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Energy consumption from central heating has rapidly increased in the cities of the North China Plain (NCP). The increasing use of natural gas in the central heating supply system may have altered the spatial and temporal patterns of CO2 emissions from central heating, yet the quantitative impacts are poorly understood. Here we detect the spatio-temporal dynamics of CO2 emissions of central heating from 2012 to 2016 at the prefectural-city level in the NCP region, by using the satellite NPP-VIIRS nighttime light data and a panel regression model to estimate CO2 emissions on a 5 × 5 km2 grid. We find that despite a slight decrease (2%) in 2014 under the “Natural Gas Utilization Policy”, CO2 emissions continued to grow. Between 2012 and 2016, CO2 emissions from central heating in the NCP increased from 106 to 121 Tg, although CO2 emissions declined by 12% in Beijing due to the increasing contribution of natural gas boilers. The gridded CO2 emissions map shows that over 2012–2016 coal burning is the main driving force of CO2 emissions in both urban and non-urban regions, despite the increasing fraction of gas-based heating. Our results contribute to city-level policymaking on carbon reduction and climate change mitigation. The high-resolution gridded CO2 emissions can also be applied in physical models to facilitate carbon cycle studies.

Mercury (Hg) is a naturally occurring element in the Earth's crust. It can be harmful to human health when released in large quantities and/or converted to the neurotoxicant methyl mercury in aquatic ecosystems. This study analyzes global and regional trends in anthropogenic Hg releases to the atmosphere between 2010 and 2015, as well as the associated trends in modeled and measured Hg concentrations at sites around the world. In general, we find that global Hg emissions and concentrations have grown slightly in this period, as declines from the phase-out of commercial Hg use in the developed world have been more than matched by increases in Hg-related activities in the industrializing countries of the world. We estimate that global Hg emissions between 2010 and 2015 have grown at a rate of 1.8%/yr, from 2188 Mg (+44%/-20%, 80% C.I.) in 2010 to 2390 Mg (+42%/-19%, 80% C.I.) in 2015. Regionally, emissions declined over this period in the U.S. (−10%), OECD Europe (−5.8%), and Canada (−3.2%), while they increased in Central America (+5.4%), South Asia (+4.6%), and Eastern Africa (+4.0%). East Asia remained the largest emitting region at 1012 Mg in 2015, though growth there has slowed significantly in recent years. The production of Hg (+7.9%), caustic soda (+6.3%), and cement (+6.3%) showed the highest increases by source type, though artisanal and small-scale gold mining (ASGM) was the single largest source of emissions in 2015 (775 Mg). The commercial use of Hg in dental applications (−5.6%) and electrical equipment (−5.2%) continued to decline. These emission trends show a continuation of the regional and sectoral shifts that began in the 1970s, but with a resulting reversal in global trends, because the benefits from Hg phase-out in North America and Europe have been largely realized and industrial growth in developing countries has begun to dominate. The emission trends are in agreement with trends in modeled and measured concentrations, which show small declines in surface air total gaseous Hg concentrations in eastern North America and Western Europe between 2010 and 2015, but slight increases for much of the rest of the world, driven by the continued increases in emissions from Asia and from ASGM. Our results suggest that reductions of Hg in the North Atlantic region have been largely successful, and focus now needs to shift to Asia and to the continued practice of ASGM worldwide.

Emission inventory development for air pollutants, by compiling records from individual emission sources, takes many years and involves extensive multi-national effort. A complementary method to estimate air pollution emissions is in the use of satellite remote sensing. In this study, NO2 observations from the Ozone Monitoring Instrument are combined with re-analysis meteorology to estimate urban nitrogen oxide (NO X ) emissions for 80 global cities between 2005 and 2019. The global average downward trend in satellite-derived urban NOX emissions was 3.1%–4.0% yr−1 between 2009 and 2018 while inventories show a 0%–2.2% yr−1 drop over the same timeframe. This difference is primarily driven by discrepancies between satellite-derived urban NO X emissions and inventories in Africa, China, India, Latin America, and the Middle East. In North America, Europe, Korea, Japan, and Australasia, NOX emissions dropped similarly as reported in the inventories. In Europe, Korea, and Japan only, the temporal trends match the inventories well, but the satellite estimate is consistently larger over time. While many of the discrepancies between satellite-based and inventory emissions estimates represent real differences, some of the discrepancies might be related to the assumptions made to compare the satellite-based estimates with inventory estimates, such as the spatial disaggregation of emissions inventories. Our work identifies that the three largest uncertainties in the satellite estimate are the tropospheric column measurements, wind speed and direction, and spatial definition of each city.

We estimate that a cumulative total of 1540 (1060–2800) Gg (gigagrams, 109 grams or thousand tonnes) of mercury (Hg) have been released by human activities up to 2010, 73% of which was released after 1850. Of this liberated Hg, 470 Gg were emitted directly into the atmosphere, and 74% of the air emissions were elemental Hg. Cumulatively, about 1070 Gg were released to land and water bodies. Though annual releases of Hg have been relatively stable since 1880 at 8 ± 2 Gg, except for wartime, the distributions of those releases among source types, world regions, and environmental media have changed dramatically. Production of Hg accounts for 27% of cumulative Hg releases to the environment, followed by silver production (24%) and chemicals manufacturing (12%). North America (30%), Europe (27%), and Asia (16%) have experienced the largest releases. Biogeochemical modeling shows a 3.2-fold increase in the atmospheric burden relative to 1850 and a contemporary atmospheric reservoir of 4.57 Gg, both of which agr...

Understanding the different impacts of urbanization on sectorial carbon dioxide (CO2) emissions at different spatial scales is of great importance for the evaluation of energy transition policies and reduction of environmental inequality. However, how urbanization affects the CO2 emissions of central heating systems at high spatial resolution in China has not been fully studied before. Based on satellite-observed NPP-VIIRS nighttime light (NTL) data, we develop a 5 km × 5 km annual CO2 emission inventory for coal boilers, thermal power plants (TPPs), and natural gas boilers in China’s central heating systems for the period 2012–2017 by using the geographical and temporally weighted regression (GTWR) model. It is observed that nonurban areas generated 2–4 times the CO2 emissions of coal boilers in urban areas. The largest increments of CO2 emissions of gas boilers are observed in urban areas of the eastern (6.80 times) and central regions (2.86 times) in 2013–2014, due to the clean heating policy in the “2 + 26” cities in China. The effects of urbanization on CO2 emissions from natural gas boilers are approximately 2–3 times those of coal boilers, and the differences are largest in western cities with only minor differences in northeastern cities. Our results will aid in designing low-carbon development goals and provide micro-level information on central heating facilities in urbanized and less developed regions.

This study investigates the relationship between ground-level ozone variability and synoptic weather conditions in the Chicago area in the summertime over the period 1990–2014. It shows that the occurrence of dry tropical (DT) weather conditions is most likely to lead to high ozone concentrations. Both the 95th percentile of summertime daily maximum 8-hour-average ozone concentrations and the number of days > 70 ppb are shown to have a greater and more significant correlation with DT weather in recent years (2004–2014) than in the preceding period (1990–2003), indicating an increased dependence of ozone on DT weather. The DT weather is shown to be associated with increased geopotential height, warmer temperature, and slower eastward wind at 500 hPa and also with warmer temperature and increased northward wind near the surface. The results have implications for the likely effect of future climate change on ozone as a result of modified synoptic weather conditions. More frequent episodes of high ozone concentrations can be expected, leading to worsened effects on public health and the environment. It will also make it increasingly challenging for Chicago to attain the National Ambient Air Quality Standard for ozone, which has recently been tightened by the U.S. Environmental Protection Agency.

In Part II of this work we present the results of the downscaled offline Weather Research and Forecasting/Community Multiscale Air Quality (WRF/CMAQ) model, included in the “Technology Driver Model” (TDM) approach to future U.S. air quality projections (2046–2050) compared to a current-year period (2001–2005), and the interplay between future emission and climate changes. By 2046–2050, there are widespread decreases in future concentrations of carbon monoxide (CO), nitrogen oxides (NOx = NO + NO2), volatile organic compounds (VOCs), ammonia (NH3), sulfur dioxide (SO2), and particulate matter with an aerodynamic diameter ≤ 2.5 μm (PM2.5) due mainly to decreasing on-road vehicle (ORV) emissions near urban centers as well as decreases in other transportation modes that include non-road engines (NRE). However, there are widespread increases in daily maximum 8-hr ozone (O3) across the U.S., which are due to enhanced greenhouse gases (GHG) including methane (CH4) and carbon dioxide (CO2) under the Intergovernmental Panel on Climate Change (IPCC) A1B scenario, and isolated areas of larger reduction in transportation emissions of NOx compared to that of VOCs over regions with VOC-limited O3 chemistry. Other notable future changes are reduced haze and improved visibility, increased primary organic to elemental carbon ratio, decreases in PM2.5 and its species, decreases and increases in dry deposition of SO2 and O3, respectively, and decreases in total nitrogen (TN) deposition. There is a tendency for transportation emission and CH4 changes to dominate the increases in O3, while climate change may either enhance or mitigate these increases in the west or east U.S., respectively. Climate change also decreases PM2.5 in the future. Other variable changes exhibit stronger susceptibility to either emission (e.g., CO, NOx, and TN deposition) or climate changes (e.g., VOC, NH3, SO2, and total sulfate deposition), which also have a strong dependence on season and specific U.S. regions.

Emissions of nitrogen oxides (NOx) and, subsequently, atmospheric levels of nitrogen dioxide (NO2) have decreased over the U.S. due to a combination of environmental policies and technological change. Consequently, NO2 levels have decreased by 30–40% in the last decade. We quantify NO2 trends (2005–2013) over the U.S. using surface measurements from the U.S. Environmental Protection Agency (EPA) Air Quality System (AQS) and an improved tropospheric NO2 vertical column density (VCD) data product from the Ozone Monitoring Instrument (OMI) on the Aura satellite. We demonstrate that the current OMI NO2 algorithm is of sufficient maturity to allow a favorable correspondence of trends and variations in OMI and AQS data. Our trend model accounts for the non-linear dependence of NO2 concentration on emissions associated with the seasonal variation of the chemical lifetime, including the change in the amplitude of the seasonal cycle associated with the significant change in NOx emissions that occurred over the last decade. The direct relationship between observations and emissions becomes more robust when one accounts for these non-linear dependencies. We improve the OMI NO2 standard retrieval algorithm and, subsequently, the data product by using monthly vertical concentration profiles, a required algorithm input, from a high-resolution chemistry and transport model (CTM) simulation with varying emissions (2005–2013). The impact of neglecting the time-dependence of the profiles leads to errors in trend estimation, particularly in regions where emissions have changed substantially. For example, trends calculated from retrievals based on time-dependent profiles offer 18% more instances of significant trends and up to 15% larger total NO2 reduction versus the results based on profiles for 2005. Using a CTM, we explore the theoretical relation of the trends estimated from NO2 VCDs to those estimated from ground-level concentrations. The model-simulated trends in VCDs strongly correlate with those estimated from surface concentrations (r = 0.83, N = 355). We then explore the observed correspondence of trends estimated from OMI and AQS data. We find a significant, but slightly weaker, correspondence (i.e., r = 0.68, N = 208) than predicted by the model and discuss some of the important factors affecting the relationship, including known problems (e.g., NOz interferents) associated with the AQS data. This significant correspondence gives confidence in trend and surface concentration estimates from OMI VCDs for locations, such as the majority of the U.S. and globe, that are not covered by surface monitoring networks. Using our improved trend model and our enhanced OMI data product, we find that both OMI and AQS data show substantial downward trends from 2005 to 2013, with an average reduction of 38% for each over the U.S. The annual reduction rates inferred from OMI and AQS measurements are larger (−4.8 ± 1.9%/yr, −3.7 ± 1.5%/yr) from 2005 to 2008 than 2010 to 2013 (−1.2 ± 1.2%/yr, −2.1 ± 1.4%/yr). We quantify NO2 trends for major U.S. cities and power plants; the latter suggest larger negative trend (−4.0 ± 1.5%/yr) between 2005 and 2008 and smaller or insignificant changes (−0.5 ± 1.2%/yr) during 2010–2013.

Organic aerosols (OAs) in the atmosphere affect Earth's energy budget by not only scattering but also absorbing solar radiation due to the presence of the so-called "brown carbon" (BrC) component. However, the absorptivities of OAs are not represented or are poorly represented in current climate and chemical transport models. In this study, we provide a method to constrain the BrC absorptivity at the emission inventory level using recent laboratory and field observations. We review available measurements of the light-absorbing primary OA (POA), and quantify the wavelength-dependent imaginary refractive indices (kOA, the fundamental optical parameter determining the particle's absorptivity) and their uncertainties for the bulk POA emitted from biomass/biofuel, lignite, propane, and oil combustion sources. In particular, we parametrize the kOA of biomass/biofuel combustion sources as a function of the black carbon (BC)-to-OA ratio, indicating that the absorptive properties of POA depend strongly on burning conditions. The derived fuel-type-based kOA profiles are incorporated into a global carbonaceous aerosol emission inventory, and the integrated kOA values of sectoral and total POA emissions are presented. Results of a simple radiative transfer model show that the POA absorptivity warms the atmosphere significantly and leads to ∼27% reduction in the amount of the net global average POA cooling compared to results from the nonabsorbing assumption.

Current emission inventories provide information about the mass emissions of different chemical species from different emitting sources without information concerning the size distribution of primary particulate matter (PM). The size distribution information, however, is an important input into chemical transport models that determine the fate of PM and its impacts on climate and public health. At present, models usually make rather rudimentary assumptions about the size distribution of primary PM emissions in their model inputs. In this study, we develop a global and regional, size-resolved, mass emission inventory of primary PM emissions from source-specific combustion components of the residential, industrial, power, and transportation sectors for the year 2010. Uncertainties in the emission profiles are also provided. The global size-resolved PM emissions show a distribution with a single peak and the majority of the mass of particles in size ranges smaller than 1 μm. The PM size distributions for different sectors and world regions vary considerably, due to the different combustion characteristics. Typically, the sizes of particles decrease in the order: power sector > industrial sector > residential sector > transportation sector. Three emission scenarios are applied to the baseline distributions to study the likely changes in size distribution of emissions as clean technologies are implemented.

Despite strenuous efforts to reduce the emissions of ozone precursors such as nitrogen oxides (NO x ), concentrations of ground-level ozone (O 3 ) still often exceed the National Ambient Air Quality Standard in U.S. cities in summertime, including Chicago. Furthermore, studies have projected a future increase in O 3 formation due to global climate change. This study examines the response of summertime O 3 to emission controls and temperature change in the Chicago area from 2005 to 2013 by employing observations of O 3 , O 3 precursors, and meteorological variables. We find that meteorology explains about 53% of the O 3 variance in Chicago. O 3 mixing ratios over Chicago are found to show no clear decline over the 2005–2013 period. The summertime ground-level O 3 trend consists of a decrease of 0.08 ppb/year between 2005 and 2009 and an increase of 1.49 ppb/year between 2009 and 2013. Emissions of NO x and concentrations of NO 2 have been decreasing steadily from 2005 to 2013 in the Chicago area. Concentrations of volatile organic compounds (VOCs) in Chicago, however, have more than doubled since 2009, even though emission inventories suggest that VOC emissions have decreased. We believe that O 3 production in Chicago became more sensitive to VOCs starting in 2008/2009 and may have switched from being NO x -limited to VOC-limited. The warmer climate since 2008 has also contributed to the increasing ozone trend in the Chicago area. Increased attention should be paid to improving the quantification of VOC sources, enhancing the monitoring of reactive VOC concentrations, and designing VOC mitigation measures.

Intercontinental transport of atmospheric pollution (ITAP) can offset the impact of local emission control efforts, impact human and ecosystem health, and play a role in climate forcing. This study aims to determine the role of ITAP caused by East Asian anthropogenic emissions (EAAEs) under current and future emission and climate scenarios. The contribution from EAAEs is determined using a "brute force method" in which results from simulations with and without EAAEs are compared. ITAP from East Asia is enhanced in the future due to faster wind speeds aloft and a stronger low pressure center near eastern Russia that facilitate enhanced westerly export in the free troposphere and stronger southerly transport near the surface, increased gaseous precursor emissions, and increased temperatures. As a result, the contribution of ozone (O3) generated by EAAEs to the global average O3 mixing ratio increases by ~0.8 ppb from 1.2 ppb in 2001 to 2.0 ppb in 2050. The contribution of PM2.5 generated by EAAEs to the global PM2.5 level increases by ~0.07 μg m−3 from 0.32 μg m−3 in 2001 to 0.39 μg m−3 in 2050, despite a non-homogenous response in PM2.5 resulting from cloud and radiative feedbacks. EAAEs can increase East Asian biogenic secondary organic aerosol by 10–81%, indicating that it is largely controllable. EAAEs also increase the deposition of nitrogen, black carbon, and mercury both locally and downwind, implying that they may play a role in climate feedbacks and ecosystem health of these regions. These results show that EAAEs have a large impact on global air quality and climate, especially on downwind regions. Such impacts may be enhanced under future climate and emission scenarios, demonstrating a need to synergize global pollution control and climate mitigation efforts.

A suite of mechanistic atmospheric and mercury (Hg) cycling and bioaccumulation models is applied to simulate atmospheric Hg deposition and Hg concentrations in the water column and in fish in a Hg-impaired freshwater lake located in the northeastern United States that receives its Hg loading primarily through deposition. Two future-year scenarios evaluate the long-term response of fish tissue Hg concentrations to reductions in local and nationwide coal-fired electric-generating utility and other Hg emissions and an increase or decrease in global (non-US) Hg emissions. Results indicate that fish tissue Hg concentrations in this ecosystem could require approximately 3 yr to 8 yr to begin to respond to declines in US emissions and deposition with a fish Hg reduction proportional to deposition reduction requiring over 50 yr. Furthermore, recovery could potentially be partially or completely offset by growth in non-US Hg emissions. Environ Toxicol Chem 2014;33:1238–1247. © 2014 SETAC

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When released to the biosphere, mercury (Hg) is very mobile and can take millennia to be returned to a secure, long-term repository. Understanding where and when Hg was released as a result of human activities allows better quantification of present-day reemissions and future trajectories of environmental concentrations. In this work, we estimate the time-varying releases of Hg in seven world regions over the 500 year period, 1510–2010. By our estimation, this comprises 95% of all-time anthropogenic releases. Globally, 1.47 Tg of Hg were released in this period, 23% directly to the atmosphere and 77% to land and water bodies. Cumulative releases have been largest in Europe (427 Gg) and North America (413 Gg). In some world regions (Africa/Middle East and Oceania), almost all (>99%) of the Hg is relatively recent (emitted since 1850), whereas in South America it is mostly of older vintage (63% emitted before 1850). Asia was the greatest-emitting region in 2010, while releases in Europe and North America have declined since the 1970s, as recognition of the risks posed by Hg have led to its phase-out in commercial usage. The continued use of Hg in artisanal and small-scale gold mining means that the Africa/Middle East region is now a major contributor. We estimate that 72% of cumulative Hg emissions to air has been in the form of elemental mercury (Hg0), which has a long lifetime in the atmosphere and can therefore be transported long distances. Our results show that 83% of the total Hg has been released to local water bodies, onto land, or quickly deposited from the air in divalent (HgII) form. Regionally, this value ranges from 77% in Africa/Middle East and Oceania to 89% in South America. Results from global biogeochemical modeling indicate improved agreement of the refined emission estimates in this study with archival records of Hg accumulation in estuarine and deep ocean sediment.

We show that Aura Ozone Monitoring Instrument (OMI) nitrogen dioxide (NO2) tropospheric column data may be used to assess changes of the emissions of nitrogen oxides (NOx) from power plants in the United States, though careful interpretation of the data is necessary. There is a clear response for OMI NO2 data to NOx emission reductions from power plants associated with the implementation of mandated emission control devices (ECDs) over the OMI record (2005–2011). This response is scalar for all intents and purposes, whether the reduction is rapid or incremental over several years. However, it is variable among the power plants, even for those with the greatest absolute decrease in emissions. We document the primary causes of this variability, presenting case examples for specific power plants.

[1] Elevated mercury (Hg) in marine and terrestrial ecosystems is a global health concern because of the formation of toxic methylmercury. Humans have emitted Hg to the atmosphere for millennia, and this Hg has deposited and accumulated into ecosystems globally. Here we present a global biogeochemical model with fully coupled atmospheric, terrestrial, and oceanic Hg reservoirs to better understand human influence on Hg cycling and timescales for responses. We drive the model with a historical inventory of anthropogenic emissions from 2000 BC to present. Results show that anthropogenic perturbations introduced to surface reservoirs (atmosphere, ocean, or terrestrial) accumulate and persist in the subsurface ocean for decades to centuries. The simulated present-day atmosphere is enriched by a factor of 2.6 relative to 1840 levels, consistent with sediment archives, and by a factor of 7.5 relative to natural levels (2000 BC). Legacy anthropogenic Hg re-emitted from surface reservoirs accounts for 60% of present-day atmospheric deposition, compared to 27% from primary anthropogenic emissions, and 13% from natural sources. We find that only 17% of the present-day Hg in the surface ocean is natural and that half of its anthropogenic enrichment originates from pre-1950 emissions. Although Asia is presently the dominant contributor to primary anthropogenic emissions, only 17% of the surface ocean reservoir is of Asian anthropogenic origin, as compared to 30% of North American and European origin. The accumulated burden of legacy anthropogenic Hg means that future deposition will increase even if primary anthropogenic emissions are held constant. Aggressive global Hg emission reductions will be necessary just to maintain oceanic Hg concentrations at present levels.

China’s twelfth Five-Year Plan included pollution control measures with a goal of reducing national emissions of nitrogen oxides (NOx) by 10% by 2015 compared with 2010. Multiple linear regression analysis was used on 11-year time series of all nitrogen dioxide (NO2) pixels from the Ozone Monitoring Instrument (OMI) over 18 NO2 hotspots in China. The regression analysis accounted for variations in meteorology, pixel resolution, seasonal effects, weekday variability and year-to-year variability. The NO2 trends suggested that there was an increase in NO2 columns in most areas from 2005 to around 2011 which was followed by a strong decrease continuing through 2015. The satellite results were in good agreement with the annual official NOx emission inventories which were available up until 2014. This shows the value of evaluating trends in emission inventories using satellite retrievals. It further shows that recent control strategies were effective in reducing emissions and that recent economic transformations in China may be having an effect on NO2 columns. Satellite information for 2015 suggests that emissions have continued to decrease since the latest inventories available and have surpassed the goals of the twelfth Five-Year Plan.

Mercury (Hg) stable isotopes provide a new tool to trace the biogeochemical cycle of Hg. An inventory of the isotopic composition of historical anthropogenic Hg emissions is important to understand sources and post-emission transformations of Hg. We build on existing global inventories of anthropogenic Hg emissions to the atmosphere to develop the first corresponding historical Hg isotope inventories for total Hg (THg) and three Hg species: gaseous elemental Hg (GEM), gaseous oxidized Hg (GOM) and particulate-bound Hg (PBM). We compile δ202Hg and Δ199Hg of major Hg emissions source materials. Where possible, δ202Hg and Δ199Hg values in emissions are corrected for the mass dependent Hg isotope fractionation during industrial processing. The framework and Hg isotope inventories can be updated and improved as new data become available. Simulated THg emissions from all sectors between 1850s and 2010s generally show an increasing trend (−1.1‰ to −0.7‰) for δ202Hg, and a stable trend (−0.02‰ to −0.04‰) for Δ199Hg. Δ200Hg are near-zero in source materials and therefore emissions. The δ202Hg trend generally reflects a shift of historically dominant Hg emissions from 19th century Hg mining and liquid Hg0 uses in Au/Ag refining to 20th century coal combustion and non-ferrous metal production. The historical δ202Hg and Δ199Hg curves of GEM closely follow those of THg. The δ202Hg curves of GOM and PBM show no trends. Δ199Hg values for both GOM and PBM decrease from the 1850s to 1950s by ∼0.1‰, and then gradually rebound towards the 2010s. Our updated δ202Hg values (−0.76 ± 0.11 ‰, 1SD, n=9) of bulk emissions from passively degassing volcanoes overlap with δ202Hg of present-day anthropogenic THg emissions.

The sectoral and regional contributions from northern hemisphere anthropogenic and biomass burning emission sectors to black carbon (BC) distributions over the continental United States (CONUS) in summer 2008 are studied using the Sulfur Transport and dEposition Model (STEM). North American (NA) emissions heavily (>70% of total emissions) affect the BC levels from the surface to w5 km, while non-NA plumes compose more than half of the BC above w5 km. Among all sectors, NA and non-NA biomass burning, NA transportation and non-NA residential emissions are the major contributors. The sectoral contributions vary among ten regions defined by the US Environmental Protection Agency (EPA): NA anthropogenic emissions enhance northeastern US BC levels; biomass burning strongly impacts northern California and southeastern US; and the influence of extra-regional plumes is largest in the northwestern US but extends to eastern US. The mean contribution from non-NA sources to US surface BC is w0.05 m gm �3 , with a maximum value of w0.11 m gm �3 in the northwestern US. The non-NA contributions to column BC are higher than to surface BC, ranging from 30% to 80%, depending on region. EPA region 8 is most sensitive to extra-regional BC, partially explaining the observed increasing BC trend there during the past decades associated with the increasing Asian BC emissions. Measurements from the June 24 DC-8 flight during the ARCTAS-CARB field campaign show that BC/(organic matter þ nitrate þ sulfate) mass ratios fairly well represent BC’s warming potential over southern California, which can be approximated by BC/(organic matter þ sulfate) and BC/sulfate for plumes affected and unaffected by fires, respectively. The responses of BC/(organic matter þ sulfate) and BC/sulfate to removing each emission sector are further discussed, indicating that mitigating NA transportation emissions has the highest potential for regional air quality and climate co-benefits.

We calculate decadal aerosol direct and indirect (warm cloud) radiative forcings from US anthropogenic sources over the 1950–2050 period. Past and future aerosol distributions are constructed using GEOS-Chem and historical emission inventories and future projections from the IPCC A1B scenario. Aerosol simulations are evaluated with observed spatial distributions and 1980–2010 trends of aerosol concentrations and wet deposition in the contiguous US. Direct and indirect radiative forcing is calculated using the GISS general circulation model and monthly mean aerosol distributions from GEOS-Chem. The radiative forcing from US anthropogenic aerosols is strongly localized over the eastern US. We find that its magnitude peaked in 1970–1990, with values over the eastern US (east of 100° W) of −2.0 W m−2 for direct forcing including contributions from sulfate (−2.0 W m−2), nitrate (−0.2 W m−2), organic carbon (−0.2 W m−2), and black carbon (+0.4 W m−2). The uncertainties in radiative forcing due to aerosol radiative properties are estimated to be about 50%. The aerosol indirect effect is estimated to be of comparable magnitude to the direct forcing. We find that the magnitude of the forcing declined sharply from 1990 to 2010 (by 0.8 W m−2 direct and 1.0 W m−2 indirect), mainly reflecting decreases in SO2 emissions, and project that it will continue declining post-2010 but at a much slower rate since US SO2 emissions have already declined by almost 60% from their peak. This suggests that much of the warming effect of reducing US anthropogenic aerosol sources has already been realized. The small positive radiative forcing from US BC emissions (+0.3 W m−2 over the eastern US in 2010; 5% of the global forcing from anthropogenic BC emissions worldwide) suggests that a US emission control strategy focused on BC would have only limited climate benefit.

Global policies regulating anthropogenic mercury require an understanding of the relationship between emitted and deposited mercury on intercontinental scales. Here, we examine source-receptor relationships for present-day conditions and four 2050 IPCC scenarios encompassing a range of economic development and environmental regulation projections. We use the GEOS-Chem global model to track mercury from its point of emission through rapid cycling in surface ocean and land reservoirs to its accumulation in longer lived ocean and soil pools. Deposited mercury has a local component (emitted Hg(II), lifetime of 3.7 days against deposition) and a global component (emitted Hg(0), lifetime of 6 months against deposition). Fast recycling of deposited mercury through photoreduction of Hg(II) and re-emission of Hg(0) from surface reservoirs (ice, land, surface ocean) increases the effective lifetime of anthropogenic mercury to 9 months against loss to legacy reservoirs (soil pools and the subsurface ocean). This lifetime is still sufficiently short that source-receptor relationships have a strong hemispheric signature. Asian emissions are the largest source of anthropogenic deposition to all ocean basins, though there is also regional source influence from upwind continents. Current anthropogenic emissions account for only about one-third of mercury deposition to the global ocean with the remainder from natural and legacy sources. However, controls on anthropogenic emissions would have the added benefit of reducing the legacy mercury re-emitted to the atmosphere. Better understanding is needed of the time scales for transfer of mercury from active pools to stable geochemical reservoirs.

China and India are the two largest anthropogenic aerosol generating countries in the world. In this study, we develop a new inventory of sulfur dioxide (SO2) and primary carbonaceous aerosol (i.e., black and organic carbon, BC and OC) emissions from these two countries for the period 1996–2010, using a technology-based methodology. Emissions from major anthropogenic sources and open biomass burning are included, and time-dependent trends in activity rates and emission factors are incorporated in the calculation. Year-specific monthly temporal distributions for major sectors and gridded emissions at a resolution of 0.1°×0.1° distributed by multiple year-by-year spatial proxies are also developed. In China, the interaction between economic development and environmental protection causes large temporal variations in the emission trends. From 1996 to 2000, emissions of all three species showed a decreasing trend (by 9 %–17 %) due to a slowdown in economic growth, a decline in coal use in non-power sectors, and the implementation of air pollution control measures. With the economic boom after 2000, emissions from China changed dramatically. BC and OC emissions increased by 46 % and 33 % to 1.85 Tg and 4.03 Tg in 2010. SO2 emissions first increased by 61 % to 34.0 Tg in 2006, and then decreased by 9.2 % to 30.8 Tg in 2010 due to the wide application of flue-gas desulfurization (FGD) equipment in power plants. Driven by the remarkable energy consumption growth and relatively lax emission controls, emissions from India increased by 70 %, 41 %, and 35 % to 8.81 Tg, 1.02 Tg, and 2.74 Tg in 2010 for SO2, BC, and OC, respectively. Monte Carlo simulations are used to quantify the emission uncertainties. The average 95 % confidence intervals (CIs) of SO2, BC, and OC emissions are estimated to be −16 %–17 %, −43 %–93 %, and −43 %–80 % for China, and −15 %–16 %, −41 %–87 %, and −44 %–92 % for India, respectively. Sulfur content, fuel use, and sulfur retention of hard coal and the actual FGD removal efficiency are the main contributors to the uncertainties of SO2 emissions. Biofuel combustion related parameters (i.e., technology divisions, fuel use, and emission factor determinants) are the largest source of OC uncertainties, whereas BC emissions are also sensitive to the parameters of coal combustion in the residential and industrial sectors and the coke-making process. Comparing our results with satellite observations, we find that the trends of estimated emissions in both China and India are in good agreement with the trends of aerosol optical depth (AOD) and SO2 retrievals obtained from different satellites.

Chronic high surface ozone (O3) levels and the increasing sulfur oxides (SOx = SO2+SO4) ambient concentrations over South Coast (SC) and other areas of California (CA) are affected by both local emissions and long-range transport. In this paper, multi-scale tracer, full-chemistry and adjoint simulations using the STEM atmospheric chemistry model are conducted to assess the contribution of local emission sourcesto SC O3 and to evaluate the impacts of transported sulfur and local emissions on the SC sulfur budgetduring the ARCTAS-CARB experiment period in 2008. Sensitivity simulations quantify contributions of biogenic and fire emissions to SC O3 levels. California biogenic and fire emissions contribute 3–4 ppb to near-surface O3 over SC, with larger contributions to other regions in CA. During a long-range transport event from Asia starting from 22 June, high SOx levels (up to ~0.7 ppb of SO2 and ~1.3 ppb of SO4) is observed above ~6 km, but they did not affect CA surface air quality. The elevated SOx observed at 1–4 km is estimated to enhance surface SOx over SC by ~0.25 ppb (upper limit) on ~24 June. The near-surface SOx levels over SC during the flight week are attributed mostly to local emissions. Two anthropogenic SOx emission inventories (EIs) from the California Air Resources Board (CARB) and the US Environmental Protection Agency (EPA) are compared and applied in 60 km and 12 km chemical transport simulations, and the results are compared withobservations. The CARB EI shows improvements over the National Emission Inventory (NEI) by EPA, but generally underestimates surface SC SOx by about a factor of two. Adjoint sensitivity analysis indicated that SO2 levels at 00:00 UTC (17:00 local time) at six SC surface sites were influenced by previous day maritime emissions over the ocean, the terrestrial emissions over nearby urban areas, and by transported SO2 from the north through both terrestrial and maritime areas. Overall maritime emissions contribute 10–70% of SO2 and 20–60% fine SO4 on-shore and over the most terrestrial areas, with contributions decreasing with in-land distance from the coast. Maritime emissions also modify the photochemical environment, shifting O3 production over coastal SC to more VOC-limited conditions. These suggest an important role for shipping emission controls in reducing fine particle and O3 concentrations in SC.

We use GEOS-Chem chemical transport model simulations of sulfate-ammonium aerosol data from the NASA ARCTAS and NOAA ARCPAC aircraft campaigns in the North American Arctic in April 2008, together with longer-term data from surface sites, to better understand aerosol sources in the Arctic in winter-spring and the implications for aerosol acidity. Arctic pollution is dominated by transport from mid-latitudes, and we test the relevant ammonia and sulfur dioxide emission inventories in the model by comparison with wet deposition flux data over the source continents. We find that a complicated mix of natural and anthropogenic sources with different vertical signatures is responsible for sulfate concentrations in the Arctic. East Asian pollution influence is weak in winter but becomes important in spring through transport in the free troposphere. European influence is important at all altitudes but never dominant. West Asia (non-Arctic Russia and Kazakhstan) is the largest contributor to Arctic sulfate in surface air in winter, reflecting a southward extension of the Arctic front over that region. Ammonium in Arctic spring mostly originates from anthropogenic sources in East Asia and Europe, with added contribution from boreal fires, resulting in a more neutralized aerosol in the free troposphere than at the surface. The ARCTAS and ARCPAC data indicate a median aerosol neutralization fraction [NH^(+)_(4)]/(2[SO^(2-)_(4)] + [NO^(-)_(3)]) of 0.5 mol mol^(-1) below 2 km and 0.7 mol mol^(-1) above. We find that East Asian and European aerosol transported to the Arctic is mostly neutralized, whereas West Asian and North American aerosol is highly acidic. Growth of sulfur emissions in West Asia may be responsible for the observed increase in aerosol acidity at Barrow over the past decade. As global sulfur emissions decline over the next decades, increasing aerosol neutralization in the Arctic is expected, potentially accelerating Arctic warming through indirect radiative forcing and feedbacks.

Mercury concentrations of flue gas at inlet/outlet of the flue gas cleaning, electrostatic demister, reclaiming tower, acid plant, and mercury contents in zinc concentrate and by-products were measured in a hydrometallurgical zinc smelter. The removal efficiency of flue gas cleaning, electrostatic demister, mercury reclaiming and acid plant was about 17.4%, 30.3%, 87.9% and 97.4% respectively. Flue gas cleaning and electrostatic demister captured 11.7% and 25.3% of the mercury in the zinc concentrate, respectively. The mercury reclaiming tower captured 58.3% of the mercury in the zinc concentrate. About 4.2% of the mercury in the zinc concentrate was captured by the acid plant. Consequently, only 0.8% of the mercury in the zinc concentrate was emitted to the atmosphere. The atmospheric mercury emission factor was 0.5 g t(-1) of zinc produced for the tested smelter, indicating that this process offers the potential to effectively reduce mercury emissions from zinc smelting.

We interpret observations from the Intercontinental Chemical Transport Experiment, Phase B (INTEX-B) in spring 2006 using a global chemical transport model (GEOS-Chem) to evaluate sensitivities of the free troposphere above the North Pacific Ocean and North America to Asian anthropogenic emissions. We develop a method to use satellite observations of tropospheric NO2 columns to provide timely estimates of trends in NOx emissions. NOx emissions increased by 33% for China and 29% for East Asia from 2003 to 2006. We examine measurements from three aircraft platforms from the INTEX-B campaign, including a Canadian Cessna taking vertical profiles of ozone near Whistler Peak. The contribution to the mean simulated ozone profiles over Whistler below 5.5 km is at least 7.2 ppbv for Asian anthropogenic emissions and at least 3.5 ppbv for global lightning NOx emissions. Tropospheric ozone columns from OMI exhibit a broad Asian outflow plume across the Pacific, which is reproduced by simulation. Mean modelled sensitivities of Pacific (30° N–60° N) tropospheric ozone columns are at least 4.6 DU for Asian anthropogenic emissions and at least 3.3 DU for lightning, as determined by simulations excluding either source. Enhancements of ozone over Canada from Asian anthropogenic emissions reflect a combination of trans-Pacific transport of ozone produced over Asia, and ozone produced in the eastern Pacific through decomposition of peroxyacetyl nitrates (PANs). A sensitivity study decoupling PANs globally from the model's chemical mechanism establishes that PANs increase ozone production by removing NOx from regions of low ozone production efficiency (OPE) and injecting it into regions with higher OPE, resulting in a global increase in ozone production by 2% in spring 2006. PANs contribute up to 4 ppbv to surface springtime ozone concentrations in western Canada. Ozone production due to PAN transport is greatest in the eastern Pacific; commonly occurring transport patterns advect this ozone northeastward into Canada. Transport events observed by the aircraft confirm that polluted airmasses were advected in this way.

Following the meteorological evaluation in Part I, this Part II paper presents the statistical evaluation of air quality predictions by the U.S. Environmental Protection Agency (U.S. EPA)’s Community Multi-Scale Air Quality (Models-3/CMAQ) model for the four simulated months in the base year 2005. The surface predictions were evaluated using the Air Pollution Index (API) data published by the China Ministry of Environmental Protection (MEP) for 31 capital cities and daily fine particulate matter (PM2.5, particles with aerodiameter less than or equal to 2.5 mm) observations of an individual site in Tsinghua University (THU). To overcome the shortage in surface observations, satellite data are used to assess the column predictions including tropospheric nitrogen dioxide (NO2) column abundance and aerosol optical depth (AOD). The result shows that CMAQ gives reasonably good predictions for the air quality. The air quality improvement that would result from the targeted sulfur dioxide (SO2) and nitrogen oxides (NOx) emission controls in China were assessed for the objective year 2010. The results show that the emission controls can lead to significant air quality benefits. SO2 concentrations in highly polluted areas of East China in 2010 are estimated to be decreased by 30e60% compared to the levels in the 2010 Business-As-Usual (BAU) case. The annual PM2.5 can also decline by 3e15 mgm �3 (4e25%) due to the lower SO2 and sulfate concentrations. If similar controls are implemented for NOx emissions, NOx concentrations are estimated to decrease by 30e60% as compared with the 2010 BAU scenario. The annual mean PM2.5 concentrations will also decline by 2e14 mgm �3 (3e12%). In addition, the number of

Following model evaluation inpart I, this part II paper focuses on the process analysis and chemical regime analysis for the formation of ozone (O3) and particulate matter with aerodynamic diameter less than or equal to 10 mm (PM10) in China. The process analysis results show that horizontal transport is the main contributortothe accumulation of O3in Jan., Apr., and Oct., and gas-phase chemistryand vertical transport contribute to the production and accumulation of O3 in Jul. Removal pathways of O3 include vertical and horizontal transport, gas-phase chemistry, and cloud processes, depending on locations and seasons. PM10 is mainly produced by primary emissions and aerosol processes and removed by horizontal transport. Cloud processes could either decrease or increase PM10 concentrations, depending on locations and seasons. Among all indicators examined, the ratio of PHNO3=PH2O2 provides the most robust indicator for O3 chemistry,indicatingaVOC-limitedO3chemistryover mostof the easternChina in Jan., NOx-limitedin Jul., and either VOC- or NOx-limited in Apr. and Oct. O3 chemistry is NOx-limited in most central and western China and VOC-limitedin majorcitiesthroughout theyear.The adjustedgas ratio,AdjGR,indicates that PM formation in the eastern China is most sensitive to the emissions of SO2 and may be more sensitive to emission reductions in NOx than in NH3. These results are fairly consistent with the responses of O3

Multi-scale tracer and full-chemistry simulations with the STEM atmospheric chemistry model are used to analyze the effects of transported background ozone (O3) from the eastern Pacific on California air quality during the ARCTAS-CARB experiment conducted in June, 2008. Previous work has focused on the importance of long-range transport of O3 to North America air quality in springtime. However during this summer experiment the long-range transport of O3 is also shown to be important. Simulated and observed O3 transport patterns from the coast to inland northern California are shown to vary based on meteorological conditions and the O3 profiles over the oceans, which are strongly episodically affected by Asian inflows. Analysis of the correlations of O3 at various altitudes above the coastal site at Trinidad Head and at a downwind surface site in northern California, show that under long-range transport events, high O3 air-masses (O3>60 ppb) at altitudes between about 2 and 4 km can be transported inland and can significantly influence surface O3 20–30 h later. These results show the importance of characterizing the vertical structure of the lateral boundary conditions (LBC) needed in air quality simulations. The importance of the LBC on O3 prediction during this period is further studied through a series of sensitivity studies using different forms of LBC. It is shown that the use of the LBC downscaled from RAQMS global model that assimilated MLS and OMI data improves the model performance. We also show that the predictions can be further improved through the use of LBC based on NASA DC-8 airborne observations during the ARCTAS-CARB experiment. These results indicate the need to develop observational strategies to provide information on the three-dimensional nature of pollutant distributions, in order to improve our capability to predict pollution levels and to better quantify the influence of these Asian inflows on the US west coast air quality.

East Asia is the largest source region of global anthropogenic mercury emissions, and contributes to atmospheric mercury concentration and deposition in other regions. Similarly, mercury from the global pool also plays a role in the chemical transport of mercury in East Asia. Annual simulations of atmospheric mercury in East Asia were performed using the STEM-Hg modeling system to study the mass budgets of mercury in the region. The model results showed strong seasonal variation in mercury concentration and deposition, with signals from large point sources. The annual mean concentrations for gaseous elemental mercury, reactive gaseous mercury and particulate mercury in central China and eastern coastal areas were 1.8 ng m(-3), 100 pg m(-3) and 150 pg m(-3), respectively. Boundary conditions had a strong influence on the simulated mercury concentration and deposition, contributing to 80% of the concentration and 70% of the deposition predicted by the model. The rest was caused by the regional emissions before they were transported out of the model domain. Using different oxidation rates reported for the Hg(0)-O(3) reaction (i.e., by Hall, 1995 vs. by Pal and Ariya, 2004) led to a 9% difference in the predicted mean concentration and a 40% difference in the predicted mean deposition. The estimated annual dry and wet deposition for East Asia in 2001 was in the range of 590-735 Mg and 482-696 Mg, respectively. The mercury mass outflow caused by the emissions in the domain was estimated to be 681-714 Mg yr(-1). This constituted 70% of the total mercury emission in the domain. The greatest outflow occurred in spring and early summer.

With the rapid development of the economy, the sulfur dioxide (SO2) emission from China since 2000 is of increasing concern. In this study, we estimate the annual SO2 emission in China after 2000 using a technology-based methodology specifically for China. From 2000 to 2006, total SO2 emission in China increased by 53%, from 21.7 Tg to 33.2 Tg, at an annual growth rate of 7.3%. Emissions from power plants are the main sources of SO2 in China and they increased from 10.6 Tg to 18.6 Tg in the same period. Geographically, emission from north China increased by 85%, whereas that from the south increased by only 28%. The emission growth rate slowed around 2005, and emissions began to decrease after 2006 mainly due to the wide application of flue-gas desulfurization (FGD) devices in power plants in response to a new policy of China's government. This paper shows that the trend of estimated SO2 emission in China is consistent with the trends of SO2 concentration and acid rain pH and frequency in China, as well as with the increasing trends of background SO2 and sulfate concentration in East Asia. A longitudinal gradient in the percentage change of urban SO2 concentration in Japan is found during 2000–2007, indicating that the decrease of urban SO2 is lower in areas close to the Asian continent. This implies that the transport of increasing SO2 from the Asian continent partially counteracts the local reduction of SO2 emission downwind. The aerosol optical depth (AOD) products of Moderate Resolution Imaging Spectroradiometer (MODIS) are found to be highly correlated with the surface solar radiation (SSR) measurements in East Asia. Using MODIS AOD data as a surrogate of SSR, we found that China and East Asia excluding Japan underwent a continuous dimming after 2000, which is in line with the dramatic increase in SO2 emission in East Asia. The trends of AOD from both satellite retrievals and model over East Asia are also consistent with the trend of SO2 emission in China, especially during the second half of the year, when sulfur contributes the largest fraction of AOD. The arrested growth in SO2 emissions since 2006 is also reflected in the decreasing trends of SO2 and SO42− concentrations, acid rain pH values and frequencies, and AOD over East Asia.

This paper provides an up-to-date assessment of global mercury emissions from anthropogenic and natural sources. On an annual basis, natural sources account for 5207 Mg of mercury released to the global atmosphere, including the contribution from re-emission processes, which are emissions of previously deposited mercury originating from anthropogenic and natural sources, and primary emissions from natural reservoirs. Anthropogenic sources, which include a large number of industrial point sources, are estimated to account for 2320 Mg of mercury emitted annually. The major contributions are from fossil-fuel fired power plants (810 Mg yr−1), artisanal small scale gold mining (400 Mg yr−1), non-ferrous metals manufacturing (310 Mg yr−1), cement production (236 Mg yr−1), waste disposal (187 Mg yr−1) and caustic soda production (163 Mg yr−1). Therefore, our current estimate of global mercury emissions suggests that the overall contribution from natural sources (primary emissions + re-emissions) and anthropogenic sources is nearly 7527 Mg per year, the uncertainty associated with these estimates are related to the typology of emission sources and source regions.

Ambient VOCs were measured by a proton transfer reaction-mass spectrometer (PTR-MS) at a receptor site in the Pearl River Delta (PRD) during October 19-November 18, 2008. Biomass burning plumes are identified by using acetonitrile as tracer, and enhancement ratios (ERs) of nine VOCs species relative to acetonitrile are obtained from linear regression analysis and the source-tracer-ratio method. Enhancement ratios determined by the two different methods show good agreement for most VOCs species. Biomass burning contributions are investigated by using the source-tracer-ratio method. Biomass burning contributed 9.5%-17.7% to mixing ratios of the nine VOCs. The estimated biomass burning contributions are compared with local emission inventories. Large discrepancies are observed between our results and the estimates in two emission inventories. Though biomass burning emissions in TRACE-P inventory agree well with our results, the VOCs speciation for aromatic compounds may be not appropriate for Guangdong.

A detailed multiple-year inventory of mercury emissions from anthropogenic activities in China has been developed. Coal combustion and nonferrous metals production continue to be the two leading mercury sources in China, together contributing ~80% of total mercury emissions. However, many uncertainties still remain in our knowledge of primary anthropogenic releases of mercury to the atmosphere in China. In situations involving large uncertainties, our previous mercury emission inventory that used a deterministic approach could produce results that might not be a true reflection of reality; and in such cases stochastic simulations incorporating uncertainties need to be performed. Within our inventory, a new comprehensive sub-module for estimation of mercury emissions from coal-fired power plants in China is constructed as an uncertainty case study. The new sub-module integrates up-to-date information regarding mercury content in coal by province, coal washing and cleaning, coal consumption by province, mercury removal efficiencies by control technology or technology combinations, etc. Based on these detailed data, probability-based distribution functions are built into the sub-module to address the uncertainties of these key parameters. The sub-module incorporates Monte Carlo simulations to take into account the probability distributions of key input parameters and produce the mercury emission results in the form of a statistical distribution. For example, the best estimate for total mercury emissions from coal-fired power plants in China in 2003 is 90.5 Mg, with the uncertainty range from 57.1 Mg (P10) to 154.6 Mg (P90); and the best estimate for elemental mercury emissions is 43.0 Mg, with the uncertainty range from 25.6 Mg (P10) to 75.7 Mg (P90). The results further indicate that the majority of the uncertainty in mercury emission estimation comes from two factors: mercury content of coal and mercury removal efficiency.

East Asia contributes to nearly 50% of the global anthropogenic mercury emissions into the atmosphere. Recently, there have been concerns about the long-range transport of mercury from East Asia, which may lead to enhanced dry and wet depositions in other regions. In this study, we performed four monthly simulations (January, April, July and October in 2005) using CMAQ-Hg v4.6 for a number of emission inventory scenarios in an East Asian model domain. Coupled with mass balance analyses, the chemical transport of mercury in East Asia and the resulted mercury emission outflow were investigated. The total annual mercury deposition in the region was estimated to be 821 Mg, with 396 Mg contributed by wet deposition and 425 Mg by dry deposition. Anthropogenic emissions were responsible for most of the estimated deposition (75%). The deposition caused by emissions from natural sources was less important (25%). Regional mercury transport budgets showed strong seasonal variability, with a net removal of RGM (7–15 Mg month−1) and PHg (13–21 Mg month−1) in the domain, and a net export of GEM (60–130 Mg month−1) from the domain. The outflow caused by East Asian emissions (anthropogenic plus natural) was estimated to be in the range of 1369–1671 Mg yr−1, of which 50–60% was caused by emissions from natural sources. The emission outflow represented about 75% of the total mercury emissions in the region, and would contribute to 20–30% of mercury deposition in remote receptors.

Aerosol distributions in Asia calculated over a 4-year period and constrained by satellite observations of aerosol optical depth (AOD) are presented. Vast regions in Asia that include80% of the population have PM2.5 concentrations that exceed on an annual basis the WHO guideline of 10 microg/m3, often by factors of 2 to 4. These high aerosol loadings also have important radiative effects, causing a significant dimming at the surface, and mask approximately 45% of the warming by greenhouse gases. Black carbon (BC) concentrations are high throughout Asia, representing 5-10% of the total AOD, and contributing significantly to atmospheric warming (its warming potential is approximately 55% of that due to CO2). PM levels and AODs in year 2030, estimated based on simulations that consider future changes in emissions, are used to explore opportunities for win-win strategies built upon addressing air quality and climate change together. It is found that in 2030 the PM2.5 levels in significant parts of Asia will increase and exacerbate health impacts; but the aerosols will have a larger masking effect on radiative forcing, due to a decrease in BC and an increase in SO2 emissions.

We use a global chemical transport model (GEOS-Chem) with 1� � 1� horizontal resolution to quantify the effects of anthropogenic emissions from Canada, Mexico, and outside North America on daily maximum 8-hour average ozone concentrations in US surface air. Simulations for summer 2001 indicate mean North American and US background concentrations of 26 � 8 ppb and 30 � 8 ppb, as obtained by eliminating anthropogenic emissions in North America vs. in the US only. The US background never exceeds 60 ppb in the model. The Canadian and Mexican pollution enhancement averages 3 � 4 ppb in the US in summer but can be occasionally much higher in downwind regions of the northeast and southwest, peaking at 33 ppb in upstate New York (on a day with 75 ppb total ozone) and 18 ppb in southern California (on a day with 68 ppb total ozone). The model is successful in reproducing the observed variability of ozone in these regions, including the occurrence and magnitude of high-ozone episodes influenced by transboundary pollution. We find that exceedances of the 75 ppb US air quality standard in eastern Michigan, western New York, New Jersey, and southern California are often associated with Canadian and Mexican pollution enhancements in excess of 10 ppb. Sensitivity simulations with 2020 emission projections suggest that Canadian pollution influence in the Northeast US will become comparable in magnitude to that from domestic power plants.

This paper examines Beijing air quality in the winter and summer of 2001 using an integrated air quality modeling system (Fifth Generation Mesoscale Meteorological Model [MM5]/Community Multiscale Air Quality [CMAQ]) in nested mode. The National Aeronautics and Space Administration (NASA) Transport and Chemical Evolution over the Pacific (TRACE-P) emission inventory is used in the 36- (East Asia), 12- (East China), and 4-km (greater Beijing area) domains. Furthermore, we develop a local Beijing emission inventory that is used in the 4-km domain. We also construct a corroborated mapping of chemical species between the TRACE-P inventory and the Carbon Bond IV (CB-IV) chemical mechanism before the integrated modeling system is applied to study ozone (O3) and particulate matter (PM) in Beijing. Meteorological data for the integrated modeling runs are extracted from MM5. Model results show O3 hourly concentrations in the range of 80-159 parts per billion (ppb) during summer in the urban areas and up to 189 ppb downwind of the city. High fine PM (PM2.5) concentrations (monthly average of 75 microg x m(-3) in summer and 150 microg x m(-3) in winter) are simulated over the metropolitan and down-wind areas with significant secondary constituents. A comparison against available O3 and PM measurement data in Beijing is described. We recommend refinements to the developed local Beijing emission inventory to improve the simulation of Beijing's air quality. The 4-km modeling configuration is also recommended for the development of air pollution control strategies.

East Asia is one of the largest source regions that release mercury into the atmosphere. Although extensive studies have been devoted to estimating the anthropogenic mercury emission, little is known about mercury emission from natural sources in the region. In this study, we adapt the algorithms developed previously, coupled with detailed GIS data and satellite LAI products, to estimate mercury emission from natural sources including vegetation, soil, and water surfaces in an East Asian domain containing 164 × 97 grid cells at a spatial resolution of 36 km. Seasonal simulations were performed to project the annual emission quantity. The simulated emission shows strong diurnal and seasonal variations due to meteorology and vegetation coverage. The annual emission in the form of gaseous elemental mercury (GEM) from the domain in 2001 is estimated to be 834 Mg, with 462 Mg contributed from China. The estimated GEM emission is comparable to the reported anthropogenic emission of 575 ± 261 Mg (56% GEM, 32% reactive gaseous mercury, 12% particulate mercury; Wu, Y., Wang, S., Streets, D.G., Hao, J., Chan, M., Jiang, J., 2006. Trends in anthropogenic mercury emissions in China from 1995 to 2003. Environmental Science & Technology 40, 5312–5318) in China for the year 2001, and dominates the anthropogenic emission during the warm season. Combining the anthropogenic and natural emission estimates, the total mercury emission from China is 776–1298 Mg, with GEM being in the range of 660–1000 Mg. The latter is similar to the GEM emission quantity inferred from aircraft measurement (765 Mg; Friedli, H.R., Radke, L.F., Prescott, R., Li, P., Woo, J.-H., Carmichael, G.R., 2004. Mercury in the atmosphere around Japan, Korea and China as observed during the 2001 ACE Asia field campaign: measurements, distributions, sources, and implications. Journal of Geophysical Research 109, D19 S25) and modeling estimate (1140 Mg; Pan, L., Chai, T., Carmichael, G.R., Tang, Y., Streets, G.G., Woo, J.-H., Friedli, H.R., Radke, L.F., 2007a. Top-down estimate of mercury emissions in China using four-dimensional variational data assimilation. Atmospheric Environment 41, 2804–2819) in China for the year 2001. The estimated natural emission helps explain the gap between the anthropogenic emission estimates based on activity data (e.g., Pacyna, J.M., Pacyna, E., Steenhuisen, F., Wilson, S., 2006. Global anthropogenic mercury emission inventory for 2000. Atmospheric Environment 40, 4048–4063; Wu, Y., Wang, S., Streets, D.G., Hao, J., Chan, M., Jiang, J., 2006. Trends in anthropogenic mercury emissions in China from 1995 to 2003. Environmental Science & Technology 40, 5312–5318) and the emission inferred from field observations (e.g., Jaffe, D., Prestbo, E., Swartzendruber, P., Weiss-Penzias, P., Kato, S., Takami, A., Hatakeyama, S., Kajii, Y., 2005. Export of atmospheric mercury from Asia. Atmospheric Environment 39, 3029–3038; Weiss-Penzias, P., Jaffe, D., Swartzendruber, P., Hafner, W., Chand, D., Prestbo, E., 2007. Quantifying Asian and biomass burning sources of mercury using the Hg/CO ratio in pollution plumes observed at the Mount Bachelor observatory. Atmospheric Environment 41, 4366–4379) in the region.

We interpret a suite of satellite, aircraft, and ground-based measurements over the North Pacific Ocean and western North America during April–May 2006 as part of the Intercontinental Chemical Transport Experiment Phase B (INTEX-B) campaign to understand the implications of long-range transport of East Asian emissions to North America. The Canadian component of INTEX-B included 33 vertical profiles from a Cessna 207 aircraft equipped with an aerosol mass spectrometer. Long-range transport of organic aerosols was insignificant, contrary to expectations. Measured sulfate plumes in the free troposphere over British Columbia exceeded 2 μg/m3. We update the global anthropogenic emission inventory in a chemical transport model (GEOS-Chem) and use it to interpret the observations. Aerosol Optical Depth (AOD) retrieved from two satellite instruments (MISR and MODIS) for 2000–2006 are analyzed with GEOS-Chem to estimate an annual growth in Chinese sulfur emissions of 6.2% and 9.6%, respectively. Analysis of aircraft sulfate measurements from the NASA DC-8 over the central Pacific, the NSF C-130 over the east Pacific and the Cessna over British Columbia indicates most Asian sulfate over the ocean is in the lower free troposphere (800–600 hPa), with a decrease in pressure toward land due to orographic effects. We calculate that 56% of the measured sulfate between 500–900 hPa over British Columbia is due to East Asian sources. We find evidence of a 72–85% increase in the relative contribution of East Asian sulfate to the total burden in spring off the northwest coast of the United States since 1985. Campaign-average simulations indicate anthropogenic East Asian sulfur emissions increase mean springtime sulfate in Western Canada at the surface by 0.31 μg/m3 (~30%) and account for 50% of the overall regional sulfate burden between 1 and 5 km. Mean measured daily surface sulfate concentrations taken in the Vancouver area increase by 0.32 μg/m3 per 10% increase in the simulated fraction of Asian sulfate, and suggest current East Asian emissions episodically degrade local air quality by more than 1.5 μg/m3.

Eight chemical transport models participate in a model intercomparison study for East Asia, MICS-Asia II. This paper analyzes calculated results for particulate matter of sulfate, nitrate and ammonium through comparisons with each other and with monthly measurements at EANET (the acid deposition monitoring network in East Asia) and daily measurements at Fukue, Japan. To the EANET measurements, model ensemble means better agree with model individual results for sulfate and total ammonium, although total nitrate is consistently and considerably underestimated. To measurements at Fukue, the models show better agreement than for the EANET measurements. This is likely because Fukue is centered in many of the model domains, whereas the EANET stations are mostly in Southeast Asia and Russia. Moreover, it would be important that Fukue is in Northeast Asia, where the emission inventory is more reliable than Southeast Asia. The model-model comparisons are made in view of the total amount in the atmosphere, vertical profile, coefficient of variation in surface concentrations, and transformation changes with distance. All the models show reasonable tendencies in vertical profiles and composition ratios. However, total amounts in the atmosphere are discrepant among the models. The consistency of the total amount in the atmosphere would influence source-receptor analysis. It seems that model results would be consistent, if the models take into account the primitive processes like emission, advection/diffusion, chemical transformation and dry/wet deposition, no matter the processes are modeled simply or comprehensively. Through the comparison study, we learned that it would be difficult to find any problems from one comparison (model-observation comparison with one data or many but at one station or in a short period). Modelers tend to examine model performances only from model-observation comparisons. However, taking budget in a certain or whole model domain would be important, before the models are applied to source-receptor analysis.

This paper focuses on the comparison of chemical deposition of eight regional chemical models used in Model Inter-Comparison Study for Asia (MICS-Asia) II. Monthly-mean depositions of chemical species simulated by these models, including dry deposition of SO2, HNO3, NH3, sulfate, nitrate and ammonium and wet deposition of SO42−, NO3− and NH4+, have been provided for four periods (March, July, December 2001 and March 2002) in this work. Observations at 37 sites of the Acid Deposition Monitoring Network in East Asia (EANET) are compared with SO42−, NO3− and NH4+ wet deposition model results. Significant correlations appeared between the observation and computed ensemble mean of participant models. Also, differences among modeled sulfur and nitrogen dry depositions have been studied at the EANET sites. Based on the analysis of acid deposition for various species from different models, total depositions of sulfur (SO2 and sulfate) and nitrogen (nitrate and ammonium) have been evaluated as the ensemble mean of the eight models. In general, all models capture the observed spatial distribution of sulfur and nitrogen deposition, although the absolute values may differ from measurements. High deposition often occurs in eastern China, Japan, the Republic of Korea, Thailand, Vietnam, Philippines and other parts of Southeast Asia. The magnitude of model bias is quite large for many of the models. In examining the reasons for model–measurement disagreement, we find that differences in chemical processes, deposition parameterization, and modeled precipitation are the main reasons for large model disparities.

A numerical simulation study to quantify the effect of upstream transport and fossil-fuel and biomass-burning emissions from East Asia on the surface ozone near Taiwan has been performed based on data taken April 8-13, 2001, when a cold air outbreak occurred. The TAQM (Taiwan Air Quality Model) is employed in this study. Results show that, without considering emissions in East Asia, upstream transport of chemical species associated with the movement of the cold air mass increased the levels of CO and ozone near Taiwan from 75 to 180ppbv, and 35 to 55ppbv, respectively. Fossil-fuel and biomass-burning emissions can thus result in a significant increase of CO and ozone levels (70-150% and 50-100%, respectively) from the emissionless background. The most noteworthy phenomenon is that biomass burning in Eastern China alone can contribute up to 20% of the increase for these species, while the biomass burning in Southeast Asia has negligible influence.

The fate and transport of mercury in East Asia is evaluated using the Sulfur Transport and dEposition Model (STEM)-Hg 3-D model. The model calculates mercury transport, transformation and deposition in East Asia during April 2001, the period of the ACE-Asia field campaign. Model predictions of dry and wet deposition are compared with the observations from 10 sampling sites in Japan. The model results are consistent with the observations, but tend to over-predict dry deposition. Sensitivity analysis of predicted results to uncertainties in the mercury reaction rates suggests that the oxidation of Hg0 to Hg(II) in the gas phase is the dominant pathway for atmospheric mercury removal processes. Simulation based on the most recently published reaction rate constants for gas phase oxidation of Hg0 to Hg(II) overestimates the production of Hg(II) in the gas phase. The regional mercury budget is calculated which shows that most of the reactive gas phase mercury (RGM) and particulate mercury (Hgp) are deposited around the source region while 28.5 Mg of Hg0 is exported out of East Asia during April 2001. The sensitivity analysis in the regional Hg budget to major uncertainties associated with Hg emission estimates and Hg chemistry are also evaluated.

Region-to-grid source–receptor (S/R) relationships are established for sulfur and reactive nitrogen deposition in East Asia, using the Eulerian-type Community Multiscale Air Quality (CMAQ) model with emission and meteorology data for 2001. We proposed a source region attribution methodology by analyzing the non-linear responses of the CMAQ model to emission changes. Sensitivity simulations were conducted where emissions of SO2, NO x , and primary particles from a source region were reduced by 25%. The difference between the base and sensitivity simulations was multiplied by a factor of four, and then defined as the contribution from that source region. The transboundary influence exhibits strong seasonal variation and generally peaks during the dry seasons. Long-range transport from eastern China contributes a significant percentage ( > 20 % ) of anthropogenic reactive nitrogen as well as sulfur deposition in East Asia. At the same time, northwestern China receives approximately 35% of its sulfur load and 45% of its nitrogen load from foreign emissions. Sulfur emissions from Miyakejima and other volcanoes contribute approximately 50% of the sulfur load in Japan in 2001. Sulfur inflows from regions outside the study domain, which is attributed by using boundary conditions derived from the MOZART global atmospheric chemistry model, are pronounced (10–40%) over most parts of Asia. Compared with previous studies using simple Lagrangian models, our results indicate higher influence from long-range transport. The estimated S/R relationships are believed to be more realistic since they include global influence as well as internal interactions among different parts of China.

Nitrate aerosols are expected to become more important in the future atmosphere due to the expected increase in nitrate precursor emissions and the decline of ammonium-sulphate aerosols in wide regions of this planet. The GISS climate model is used in this study, including atmospheric gas- and aerosol phase chemistry to investigate current and future (2030, following the SRES A1B emission scenario) atmospheric compositions. A set of sensitivity experiments was carried out to quantify the individual impact of emission- and physical climate change on nitrate aerosol formation. We found that future nitrate aerosol loads depend most strongly on changes that may occur in the ammonia sources. Furthermore, microphysical processes that lead to aerosol mixing play a very important role in sulphate and nitrate aerosol formation. The role of nitrate aerosols as climate change driver is analyzed and set in perspective to other aerosol and ozone forcings under pre-industrial, present day and future conditions. In the near future, year 2030, ammonium nitrate radiative forcing is about −0.14 W/m² and contributes roughly 10% of the net aerosol and ozone forcing. The present day nitrate and pre-industrial nitrate forcings are −0.11 and −0.05 W/m², respectively. The steady increase of nitrate aerosols since industrialization increases its role as a non greenhouse gas forcing agent. However, this impact is still small compared to greenhouse gas forcings, therefore the main role nitrate will play in the future atmosphere is as an air pollutant, with annual mean near surface air concentrations, in the fine particle mode, rising above 3 μg/m³ in China and therefore reaching pollution levels, like sulphate aerosols.

An inverse modeling method using the four-dimensional variational data assimilation approach is developed to provide a top-down estimate of mercury emission inventory in China. The mercury observations on board the C130 aircraft during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign in April 2001 are assimilated into a regional chemical transport model, STEM. Using a 340 Mg of elemental mercury emitted in 1999, the assimilation results in an increase in Hg 0 emissions for China to 1140 Mg in 2001. This is an upper limit amount of the elemental mercury required in China. The average emission-scaling factor is ∼3.4 in China. The spatial changes in the mercury emissions after the assimilation are also evaluated. The largest changes are estimated on the China north-east coastal areas and the areas of north-center China. The influences of the observation and inventory uncertainties and the initial and boundary conditions on the emission estimates are discussed. Increasing the boundary conditions of Hg from 1.2 to 1.5 ng m −3 , results in a top-down estimate of Hg 0 emissions for China of 718 Mg, and leads the average scaling factor from 3.4 to 2.1.

An inventory of mercury emissions from anthropogenic activities in China is compiled for the year 1999 from official statistical data. We estimate that China's emissions were 536 (±236) t of total mercury. This value includes open biomass burning, but does not include natural sources or re-emission of previously deposited mercury. Approximately 45% of the Hg comes from non-ferrous metals smelting, 38% from coal combustion, and 17% from miscellaneous activities, of which battery and fluorescent lamp production and cement production are the largest. Emissions are heaviest in Liaoning and Guangdong Provinces, where extensive smelting occurs, and in Guizhou Province, where there is much small-scale combustion of high-Hg coal without emission control devices. Emissions are gridded at 30×30 min spatial resolution. We estimate that 56% of the Hg in China is released as Hg 0 , 32% as Hg 2+ , and 12% as Hg p . Particulate mercury emissions are high in China due to heavy burning of coal in residential and small industrial settings without PM controls. Emissions of Hg 2+ from coal-fired power plants are high due to the absence of flue-gas desulfurization units, which tend to dissolve the soluble divalent mercury. Metals smelting operations favor the production of elemental mercury. Much of the Hg is released from small-scale activities in rather remote areas, and therefore the activity levels are quite uncertain. Also, emissions test data for Chinese sources are lacking, causing uncertainties in Hg emission factors and removal efficiencies. Overall, we calculate an uncertainty level of ±44% (95% confidence interval) in the estimate of total emissions. We recommend field testing of coal combustors and smelters in China to improve the accuracy of these estimates.