Showing papers in "Atmospheric Chemistry and Physics in 2016"

Aura OMI observations of regional SO2 and NO2 pollution changes from 2005 to 2015

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. OMI confirmed large reductions in SO2 over eastern Europe's largest coal-fired power plants after installation of flue gas desulfurization devices. The North China Plain has the world's most severe SO2 pollution, but a decreasing trend has been observed since 2011, with about a 50 % reduction in 2012–2015, due to an economic slowdown and government efforts to restrain emissions from the power and industrial sectors. In contrast, India's SO2 and NO2 levels from coal power plants and smelters are growing at a fast pace, increasing by more than 100 and 50 %, respectively, from 2005 to 2015. Several SO2 hot spots observed over the Persian Gulf are probably related to oil and gas operations and indicate a possible underestimation of emissions from these sources in bottom-up emission inventories. Overall, OMI observations have proved valuable in documenting rapid changes in air quality over different parts of the world during last decade. The baseline established during the first 11 years of OMI is indispensable for the interpretation of air quality measurements from current and future satellite atmospheric composition missions.

Ice melt, sea level rise and superstorms: evidence from paleoclimate data, climate modeling, and modern observations that 2 °C global warming could be dangerous

Abstract: . We use numerical climate simulations, paleoclimate data, and modern observations to study the effect of growing ice melt from Antarctica and Greenland. Meltwater tends to stabilize the ocean column, inducing amplifying feedbacks that increase subsurface ocean warming and ice shelf melting. Cold meltwater and induced dynamical effects cause ocean surface cooling in the Southern Ocean and North Atlantic, thus increasing Earth's energy imbalance and heat flux into most of the global ocean's surface. Southern Ocean surface cooling, while lower latitudes are warming, increases precipitation on the Southern Ocean, increasing ocean stratification, slowing deepwater formation, and increasing ice sheet mass loss. These feedbacks make ice sheets in contact with the ocean vulnerable to accelerating disintegration. We hypothesize that ice mass loss from the most vulnerable ice, sufficient to raise sea level several meters, is better approximated as exponential than by a more linear response. Doubling times of 10, 20 or 40 years yield multi-meter sea level rise in about 50, 100 or 200 years. Recent ice melt doubling times are near the lower end of the 10–40-year range, but the record is too short to confirm the nature of the response. The feedbacks, including subsurface ocean warming, help explain paleoclimate data and point to a dominant Southern Ocean role in controlling atmospheric CO2, which in turn exercised tight control on global temperature and sea level. The millennial (500–2000-year) timescale of deep-ocean ventilation affects the timescale for natural CO2 change and thus the timescale for paleo-global climate, ice sheet, and sea level changes, but this paleo-millennial timescale should not be misinterpreted as the timescale for ice sheet response to a rapid, large, human-made climate forcing. These climate feedbacks aid interpretation of events late in the prior interglacial, when sea level rose to +6–9 m with evidence of extreme storms while Earth was less than 1 °C warmer than today. Ice melt cooling of the North Atlantic and Southern oceans increases atmospheric temperature gradients, eddy kinetic energy and baroclinicity, thus driving more powerful storms. The modeling, paleoclimate evidence, and ongoing observations together imply that 2 °C global warming above the preindustrial level could be dangerous. Continued high fossil fuel emissions this century are predicted to yield (1) cooling of the Southern Ocean, especially in the Western Hemisphere; (2) slowing of the Southern Ocean overturning circulation, warming of the ice shelves, and growing ice sheet mass loss; (3) slowdown and eventual shutdown of the Atlantic overturning circulation with cooling of the North Atlantic region; (4) increasingly powerful storms; and (5) nonlinearly growing sea level rise, reaching several meters over a timescale of 50–150 years. These predictions, especially the cooling in the Southern Ocean and North Atlantic with markedly reduced warming or even cooling in Europe, differ fundamentally from existing climate change assessments. We discuss observations and modeling studies needed to refute or clarify these assertions.

Global anthropogenic emissions of particulate matter including black carbon

Abstract: . This paper presents a comprehensive assessment of historical (1990–2010) global anthropogenic particulate matter (PM) emissions including the 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, refuse 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 172 source regions (as well as international shipping), presented for 25 global regions, and allocated to 0.5° × 0.5° longitude–latitude grids. No independent estimates of emissions from forest fires and savannah burning are provided and neither windblown dust nor unpaved roads emissions are included. We estimate that global emissions of PM have not changed significantly between 1990 and 2010, showing a strong decoupling from the global increase in energy consumption and, consequently, CO2 emissions, but there are significantly different regional trends, with a particularly strong increase in East Asia and Africa and a strong decline in Europe, North America, and the Pacific region. This in turn resulted in important changes in the spatial pattern of PM burden, e.g. European, North American, and Pacific contributions to global emissions dropped from nearly 30 % in 1990 to well below 15 % in 2010, while Asia's contribution grew from just over 50 % to nearly two-thirds of the global total in 2010. For all PM species considered, Asian sources represented over 60 % of the global anthropogenic total, and residential combustion was the most important sector, contributing about 60 % for BC and OC, 45 % for PM2. 5, and less than 40 % for PM10, where large combustion sources and industrial processes are equally important. Global anthropogenic emissions of BC were estimated at about 6.6 and 7.2 Tg in 2000 and 2010, respectively, and represent about 15 % of PM2. 5 but for some sources reach nearly 50 %, i.e. for the transport sector. Our global BC numbers are higher than previously published owing primarily to the inclusion of new sources. This PM estimate fills the gap in emission data and emission source characterization required in air quality and climate modelling studies and health impact assessments at a regional and global level, as it includes both carbonaceous and non-carbonaceous constituents of primary particulate matter emissions. The developed emission dataset has been used in several regional and global atmospheric transport and climate model simulations within the ECLIPSE (Evaluating the Climate and Air Quality Impacts of Short-Lived Pollutants) project and beyond, serves better parameterization of the global integrated assessment models with respect to representation of black carbon and organic carbon emissions, and built a basis for recently published global particulate number estimates.

The climatology of planetary boundary layer height in China derived fromradiosonde and reanalysis data

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 positively associated with the near-surface wind speed and temperature. In addition, cloud tends to suppress the development of PBL, particularly in the early afternoon. This indicates that meteorology plays a significant role in the PBL processes. Overall, the key findings obtained from this study lay a solid foundation for us to gain a deep insight into the fundamentals of PBL in China, which helps to understand the roles that the PBL plays in the air pollution, weather and climate of China.

Mixing layer height and its implications for air pollution over Beijing, China

Abstract: . The mixing layer is an important meteorological factor that affects air pollution. In this study, the atmospheric mixing layer height (MLH) was observed in Beijing from July 2009 to December 2012 using a ceilometer. By comparison with radiosonde data, we found that the ceilometer underestimates the MLH under conditions of neutral stratification caused by strong winds, whereas it overestimates the MLH when sand-dust is crossing. Using meteorological, PM2.5, and PM10 observational data, we screened the observed MLH automatically; the ceilometer observations were fairly consistent with the radiosondes, with a correlation coefficient greater than 0.9. Further analysis indicated that the MLH is low in autumn and winter and high in spring and summer in Beijing. There is a significant correlation between the sensible heat flux and MLH, and the diurnal cycle of the MLH in summer is also affected by the circulation of mountainous plain winds. Using visibility as an index to classify the degree of air pollution, we found that the variation in the sensible heat and buoyancy term in turbulent kinetic energy (TKE) is insignificant when visibility decreases from 10 to 5 km, but the reduction of shear term in TKE is near 70 %. When visibility decreases from 5 to 1 km, the variation of the shear term in TKE is insignificant, but the decrease in the sensible heat and buoyancy term in TKE is approximately 60 %. Although the correlation between the daily variation of the MLH and visibility is very poor, the correlation between them is significantly enhanced when the relative humidity increases beyond 80 %. This indicates that humidity-related physicochemical processes is the primary source of atmospheric particles under heavy pollution and that the dissipation of atmospheric particles mainly depends on the MLH. The presented results of the atmospheric mixing layer provide useful empirical information for improving meteorological and atmospheric chemistry models and the forecasting and warning of air pollution.

Nitrate radicals and biogenic volatile organic compounds: oxidation, mechanisms, and organic aerosol

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 constructing appropriate boundary layer schemes and non-photochemical mechanisms for use in state-of-the-art chemical transport and chemistry–climate models. This review is the result of a workshop of the same title held at the Georgia Institute of Technology in June 2015. The first half of the review summarizes the current literature on NO3-BVOC chemistry, with a particular focus on recent advances in instrumentation and models, and in organic nitrate and secondary organic aerosol (SOA) formation chemistry. Building on this current understanding, the second half of the review outlines impacts of NO3-BVOC chemistry on air quality and climate, and suggests critical research needs to better constrain this interaction to improve the predictive capabilities of atmospheric models.

Why do models overestimate surface ozone in the Southeast United States

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 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. This finding is based on SEAC4RS observations of NOx and its oxidation products, surface network observations of nitrate wet deposition fluxes, and OMI satellite observations of tropospheric NO2 columns. Our results indicate that NEI NOx emissions from mobile and industrial sources must be reduced by 30–60 %, dependent on the assumption of the contribution by soil NOx emissions. Upper-tropospheric NO2 from lightning makes a large contribution to satellite observations of tropospheric NO2 that must be accounted for when using these data to estimate surface NOx emissions. We find that only half of isoprene oxidation proceeds by the high-NOx pathway to produce ozone; this fraction is only moderately sensitive to changes in NOx emissions because isoprene and NOx emissions are spatially segregated. GEOS-Chem with reduced NOx emissions provides an unbiased simulation of ozone observations from the aircraft and reproduces the observed ozone production efficiency in the boundary layer as derived from a regression of ozone and NOx oxidation products. However, the model is still biased high by 6 ± 14 ppb relative to observed surface ozone in the Southeast US. Ozonesondes launched during midday hours show a 7 ppb ozone decrease from 1.5 km to the surface that GEOS-Chem does not capture. This bias may reflect a combination of excessive vertical mixing and net ozone production in the model boundary layer.

New insights into PM 2.5 chemical composition and sources in two major cities in China during extreme haze events using aerosol mass spectrometry

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 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 substantially during the extreme haze periods, with increased contributions of the inorganic components (mostly sulfate and nitrate). Our results suggest that the high relative humidity present during the extreme haze events had a strong effect on the increase of sulfate mass (via aqueous phase oxidation of sulfur dioxide). Another relevant characteristic of the extreme haze is the size of the measured particles. During the extreme haze events, the AMS showed much larger particles, with a volume weighted mode at about 800 to 1000 nm, in contrast to about 400 nm during reference periods. These large particle sizes made the use of the PM2.5 inlet crucial, especially during the severe haze events, where 39 ± 5 % of the mass would have been lost in the conventional PM1 (particulate matter with aerodynamic diameter ≤ 1 µm) inlet. A novel positive matrix factorization procedure was developed to apportion the sources of organic aerosols (OA) based on their mass spectra using the multilinear engine (ME-2) controlled via the source finder (SoFi). The procedure allows for an effective exploration of the solution space, a more objective selection of the best solution and an estimation of the rotational uncertainties. Our results clearly show an increase of the oxygenated organic aerosol (OOA) mass during extreme haze events. The contribution of OOA to the total OA increased from the reference to the extreme haze periods from 16.2 ± 1.1 to 31.3 ± 1.5 % in Xi'an and from 15.7 ± 0.7 to 25.0 ± 1.2 % in Beijing. By contrast, during the reference periods the total OA mass was dominated by domestic emissions of primary aerosols from biomass burning in Xi'an (42.2 ± 1.5 % of OA) and coal combustion in Beijing (55.2 ± 1.6 % of OA). These two sources are also mostly responsible for extremely high polycyclic aromatic hydrocarbon (PAH) concentrations measured with the AMS (campaign average of 2.1 ± 2.0 µg m−3 and frequent peak concentrations above 10 µg m−3). To the best of our knowledge, this is the first data set where the simultaneous extraction of these two primary sources could be achieved in China by conducting on-line AMS measurements at two areas with contrasted emission patterns.

High-resolution ammonia emissions inventories in China from 1980 to 2012

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 11.1 Tg from 1980 to 1996, and then decreased to 9.7 Tg in 2012. The two major contributors were livestock manure and synthetic fertilizer application, which contributed 80–90 % of the total emissions. Emissions from livestock manure rose from 2.86 Tg (1980) to 6.16 Tg (2005), and then decreased to 5.0 Tg (2012); beef cattle were the largest source followed by laying hens and pigs. The remarkable downward trend in livestock emissions that occurred in 2007 was attributed to a decrease in the numbers of various livestock animals, including beef cattle, goats, and sheep. Meanwhile, emissions from synthetic fertilizer ranged from 2.1 Tg (1980) to 4.7 Tg (1996), and then declined to 2.8 Tg (2012). Urea and ammonium bicarbonate (ABC) dominated this category of emissions, and a decline in ABC application led to the decrease in emissions that took place from the mid-1990s onwards. High emissions were concentrated in eastern and southwestern China. Seasonally, peak NH3 emissions occurred in spring and summer. The inventories had a monthly temporal resolution and a spatial resolution of 1000 m, and thus are suitable for global and regional air-quality modeling.

Cleaning up the air: effectiveness of air quality policy for SO 2 and NO x emissions in China

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 highly related to traffic. Furthermore, regulations for NOx emissions are partly decided on a provincial level. The last 3 years show a reduction both in SO2 and NOx emissions per fossil fuel unit, since the authorities have implemented several new environmental regulations. Despite an increasing fossil fuel consumption and a growing transport sector, the effects of air quality policy in China are clearly visible. Without the air quality regulations the concentration of SO2 would be about 2.5 times higher and the NO2 concentrations would be at least 25 % higher than they are today in China.

Evaluation of the absorption Ångström exponents for traffic and wood burning in the Aethalometer-based source apportionment using radiocarbon measurements of ambient aerosol

Abstract: . Equivalent black carbon (EBC) 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 absorption Angstrom exponent (α). While the spectral dependence (defined as α values) of the traffic-related EBC 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 αWB and αTR by comparing the source apportionment of EBC using the Aethalometer model with 14C measurements of the EC fraction on 16 to 40 h filter samples from several locations and campaigns across Switzerland during 2005–2012, mainly in winter. The data obtained at eight stations with different source characteristics also enabled the evaluation of the performance and the uncertainties of the Aethalometer model in different environments. The best combination of αTR and αWB (0.9 and 1.68, respectively) was obtained by fitting the Aethalometer model outputs (calculated with the absorption coefficients at 470 and 950 nm) against the fossil fraction of EC (ECF ∕ EC) derived from 14C measurements. Aethalometer and 14C source apportionment results are well correlated (r = 0.81) and the fitting residuals exhibit only a minor positive bias of 1.6 % and an average precision of 9.3 %. This indicates that the Aethalometer model reproduces reasonably well the 14C results for all stations investigated in this study using our best estimate of a single αWB and αTR pair. Combining the EC, 14C, and Aethalometer measurements further allowed assessing the dependence of the mass absorption cross section (MAC) of EBC on its source. Results indicate no significant difference in MAC at 880 nm between EBC originating from traffic or wood-burning emissions. Using ECF ∕ EC as reference and constant a priori selected αTR values, αWB was also calculated for each individual data point. No clear station-to-station or season-to-season differences in αWB were observed, but αTR and αWB values are interdependent. For example, an increase in αTR by 0.1 results in a decrease in αWB by 0.1. The fitting residuals of different αTR and αWB combinations depend on ECF ∕ EC such that a good agreement cannot be obtained over the entire ECF ∕ EC range using other α pairs. Additional combinations of αTR = 0.8, and 1.0 and αWB = 1.8 and 1.6, respectively, are possible but only for ECF ∕ EC between ∼ 40 and 85 %. Applying α values previously used in the literature such as αWB of ∼ 2 or any αWB in combination with αTR = 1.1 to our data set results in large residuals. Therefore we recommend to use the best α combination as obtained here (αTR = 0.9 and αWB = 1.68) in future studies when no or only limited additional information like 14C measurements are available. However, these results were obtained for locations impacted by black carbon (BC) mainly from traffic consisting of a modern car fleet and residential wood combustion with well-constrained combustion efficiencies. For regions of the world with different combustion conditions, additional BC sources, or fuels used, further investigations are needed.

AIRUSE-LIFE+: a harmonized PM speciation and source apportionment in five southern European cities

Abstract: . The AIRUSE-LIFE+ project aims at characterizing similarities and heterogeneities in particulate matter (PM) sources and contributions in urban areas from 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 and MLN-UB), one suburban background site (Athens, ATH-SUB) and one traffic site (Porto, POR-TR). After collecting 1047 PM10 and 1116 PM2.5 24 h samples during 12 months (from January 2013 on) simultaneously at the five 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 data sets in a harmonized way for each city. The sum of vehicle exhaust (VEX) and non-exhaust (NEX) contributes between 3.9 and 10.8 µg m−3 (16–32 %) to PM10 and 2.3 and 9.4 µg m−3 (15–36 %) to PM2.5, although a fraction of secondary nitrate is also traffic-related but could not be estimated. Important contributions arise from secondary particles (nitrate, sulfate and organics) in PM2.5 (37–82 %) but also in PM10 (40–71 %), mostly at background sites, revealing the importance of abating gaseous precursors in designing air quality plans. Biomass burning (BB) contributions vary widely, from 14–24 % of PM10 in POR-TR, MLN-UB and FI-UB, 7 % in ATH-SUB, to – Local dust, 7–12 % of PM10 at SUB and UB sites and 19 % at the TR site, revealing a contribution from road dust resuspension. In PM2.5 percentages decrease to 2–7 % at SUB-UB sites and 15 % at the TR site. – Industry, mainly metallurgy, contributing 4–11 % of PM10 (5–12 % in PM2.5), but only at BCN-UB, POR-TR and MLN-UB. No clear impact of industrial emissions was found in FI-UB and ATH-SUB. – Natural contributions from sea salt (13 % of PM10 in POR-TR, but only 2–7 % in the other cities) and Saharan dust (14 % in ATH-SUB, but less than 4 % in the other cities). During high pollution days, the largest sources (i.e. excluding secondary aerosol factors) of PM10 and PM2.5 are VEX + NEX in BCN-UB (27–22 %) and POR-TR (31–33 %), BB in FI-UB (30–33 %) and MLN-UB (35–26 %) and Saharan dust in ATH-SUB (52–45 %). During those days, there are also quite important industrial contributions in BCN-UB (17–18 %) and local dust in POR-TR (28–20 %).

One-year simulation of ozone and particulate matter in Chinausing WRF/CMAQ modeling system

Abstract: . China has been experiencing severe air pollution in recent decades. Although an 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 and Forecasting (WRF) model and the Community Multi-scale Air Quality (CMAQ) model was conducted to provide detailed temporal and spatial information of ozone (O3), total PM2.5, 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 most months, with model performance statistics meeting the performance criteria. However, overprediction of O3 generally occurs at low concentration range while underprediction of PM2.5 happens at low concentration range in summer. Spatially, the model has better performance in southern China than in northern China, central China, and Sichuan Basin. Strong seasonal variations of PM2.5 exist and wind speed and direction play important roles in high PM2.5 events. Secondary components have more boarder distribution than primary components. Sulfate (SO42−), nitrate (NO3−), ammonium (NH4+), and primary organic aerosol (POA) are the most important PM2.5 components. All components have the highest concentrations in winter except secondary organic aerosol (SOA). This study proves the ability of the CMAQ model to reproduce severe air pollution in China, identifies the directions where improvements are needed, and provides information for human exposure to multiple pollutants for assessing health effects.

Aqueous-phase mechanism for secondary organic aerosol formation from isoprene: application to the southeast United States and co-benefit of SO2 emission controls

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 coefficients (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 the observed relationship of total fine organic aerosol (OA) and formaldehyde (a product of isoprene oxidation). Isoprene SOA production is mainly contributed by two immediate gas-phase precursors, isoprene epoxydiols (IEPOX, 58 % of isoprene SOA) from the low-NOx pathway and glyoxal (28 %) from both low- and high-NOx pathways. This speciation is consistent with observations of IEPOX SOA from SOAS and SEAC4RS. Observations show a strong relationship between IEPOX SOA and sulfate aerosol that we explain as due to the effect of sulfate on aerosol acidity and volume. Isoprene SOA concentrations increase as NOx emissions decrease (favoring the low-NOx pathway for isoprene oxidation), but decrease more strongly as SO2 emissions decrease (due to the effect of sulfate on aerosol acidity and volume). The US Environmental Protection Agency (EPA) projects 2013–2025 decreases in anthropogenic emissions of 34 % for NOx (leading to a 7 % increase in isoprene SOA) and 48 % for SO2 (35 % decrease in isoprene SOA). Reducing SO2 emissions decreases sulfate and isoprene SOA by a similar magnitude, representing a factor of 2 co-benefit for PM2.5 from SO2 emission controls.

Global tropospheric hydroxyl distribution, budget and reactivity

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 mainly through the photodissociation 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 (ECHAM/MESSy Atmospheric Chemistry) and show that S is larger than previously assumed. By including emissions of a large number of primary VOC, and accounting for their complete breakdown and intermediate products, MOM is mass-conserving and calculates substantially higher OH reactivity from VOC oxidation compared to predecessor models. Whereas previously P and S were found to be of similar magnitude, the present work indicates that S may be twice as large, mostly due to OH recycling in the free troposphere. Further, we find that nighttime OH formation may be significant in the polluted subtropical boundary layer in summer. With a mean OH recycling probability of about 67 %, global OH is buffered and not sensitive to perturbations by natural or anthropogenic emission changes. Complementary primary and secondary OH formation mechanisms in pristine and polluted environments in the continental and marine troposphere, connected through long-range transport of O3, can maintain stable global OH levels.

Primary and secondary aerosols in Beijing in winter: sources, variations andprocesses

Abstract: . Winter has the worst air pollution of the year in the megacity of Beijing. Despite extensive winter studies in recent years, our knowledge of 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 17 December 2013 to 17 January 2014 along with offline filter analysis by gas chromatography/mass spectrometry. Our results suggest that submicron aerosols composition was generally similar across the winter of different years and 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 as well as 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 distinct polycyclic aromatic hydrocarbons (PAHs) spectral signatures, indicating that PAHs in winter were mainly from coal combustion (66 %) and biomass burning emissions (18 %). BBOA was highly correlated with levoglucosan, a tracer compound for biomass burning (r2 = 0.93), and made a considerable contribution to OA in winter (9 %). An aqueous-phase-processed SOA (aq-OOA) that was strongly correlated with particle liquid water content, sulfate and S-containing ions (e.g. CH2SO2+) was identified. On average aq-OOA contributed 12 % to the total OA and played a dominant role in increasing oxidation degrees of OA at high RH levels (> 50 %). Our results illustrate that aqueous-phase processing can enhance SOA production and oxidation states of OA as well in winter. Further episode analyses highlighted the significant impacts of meteorological parameters on aerosol composition, size distributions, oxidation states of OA and evolutionary processes of secondary aerosols.

Forty years of improvements in European air quality: regional policy-industry interactions with global impacts

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 abatement measures and improvement in European emissions standards, but fuel consumption occurring at historical pace, and (2) the impact of increased fuel consumption by considering unchanged energy use with constant fuel consumption since 1970, but technological development and end-of-pipe reductions. Our scenario analysis focuses on the three most important and most regulated sectors (power generation, the manufacturing industry and road transport), which are subject of multi-pollutant EU Air Quality regulations. If technology and European EOP reduction measures had stagnated at 1970 levels, EU air quality in 2010 would have suffered from 129 % higher SO2, 71 % higher NOx and 69 % higher PM2.5 emissions, demonstrating the large role of technology in reducing emissions in 2010. However, if fuel consumption had remained constant starting in 1970, the EU would have benefited from current technology and emission control standards, with reductions in NOx by even 13 % more. Such further savings are not observed for SO2 and PM2.5. If the EU consumed the same amount of fuels as in 1970 but with the current technology and emission control standards, then the emissions of SO2 and PM2.5 would be 42 % respectively 10 % higher. This scenario shows the importance for air quality of abandoning heavy residual fuel oil and shifting fuel types (from, e.g., coal to gas) in the EU. A reduced-form TM5-FASST (Fast Screening Scenario Tool based on the global chemical Transport Model 5) is applied to calculate regional and global levels of aerosol and ozone concentrations and to assess the impact of air quality improvements on human health and crop yield loss, showing substantial impacts of export of EU technologies and standards to other world regions.

Introduction to the SPARC Reanalysis Intercomparison Project (S-RIP) and overview of the reanalysis systems

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 troposphere, stratosphere, and lower mesosphere. This paper summarizes the motivation and goals of the S-RIP activity and extensively reviews key technical aspects of the reanalysis data sets that are the focus of this activity. The special issue "The SPARC Reanalysis Intercomparison Project (S-RIP)" in this journal serves to collect research with relevance to the S-RIP in preparation for the publication of the planned two (interim and full) S-RIP reports.

Significant increase of surface ozone at a rural site, north of eastern China

Abstract: . Ozone pollution in eastern China has become one of the top environmental issues. Quantifying the temporal trend of surface ozone helps to assess the impacts of the anthropogenic precursor reductions and the likely effects of emission control strategies implemented. In this paper, ozone data collected at the Shangdianzi (SDZ) regional atmospheric background station from 2003 to 2015 are presented and analyzed to obtain the variation in the trend of surface ozone in the most polluted region of China, north of eastern China or the North China Plain. A modified Kolmogorov–Zurbenko (KZ) filter method was performed on the maximum daily average 8 h (MDA8) concentrations of ozone to separate the contributions of different factors from the variation of surface ozone and remove the influence of meteorological fluctuations on surface ozone. Results reveal that the short-term, seasonal and long-term components of ozone account for 36.4, 57.6 and 2.2 % of the total variance, respectively. The long-term trend indicates that the MDA8 has undergone a significant increase in the period of 2003–2015, with an average rate of 1.13 ± 0.01 ppb year−1 (R2 = 0.92). It is found that meteorological factors did not significantly influence the long-term variation of ozone and the increase may be completely attributed to changes in emissions. Furthermore, there is no significant correlation between the long-term O3 and NO2 trends. This study suggests that emission changes in VOCs might have played a more important role in the observed increase of surface ozone at SDZ.

Radical chemistry at a rural site (Wangdu) in the North China Plain: observation and model calculations of OH, HO 2 and RO 2 radicals

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 compound (VOC) and low NOx concentrations. For HO2, good agreement is found between modeled and observed concentrations during day and night. In the case of RO2, the agreement between model calculations and measurements is good in the late afternoon when NO concentrations are below 0.3 ppbv. A significant model underprediction of RO2 by a factor of 3 to 5 is found in the morning at NO concentrations higher than 1 ppbv, which can be explained by a missing RO2 source of 2 ppbv h−1. As a consequence, the model underpredicts the photochemical net ozone production by 20 ppbv per day, which is a significant portion of the daily integrated ozone production (110 ppbv) derived from the measured HO2 and RO2. The additional RO2 production from the photolysis of ClNO2 and missing reactivity can explain about 10 % and 20 % of the discrepancy, respectively. The underprediction of the photochemical ozone production at high NOx found in this study is consistent with the results from other field campaigns in urban environments, which underlines the need for better understanding of the peroxy radical chemistry for high NOx conditions.

Introduction: Observations and Modeling of the Green Ocean Amazon (GoAmazon2014/5)

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 for 2 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 special issue of GoAmazon2014/5, 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 of the pollution, to T1 in the midst of the pollution, to T2 just downwind of the pollution, to T3 furthest downwind of the pollution (70 km). In addition to the ground sites, a low-altitude G-159 Gulfstream I (G-1) observed the atmospheric boundary layer and low clouds, and a high-altitude Gulfstream G550 (HALO) operated in the free troposphere. During the 2-year experiment, two Intensive Operating Periods (IOP1 and IOP2) also took place that included additional specialized research instrumentation at the ground sites as well as flights of the two aircraft. GoAmazon2014/5 IOP1 was carried out from 1 February to 31 March 2014 in the wet season. GoAmazon2014/5 IOP2 was conducted from 15 August to 15 October 2014 in the dry season. The G-1 aircraft flew during both IOP1 and IOP2, and the HALO aircraft flew during IOP2. In the context of the Amazon basin, the two IOPs also correspond to the clean and biomass burning seasons, respectively. The Manaus plume is present year-round, and it is transported by prevailing northeasterly and easterly winds in the wet and dry seasons, respectively. This introduction also organizes information relevant to many papers in the special issue. Information is provided on the vehicle fleet, power plants, and industrial activities of Manaus. The mesoscale and synoptic meteorologies relevant to the two IOPs are presented. Regional and long-range transport of emissions during the two IOPs is discussed based on satellite observations across South America and Africa. Fire locations throughout the airshed are detailed. In conjunction with the context and motivation of GoAmazon2014/5 as presented in this introduction, research articles including thematic overview articles are anticipated in this special issue to describe the detailed results and findings of the GoAmazon2014/5 Experiment.

A comprehensive biomass burning emission inventory with high spatial and temporal resolution in China

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 pollution, greenhouse gases, and heavy metal released from biomass burning. The results show that the emissions of SO2, NOx, PM10, PM2.5, NMVOC, NH3, CO, EC, OC, CO2, CH4, and Hg in 2012 are 336.8 Gg, 990.7 Gg, 3728.3 Gg, 3526.7 Gg, 3474.2 Gg, 401.2 Gg, 34 380.4 Gg, 369.7 Gg, 1189.5 Gg, 675 299.0 Gg, 2092.4 Gg, and 4.12 Mg, respectively. Domestic straw burning, in-field straw burning, and firewood burning are identified as the dominant biomass burning sources. The largest contributing source is different for various pollutants. Domestic straw burning is the largest source of biomass burning emissions for all the pollutants considered, except for NH3, EC (firewood), and NOx (in-field straw). Corn, rice, and wheat represent the major crop straws. The combined emission of these three straw types accounts for 80 % of the total straw-burned emissions for each specific pollutant mentioned in this study. As for the straw burning emission of various crops, corn straw burning has the largest contribution to all of the pollutants considered, except for CH4; rice straw burning has highest contribution to CH4 and the second largest contribution to other pollutants, except for SO2, OC, and Hg; wheat straw burning is the second largest contributor to SO2, OC, and Hg and the third largest contributor to other pollutants. Heilongjiang, Shandong, and Henan provinces located in the north-eastern and central-southern regions of China have higher emissions compared to other provinces in China. Gridded emissions, which were obtained through spatial allocation based on the gridded rural population and fire point data from emission inventories at county resolution, could better represent the actual situation. High biomass burning emissions are concentrated in the areas with more agricultural and rural activity. The months of April, May, June, and October account for 65 % of emissions from in-field crop residue burning, while, regarding EC, the emissions in January, February, October, November, and December are relatively higher than other months due to biomass domestic burning in heating season. There are regional differences in the monthly variations of emissions due to the diversity of main planted crops and climatic conditions. Furthermore, PM2.5 component results showed that OC, Cl−, EC, K+, NH4+, elemental K, and SO42− are the main PM2.5 species, accounting for 80 % of the total emissions. The species with relatively high contribution to NMVOC emission include ethylene, propylene, toluene, mp-xylene, and ethyl benzene, which are key species for the formation of secondary air pollution. The detailed biomass burning emission inventory developed by this study could provide useful information for air-quality modelling and could support the development of appropriate pollution-control strategies.

Global impacts of tropospheric halogens (Cl, Br, I) on oxidants and composition in GEOS-Chem

Abstract: . We present a simulation of the global present-day 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 debromination. Observations of halogen radicals (BrO, IO) are sparse but the model has some skill in reproducing these. Modelled IO shows both high and low biases when compared to different datasets, but BrO concentrations appear to be modelled low. Comparisons to the very sparse observations dataset of reactive Cl species suggest the model represents a lower limit of the impacts of these species, likely due to underestimates in emissions and therefore burdens. Inclusion of Cl, Br, and 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 tropospheric O3 burden by 18.6 %, with the O3 lifetime reducing from 26 to 22 days. Global mean OH concentrations of 1.28 × 106 molecules cm−3 are 8.2 % lower than in a simulation without halogens, leading to an increase in the CH4 lifetime (10.8 %) due to OH oxidation from 7.47 to 8.28 years. Oxidation of CH4 by Cl is small (∼ 2 %) but Cl oxidation of other VOCs (ethane, acetone, and propane) can be significant (∼ 15–27 %). Oxidation of VOCs by Br is smaller, representing 3.9 % of the loss of acetaldehyde and 0.9 % of the loss of formaldehyde.

US surface ozone trends and extremes from 1980 to 2014: quantifying the roles of rising Asian emissions, domestic controls, wildfires, and climate

Abstract: . US surface 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 h 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, and (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 have 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 50 % US NOx emission controls. Methane increases over this period contribute only 15 % of the WUS background O3 increase. Springtime O3 observed in Denver has increased at a rate similar to remote rural sites. During summer, increasing Asian emissions approximately offset the benefits of US emission reductions, leading to weak or insignificant observed O3 trends at WUS rural sites. Mean springtime WUS O3 is projected to increase by ∼ 10 ppb from 2010 to 2030 under the RCP8.5 global change scenario. While historical wildfire emissions can enhance summertime monthly mean O3 at individual sites by 2–8 ppb, high temperatures and the associated buildup of O3 produced from regional anthropogenic emissions contribute most to elevating observed summertime O3 throughout the USA. GFDL-AM3 captures the observed interannual variability of summertime EUS O3. However, O3 deposition sink to vegetation must be reduced by 35 % for the model to accurately simulate observed high-O3 anomalies during the severe drought of 1988. Regional NOx reductions alleviated the O3 buildup during the recent heat waves of 2011 and 2012 relative to earlier heat waves (e.g., 1988, 1999). The O3 decreases driven by NOx controls were more pronounced in the southeastern US, where the seasonal onset of biogenic isoprene emissions and NOx-sensitive O3 production occurs earlier than in the northeast. Without emission controls, the 95th percentile summertime O3 in the EUS would have increased by 0.2–0.4 ppb yr−1 over 1988–2014 due to more frequent hot extremes and rising biogenic isoprene emissions.

Satellite observations of atmospheric methane and their value for quantifying methane emissions

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, from the global scale down to the scale of point sources and in combination with suborbital (surface and aircraft) data. Current global observations from Greenhouse Gases Observing Satellite (GOSAT) are of high quality but have sparse spatial coverage. They can quantify methane emissions on a regional scale (100–1000 km) through multiyear averaging. The Tropospheric Monitoring Instrument (TROPOMI), to be launched in 2017, is expected to quantify daily emissions on the regional scale and will also effectively detect large point sources. A different observing strategy by GHGSat (launched in June 2016) is to target limited viewing domains with very fine pixel resolution in order to detect a wide range of methane point sources. Geostationary observation of methane, still in the proposal stage, will have the unique capability of mapping source regions with high resolution, detecting transient "super-emitter" point sources and resolving diurnal variation of emissions from sources such as wetlands and manure. Exploiting these rapidly expanding satellite measurement capabilities to quantify methane emissions requires a parallel effort to construct high-quality spatially and sectorally resolved emission inventories. Partnership between top-down inverse analyses of atmospheric data and bottom-up construction of emission inventories is crucial to better understanding methane emission processes and subsequently informing climate policy.

Decadal changes in global surface NO x emissions from multi-constituent satellite data assimilation

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 over the 10-year period. The estimated regional total emissions show a strong positive trend over India (+29 % decade−1), China (+26 % decade−1), and the Middle East (+20 % decade−1), and a negative trend over the USA (−38 % decade−1), southern Africa (−8.2 % decade−1), and western Europe (−8.8 % decade−1). The negative trends in the USA and western Europe are larger during 2005–2010 relative to 2011–2014, whereas the trend in China becomes negative after 2011. The data assimilation also suggests a large uncertainty in anthropogenic and fire-related emission factors and an important underestimation of soil NOx sources in the emission inventories. Despite the large trends observed for individual regions, the global total emission is almost constant between 2005 (47.9 Tg N yr−1) and 2014 (47.5 Tg N yr−1).

Oxidative potential of ambient water-soluble PM 2.5 in the southeastern United States: contrasts in sources and health associations between ascorbic acid (AA) and dithiothreitol (DTT) assays

Abstract: . The ability of certain components of particulate matter to induce oxidative stress through the 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 report here the development of a similar semi-automated system for the ascorbic acid (AA) assay. Approximately 500 PM2.5 filter samples collected in contrasting locations in the southeastern US were analyzed for a host of aerosol species, along with AA and DTT activities. We present a detailed contrast in findings from these two assays. Water-soluble AA activity was higher in summer and fall than in winter, with highest levels near heavily trafficked highways, whereas DTT activity was higher in winter compared to summer and fall and more spatially homogeneous. AA activity was nearly exclusively correlated with water-soluble Cu (r = 0.70–0.94 at most sites), whereas DTT activity was correlated with organic and metal species. Source apportionment models, positive matrix factorization (PMF) and a chemical mass balance method with ensemble-averaged source impact profiles (CMB-E), suggest a strong contribution from traffic emissions and secondary processes (e.g., organic aerosol oxidation or metals mobilization by secondary acids) to both AA and DTT activities in urban Atlanta. In contrast, biomass burning was a large source for DTT activity, but insignificant for AA. AA activity was not correlated with PM2.5 mass, while DTT activity co-varied strongly with mass (r = 0.49–0.86 across sites and seasons). Various linear models were developed to estimate AA and DTT activities for the central Atlanta Jefferson Street site, based on the CMB-E sources. The models were then used to estimate daily oxidative potential at this site over the 1998–2009 period. Time series epidemiological analyses were conducted to assess daily emergency department (ED) visits data for the five-county Atlanta metropolitan area based on the estimated 10-year backcast oxidative potential. Estimated AA activity was not statistically associated with any tested health outcome, while DTT activity was associated with ED visits for both asthma or wheeze and congestive heart failure. The findings point to the importance of both organic components and transition metals from biomass burning and mobile sources to adverse health outcomes in this region.

Understanding the Recent Trend of Haze Pollution in Eastern China: Roles of Climate Change

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 South China after 2000, with the precipitation effect being smaller and spatially inconsistent.

Rethinking the global secondary organic aerosol (SOA) budget: stronger production, faster removal, shorter lifetime

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 life cycle of atmospheric SOA, with production rates 3.9 times higher and sinks a factor of 3.6 more efficient than in the base model. In particular, the updated model predicts larger SOA concentrations in the boundary layer and lower concentrations in the upper troposphere, leading to better agreement with surface and aircraft measurements of organic aerosol compared to the base model. Our analysis thus suggests that the long-standing discrepancy in model predictions of the vertical SOA distribution can now be resolved, at least in part, by a stronger source and stronger sinks leading to a shorter lifetime. The predicted global SOA burden in the updated model is 0.88 Tg and the corresponding direct radiative effect at top of the atmosphere is −0.33 W m−2, which is comparable to recent model estimates constrained by observations. The updated model predicts a population-weighed global mean surface SOA concentration that is a factor of 2 higher than in the base model, suggesting the need for a reanalysis of the contribution of SOA to PM pollution-related human health effects. The potential importance of our estimates highlights the need for more extensive field and laboratory studies focused on characterizing organic aerosol removal mechanisms and rates.

A global catalogue of large SO 2 sources and emissions derived from theOzone Monitoring Instrument

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 OMI measurements, but that fraction has increased in recent years given that cumulative global emissions from power plants and smelters are declining while emissions from oil and gas industry remained nearly constant Anthropogenic emissions from the USA declined by 80 % over the 2005–2014 period as did emissions from western and central Europe, whereas emissions from India nearly doubled, and emissions from other large SO2-emitting regions (South Africa, Russia, Mexico, and the Middle East) remained fairly constant In total, OMI-based estimates account for about a half of total reported anthropogenic SO2 emissions; the remaining half is likely related to sources emitting less than 30 kt yr−1 and not detected by OMI