermore, the NH3 concentration in winter (5.0 ± 3.7 μg m-3; n = 2113) was similar to that in spring (5.1 ± 3.8 μg m-3; n = 2204) but…

Abstract. An assessment of current and future emissions, air concentrations, and atmospheric deposition of mercury worldwide is presented on the basis of results obtained during the performance of the EU GMOS (Global Mercury Observation System) project. Emission estimates for mercury were prepared with the main goal of applying them in models to assess current (2013) and future (2035) air concentrations and atmospheric deposition of this contaminant. The combustion of fossil fuels (mainly coal) for energy and heat production in power plants and in industrial and residential boilers, as well as artisanal and small-scale gold mining, is one of the major anthropogenic sources of Hg emissions to the atmosphere at present. These sources account for about 37 and 25 % of the total anthropogenic Hg emissions globally, estimated to be about 2000 t. Emissions in Asian countries, particularly in China and India, dominate the total emissions of Hg. The current estimates of mercury emissions from natural processes (primary mercury emissions and re-emissions), including mercury depletion events,…

Abstract. Humic-like substances (HULIS) in smoke PM2.5 emitted from the combustion of biomass materials (rice straw, corn straw, and pine branch) and fossil fuels (lignite coal and diesel fuel) were comprehensively studied in this work. The HULIS fractions were first isolated with a one-step solid phase extraction method and were then investigated with a series of analytical techniques: elemental analysis, total organic carbon analysis, UV-vis spectroscopy, excitation–emission matrix (EEM) fluorescence spectroscopy, Fourier transform infrared spectroscopy, and 1H-nuclear magnetic resonance spectroscopy. The results indicated that HULIS accounted for a significant proportion of the particle matter, total carbon (TC), and water soluble organic carbon in smoke PM2.5 emitted from the combustion of biomass materials and coal. This suggests that biomass burning and coal combustion are both important sources of HULIS in atmospheric aerosols. However, HULIS in diesel soot only accounted for ~ 0.8 % of the soot particles, suggesting that vehicular exhaust may not be a significant primary…

Abstract. The radiative impact of organic aerosols (OA) is a large source of uncertainty in estimating the global direct radiative effect (DRE) of aerosols. This radiative impact includes not only light scattering but also light absorption from a subclass of OA referred to as brown carbon (BrC). However, the absorption properties of BrC are poorly understood, leading to large uncertainties in modeling studies. To obtain observational constraints from measurements, a simple absorption Ångström exponent (AAE) method is often used to separate the contribution of BrC absorption from that of black carbon (BC). However, this attribution method is based on assumptions regarding the spectral dependence of BC that are often violated in the ambient atmosphere. Here we develop a new AAE method which improves upon previous approaches by using the information from the wavelength-dependent measurements themselves and by allowing for an atmospherically relevant range of BC properties, rather than fixing these at a single assumed value. We note that constraints on BC optical properties and mixing…

Abstract. Measurements of HONO were carried out at an urban background site near central London as part of the Clean air for London (ClearfLo) project in summer 2012. Data was collected from 22 July–18 August 2014, with peak values of up to 1.8 ppbV at night and non-zero values of between 0.2 and 0.6 ppbV seen during the day. A wide range of other gas phase, aerosol, radiation and meteorological measurements were made concurrently at the same site, allowing a detailed analysis of the chemistry to be carried out. The peak HONO/NOx ratio of 0.04 is seen at ~ 02:00 UTC, with the presence of a second, daytime peak in HONO/NOx of similar magnitude to the night-time peak suggesting a significant secondary daytime HONO source. A photostationary state calculation of HONO involving formation from the reaction of OH and NO and loss from photolysis, reaction with OH and dry deposition shows a significant underestimation during the day, with calculated values being close to zero, compared to the measurement average of 0.4 ppbV at midday. The addition of further HONO sources, including…