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The absence of up-to-date emissions has been a major impediment to accurately simulating aspects of atmospheric chemistry and to precisely quantifying the impact of changes in emissions on air pollution. Hence, a nonlinear joint analytical inversion (Gauss–Newton method) of both volatile organic compounds (VOCs) and nitrogen oxide ( NOx ) emissions is made by exploiting the Smithsonian Astrophysical Observatory (SAO) Ozone Mapping and Profiler Suite Nadir Mapper (OMPS-NM) formaldehyde (HCHO) and the National Aeronautics and Space Administration (NASA) Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide ( NO2 ) columns during the Korea–United States Air Quality (KORUS-AQ) campaign over East Asia in May–June 2016. Effects of the chemical feedback of NOx and VOCs on both NO2 and HCHO are implicitly included by iteratively optimizing the inversion. Emission uncertainties are greatly narrowed (averaging kernels > 0.8 , which is the mathematical presentation of the partition of information gained from the satellite observations with respect to the prior knowledge) over medium- to high-emitting areas such as cities and dense vegetation. The prior amount of total NOx emissions is mainly dictated by values reported in the MIX-Asia 2010 inventory. After the inversion we conclude that there is a decline in emissions (before, after, change) for China ( 87.94±44.09 Gg d −1 , 68.00±15.94 Gg d −1 , −23 %), North China Plain (NCP) ( 27.96±13.49 Gg d −1 , 19.05±2.50 Gg d −1 , −32 %), Pearl River Delta (PRD) ( 4.23±1.78 Gg d −1 , 2.70±0.32 Gg d −1 , −36 %), Yangtze River Delta (YRD) ( 9.84±4.68 Gg d −1 , 5.77±0.51 Gg d −1 , −41 %), Taiwan ( 1.26±0.57 Gg d −1 , 0.97±0.33 Gg d −1 , −23 %), and Malaysia ( 2.89±2.77 Gg d −1 , 2.25±1.34 Gg d −1 , −22 %), all of which have effectively implemented various stringent regulations. In contrast, South Korea ( 2.71±1.34 Gg d −1 , 2.95±0.58 Gg d −1 , + 9 %) and Japan ( 3.53±1.71 Gg d −1 , 3.96±1.04 Gg d −1 , +12 %) are experiencing an increase in NOx emissions, potentially due to an increased number of diesel vehicles and new thermal power plants. We revisit the well-documented positive bias (by a factor of 2 to 3) of MEGAN v2.1 (Model of Emissions of Gases and Aerosols from Nature) in terms of biogenic VOC emissions in the tropics. The inversion, however, suggests a larger growth of VOCs (mainly anthropogenic) over NCP (25 %) than previously reported (6 %) relative to 2010. The spatial variation in both the magnitude and sign of NOx and VOC emissions results in nonlinear responses of ozone production and loss. Due to a simultaneous decrease and increase in NOx∕VOC over NCP and YRD, we observe a ∼53 % reduction in the ratio of the chemical loss of NOx ( LNOx ) to the chemical loss of ROx ( RO2+HO2 ) over the surface transitioning toward NOx -sensitive regimes, which in turn reduces and increases the afternoon chemical loss and production of ozone through NO2+OH ( −0.42 ppbv h −1 ) ∕HO2 (and RO2 ) +NO ( +0.31 ppbv h −1 ). Conversely, a combined decrease in NOx and VOC emissions in Taiwan, Malaysia, and southern China suppresses the formation of ozone. Simulations using the updated emissions indicate increases in maximum daily 8 h average (MDA8) surface ozone over China (0.62 ppbv), NCP (4.56 ppbv), and YRD (5.25 ppbv), suggesting that emission control strategies on VOCs should be prioritized to curb ozone production rates in these regions. Taiwan, Malaysia, and PRD stand out as regions undergoing lower MDA8 ozone levels resulting from the NOx reductions occurring predominantly in NOx -sensitive regimes.

Atmospheric ammonia is a significant pollutant throughout the year, necessitating standardized measurement and identification of emission factors. We performed a quantized evaluation of ammonia concentrations at various locations in and around Seoul, South Korea. The established testing methods of the Radiello Passive Sampler were used for ammonia sampling, and the method was validated using annular denuder sampling. Urban and suburban areas were studied to gain a deeper understanding of the factors responsible for ammonia pollution. This study aimed to establish the fluctuations in concentration over one year, by analyzing the seasonal and regional variation in ammonia concentration. Livestock and agricultural areas recorded the highest concentration of ammonia among all sites, with the highest concentration recorded in autumn. However, at most of the other studied sites, the highest and lowest ammonia concentrations were recorded during summer and winter, respectively. This study attempted to establish a correlation between ammonia concentration and temperature, as well as ammonia concentration and altitude.

The Korea-United States Air Quality (KORUS-AQ) field study was conducted during May–June 2016 to understand the factors controlling air quality in South Korea. Extensive aircraft and ground network observations from the campaign offer an opportunity to address issues in current air quality models and reduce model-observation disagreements. This study examines these issues using model evaluation against the KORUS-AQ observations and intercomparisons between models. Six regional and two global chemistry transport models using identical anthropogenic emissions participated in the model intercomparison study and were used to conduct air quality simulations focusing on ozone (O3), aerosols, and their precursors for the campaign. Using the KORUSv5 emissions inventory, which has been updated from KORUSv1, the models successfully reproduced observed nitrogen oxides (NOx) and volatile organic compounds mixing ratios in surface air, especially in the Seoul Metropolitan Area, but showed systematic low biases for carbon monoxide (CO), implying possible missing CO sources in the inventory in East Asia. Although the DC-8 aircraft-observed O3 precursor mixing ratios were well captured by the models, simulated O3 levels were lower than the observations in the free troposphere in part due to too low stratospheric O3 influxes, especially in regional models. During the campaign, the synoptic meteorology played an important role in determining the observed variability of PM2.5 (PM diameter ≤ 2.5 μm) concentrations in South Korea. The models successfully simulated the observed PM2.5 variability with significant inorganic sulfate-nitrate-ammonium aerosols contribution, but failed to reproduce that of organic aerosols, causing a large inter-model variability. From the model evaluation, we find that an ensemble of model results, incorporating individual models with differing strengths and weaknesses, performs better than most individual models at representing observed atmospheric compositions for the campaign. Ongoing model development and evaluation, in close collaboration with emissions inventory development, are needed to improve air quality forecasting.

Nonmethane volatile organic compounds (NMVOCs) result in ozone and aerosol production that adversely affects the environment and human health. For modeling purposes, anthropogenic NMVOC emissions have been typically compiled using the “bottom-up” approach. To minimize uncertainties of the bottom-up emission inventory, “top-down” NMVOC emissions can be estimated using formaldehyde (HCHO) observations. In this study, HCHO vertical column densities (VCDs) obtained from the Geostationary Trace gas and Aerosol Sensor Optimization spectrometer during the Korea–United States Air Quality campaign were used to constrain anthropogenic volatile organic compound (AVOC) emissions in South Korea. Estimated top-down AVOC emissions differed from those of the up-to-date bottom-up inventory over major anthropogenic source regions by factors of 1.0 ± 0.4 to 6.9 ± 3.9. Our evaluation using a 3D chemical transport model indicates that simulated HCHO mixing ratios using the top-down estimates were in better agreement with observations onboard the DC-8 aircraft during the campaign relative to those with the bottom-up emission, showing a decrease in model bias from –25% to –13%. The top-down analysis used in this study, however, has some limitations related to the use of HCHO yields, background HCHO columns, and AVOC speciation in the bottom-up inventory, resulting in uncertainties in the AVOC emission estimates. Our attempt to constrain diurnal variations of the AVOC emissions using the aircraft HCHO VCDs was compromised by infrequent aircraft observations over the same source regions. These limitations can be overcome with geostationary satellite observations by providing hourly HCHO VCDs.

The U.S. National Aeronautics and Space Administration in partnership with Korea’s National Institute of Environmental Research embarked on the Korea-United States Air Quality (KORUS-AQ) study to address air quality issues over the Korean peninsula. Underestimation of volatile organic compound (VOC) emissions from various large facilities on South Korea’s northwest coast may contribute to this problem, and this study focuses on quantifying top-down emissions of formaldehyde (CH2O) and VOCs from the largest of these facilities, the Daesan petrochemical complex, and comparisons with the latest emission inventories. To accomplish this and additional goals discussed herein, this study employed a number of measurements acquired during KORUS-AQ onboard the NASA DC-8 aircraft during three Daesan overflights on June 2, 3, and 5, 2016, in conjunction with a mass balance approach. The measurements included fast airborne measurements of CH2O and ethane from an infrared spectrometer, additional fast measurements from other instruments, and a suite of 33 VOC measurements acquired by the whole air sampler. The mass balance approach resulted in consistent top-down yearly Daesan VOC emission flux estimates, which averaged (61 ± 14) × 103 MT/year for the 33 VOC compounds, a factor of 2.9 ± 0.6 (±1.0) higher than the bottom-up inventory value. The top-down Daesan emission estimate for CH2O and its four primary precursors averaged a factor of 4.3 ± 1.5 (± 1.9) times higher than the bottom-up inventory value. The uncertainty values in parentheses reflect upper limits for total uncertainty estimates. The resulting averaged top-down Daesan emission estimate for sulfur dioxide (SO2) yielded a ratio of 0.81–1.0 times the bottom-up SO2 inventory, and this provides an important cross-check on the accuracy of our mass balance analysis.

We present trace gas vertical profiles observed by instruments on the NASA DC-8 and at a ground site during the Korea-US air quality study (KORUS) field campaign in May to June 2016. We focus on the region near the Seoul metropolitan area and its surroundings where both anthropogenic and natural emission sources play an important role in local photochemistry. Integrating ground and airborne observations is the major research goal of many atmospheric chemistry field campaigns. Although airborne platforms typically aim to sample from near surface to the free troposphere, it is difficult to fly very close to the surface especially in environments with complex terrain or a populated area. A detailed analysis integrating ground and airborne observations associated with specific concentration footprints indicates that reactive trace gases are quickly oxidized below an altitude of 700 m. The total OH reactivity profile has a rapid decay in the lower part of troposphere from surface to the lowest altitude (700 m) sampled by the NASA DC-8. The decay rate is close to that of very reactive biogenic volatile organic compounds such as monoterpenes. Therefore, we argue that photochemical processes in the bottom of the boundary layer, below the typical altitude of aircraft sampling, should be thoroughly investigated to properly assess ozone and secondary aerosol formation.

Substantial mitigation of air pollutants emissions has been performed since 2013 around Beijing, and changes in the atmospheric characteristics have been expected over the downstream area of Beijing. In this study, both WRF-Chem simulation and on-site measurements were utilized for the Baengnyeong (island) supersite, one of the representative regional background sites located in the Yellow Sea, the entrance area of the long-range transport process in Korea. The changes in the chemical compositions of inorganic aerosols were examined for spring-time during the Chinese emission mitigation period from 2014 to 2016. The measured ratio of ionic species to PM2.5 at the Baengnyeong supersite showed changes in aerosol inorganic chemical compositions from sulfate in 2014 to nitrate in 2015–2016. The modeling results also showed that nitrate was low in 2014 and significantly increased in 2015 and 2016, and the acidic aerosol condition had also changed toward a more neutralized status in both the simulation and the observations. The WRF-Chem modeling study further indicated that the sulfur was not neutralized in 2014. However, in 2015 and 2016, SO2 was more sufficiently neutralized as sulfur emissions were substantially reduced in China, while at the same time nitrate had begun to increase in such a ‘SO2–poor’ condition in Beijing area in China, and thus approaching more enhanced neutralization over the Yellow Sea area. The causes of the higher nitrate based on the modeled characteristics of the ammonia-sulfate-nitrate aerosol formation in response to the SO2 emissions reduction in China are also discussed in this paper.

The Korea-United States Air Quality Study (KORUS-AQ) took place in spring 2016 to better understand air pollution in Korea. In support of KORUS-AQ, 2554 whole air samples (WAS) were collected aboard the NASA DC-8 research aircraft and analyzed for 82 C1–C10 volatile organic compounds (VOCs) using multi-column gas chromatography. Together with fast-response measurements from other groups, the air samples were used to characterize the VOC composition in Seoul and surrounding regions, determine which VOCs are major ozone precursors in Seoul, and identify the sources of these reactive VOCs. (1) The WAS VOCs showed distinct signatures depending on their source origins. Air collected over Seoul had abundant ethane, propane, toluene and n-butane while plumes from the Daesan petrochemical complex were rich in ethene, C2–C6 alkanes and benzene. Carbonyl sulfide (COS), CFC-113, CFC-114, carbon tetrachloride (CCl4) and 1,2-dichloroethane were good tracers of air originating from China. CFC-11 was also elevated in air from China but was surprisingly more elevated in air over Seoul. (2) Methanol, isoprene, toluene, xylenes and ethene were strong individual contributors to OH reactivity in Seoul. However methanol contributed less to ozone formation based on photochemical box modeling, which better accounts for radical chemistry. (3) Positive Matrix Factorization (PMF) and other techniques indicated a mix of VOC source influences in Seoul, including solvents, traffic, biogenic, and long-range transport. The solvent and traffic sources were roughly equal using PMF, and the solvents source was stronger in the KORUS-AQ emission inventory. Based on PMF, ethene and propene were primarily associated with traffic, and toluene, ethylbenzene and xylenes with solvents, especially non-paint solvents for toluene and paint solvents for ethylbenzene and xylenes. This suggests that VOC control strategies in Seoul could continue to target vehicle exhaust and paint solvents, with additional regulations to limit the VOC content in a variety of non-paint solvents.

Biogenic volatile organic compound (BVOCs) emissions are the largest VOC emission source globally, and are precursors to ozone and secondary organic aerosols, both of which are strong, short-lived climate pollutants. BVOC emissions are usually estimated using the Model of Emissions of Gases and Aerosols from Nature (MEGAN), which requires Plant Functional Types (PFTs) and Leaf Area Indexes (LAIs) as inputs. Herein, the effects of refined input data on regional BVOC emission estimates are analyzed. For LAIs, lower resolution MODerate-resolution Imaging Spectroradiometer (MODIS), and higher spatio-temporal resolution Spatial and Temporal Adaptive Reflectance Fusion Model (STARFM) LAI were generated. For PFTs, local land cover maps were developed, in addition to MODIS PFT. In South Korea, annual emissions of isoprene and monoterpenes in 2015 were estimated as 384 and 160 Gg/year, respectively, using STARFM LAI and Local PFT (Case 4). For North Korea, 340 Gg/year isoprene and 72 Gg/year monoterpenes emissions were estimated using STARFM LAI and MODIS PFT. These estimates were 14&ndash, 110% higher than when using MODIS LAI and MODIS PFT (Case 1). Inter-comparison with satellite-based inverse isoprene emission estimates from GlobEmission shows 32% (North Korea) to 34% (South Korea) overestimation in bottom-up data. Our new vegetation inputs improve MEGAN performance and resulting BVOC emission estimations. Performance of Weather Research and Forecasting (WRF) meteorological modeling requires improvement, especially for solar radiation, to avoid overestimation of isoprene emissions.

The absence of up-to-date emissions has been a major impediment to accurately simulate aspects of atmospheric chemistry, and to precisely quantify the impact of changes of emissions on air pollution. Hence, a non-linear joint analytical inversion (Gauss–Newton method) of both volatile organic compounds (VOC) and nitrogen oxides (NOx) emissions is made by exploiting the Smithsonian Astrophysical Observatory (SAO) Ozone Mapping and Profile Suite Nadir Mapper (OMPS-NM) formaldehyde (HCHO) and the National Aeronautics and Space Administration (NASA) Ozone Monitoring Instrument (OMI) tropospheric nitrogen dioxide (NO2) retrievals during the Korea-United States Air Quality (KORUS-AQ) campaign over East Asia in May–June 2016. Effects of the chemical feedback of NOx and VOCs on both NO2 and HCHO are implicitly included through iteratively optimizing the inversion. Emissions estimates are greatly improved (averaging kernels > 0.8) over medium- to high-emitting areas such as cities and dense vegetation. The amount of total NOx emissions is mainly dictated by values reported in the MIX-Asia 2010 inventory. After the inversion we conclude a decline in the emissions (before, after, change) for China (87.94 ± 44.09 Gg/day, 68.00 ± 15.94 Gg/day, −23 %), North China Plain (NCP) (27.96 ± 13.49 Gg/day, 19.05 ± 2.50 Gg/day, −32 %), Pearl River Delta (PRD) (4.23 ± 1.78 Gg/day, 2.70 ± 0.32 Gg/day, −36 %), Yangtze River Delta (YRD) (9.84 ± 4.68 Gg/day, 5.77 ± 0.51 Gg/day, −41 %), Taiwan (1.26 ± 0.57 Gg/day, 0.97 ± 0.33 Gg/day, −23 %), and Malaysia (2.89 ± 2.77 Gg/day, 2.25 ± 1.34 Gg/day, −22 %), all of which have effectively implemented various stringent regulations. In contrast, South Korea (2.71 ± 1.34 Gg/day, 2.95 ± 0.58 Gg/day, +9 %) and Japan (3.53 ± 1.71 Gg/day, 3.96 ± 1.04 Gg/day, +12 %) experience an increase in NOx emissions potentially due to risen number of diesel vehicles and new thermal power plants. We revisit the well-documented positive bias of the model in terms of biogenic VOC emissions in the tropics. The inversion, however, suggests a larger growth of VOC (mainly anthropogenic) over NCP (25 %) than previously reported (6 %) relative to 2010. The spatial variation in both magnitude and sign of NOx and VOC emissions results in non-linear responses of ozone production/loss. Due to simultaneous decrease/increase of NOx/VOC over NCP and YRD, we observe an ~ 53 % reduction in the ratio of the chemical loss of NOx (LNOx) to the chemical loss of ROx (RO2 + HO2) transitioning toward NOx-sensitive regimes, which in turn, reduces/increases the afternoon chemical loss/production of ozone through NO2 + OH (−0.42 ppbv hr−1)/HO2 (and RO2) + NO (+0.31 ppbv hr−1). Conversely, a combined decrease in NOx and VOC emissions in Taiwan, Malaysia, and the southern China suppresses the formation of ozone. Ultimately, model simulations indicate enhancements of maximum daily 8-hour average (MDA8) surface ozone over China (0.62 ppbv), NCP (4.56 ppbv), and YRD (5.25 ppbv) due to the non-linear ozone chemistry, suggesting that emissions standards should be extended to regulate VOCs to be able to curb ozone production rates. Taiwan, Malaysia, and PRD stand out as the regions undergoing lower MDA8 ozone levels resulting from the NOx reductions occurring predominantly in NOx-sensitive regimes.

Atmospheric nitrogen deposition in China has attracted huge public attention in recently years due to the increasing anthropogenic emission of reactive nitrogen (Nr) and its impacts on the terrestrial and aquatic ecosystems. However, limited long-term and multi-site measurements have restrained the understanding on the mechanism of the Nr deposition as well as the chemical transport model (CTM) improvement. In this study, the performance of the simulated wet and dry deposition for different Nr species, i.e., particulate NO3− and NH4+, gaseous NOx, HNO3 and NH3, have been conducted using the framework of Model Inter-Comparison Study for Asia (MICS-Asia) phase III. Nine Models, including 5 WRF-CAMQ models, 2 self-developed regional models, a global model and a RAMS-CMAQ model, have been selected for the comparison. For wet depositions, observation data from 83 measurement sites of EANET, CREN, CAUDN, NADMN and DEE of China have been collected and normalized to compare with model results. In general, most models showed the consistent spatial and temporal variation of both oxidized N (Nox) and reduced N (Nrd) wet depositions in China with the NME around at 50 %, which is lower than the value of 70 % based on EANET observation over Asia. Both the ratio of wet or dry deposition to the total inorganic N deposition (TIN) and the ratios of TIN to their emissions have shown the consistent results with the NNDMN estimations. The performance of ensemble results (ENM) was further assessed with the measurement from satellite. In different regions of China, the results showed that the simulated Nox wet deposition was overestimated in North East China (NE) but underestimated in south of China (SE+SW), while the Nrd wet deposition was underpredicted in all regions by all models. The deposition of Nox have large uncertainties than the Nrd especially in North China (NC), indicating chemical reaction process is one of the most importance factors that affecting the model performance. Compared to Critical load (CL) value, the Nr deposition in NC, SE and SW reached or exceeded the reported CL value and exerted serious ecological impacts. The control of Nrd in NC and SW and Nox in SE would be effective to mitigate the TIN deposition in these regions. More interestingly, the Nr deposition in Tibet plateau with the high ratio of TIN/emission (~3.0), indicating a significant import from outside should be focused in the future due to its climatical influence to the sensitive ecosystem in whole China.

We examine O3 production and its sensitivity to precursor gases and boundary layer mixing in Korea by using a 3-D global chemistry transport model and extensive observations during the KORea-US cooperative Air Quality field study in Korea, which occurred in May–June 2016. During the campaign, observed aromatic species onboard the NASA DC-8 aircraft, especially toluene, showed high mixing ratios of up to 10 ppbv, emphasizing the importance of aromatic chemistry in O3 production. To examine the role of VOCs and NOx in O3 chemistry, we first implement a detailed aromatic chemistry scheme in the model, which reduces the normalized mean bias of simulated O3 mixing ratios from –26% to –13%. Aromatic chemistry also increases the average net O3 production in Korea by 37%. Corrections of daytime PBL heights, which are overestimated in the model compared to lidar observations, increase the net O3 production rate by ~10%. In addition, increasing NOx emissions by 50% in the model shows best performance in reproducing O3 production characteristics, which implies that NOx emissions are underestimated in the current emissions inventory. Sensitivity tests show that a 30% decrease in anthropogenic NOx emissions in Korea increases the O3 production efficiency throughout the country, making rural regions ~2 times more efficient in producing O3 per NOx consumed. Simulated O3 levels overall decrease in the peninsula except for urban and other industrial areas, with the largest increase (~6 ppbv) in the Seoul Metropolitan Area (SMA). However, with simultaneous reductions in both NOx and VOCs emissions by 30%, O3 decreases in most of the country, including the SMA. This implies the importance of concurrent emission reductions for both NOx and VOCs in order to effectively reduce O3 levels in Korea.

Understanding how ozone (O3) and fine particulate matter (PM) formation respond to the precursor concentrations in the presence of biogenic emissions (BEs) and thereby changes in health effects can be a key step to design effective air quality management plans. This is particularly true in the Seoul Metropolitan Area (SMA), where future significant controls of anthropogenic sources of O3 and PM2.5 precursors are expected. In this paper, we investigate the effects of BEs on O3 and fine PM (PM2.5) concentrations during a strong photochemical air pollution season in the SMA in Korea. O3 and PM2.5 levels are modeled with and without BEs in June 2008. Further, we perform the health impact assessments (HIA) of O3 and PM2.5 concentration changes due to BEs to seek useful implications for air quality management by utilizing the adjusted exposure concentration fields for O3 and PM2.5 with an observation fusing (OBF) method. With BEs, daily maximum 8-h average O3 (maximum 8-h O3) and secondary organic aerosol (SOA) concentrations in the SMA increase by 17 and 474%, respectively. These increments are associated with significant consumption of photochemical oxidants (Ox), such as a ~ 60% reduction in OH∙ radicals. The reduction in Ox, conversely, lowers the production of secondary inorganic aerosols (SIOAs) by 2.7%. Adjusted O3 and PM2.5 exposure metrics and the subsequent HIA reveal that large mean increments of O3, about 8.43 ppb, due to BEs are responsible for approximately 62 all-cause premature mortalities in the SMA in June. However, mean increment of PM2.5 due to BEs is approximately 0.3 μg m−3 and results in negligible impacts on the all-cause mortality. Significant correlations of O3 and mortality rates (MR) with the VOC/NOx ratios across the SMA suggest that controlling volatile organic compounds (VOCs) from anthropogenic sources can be a priority to reduce O3 levels and population health risks in the SMA. Specifically, linear relationships of log [O3] and log [MR] to log [VOC/NOx] ensure that a 10% decrease in the VOC/NOx ratios through the VOC abatements would lead to a 1.5% decrease in the O3 levels and a 4.3% decrease in the MR on average across the SMA.

Recent regulatory policies in East Asia reduce ozone precursors, but these changes are spatially and temporally nonuniform. This study investigates variations in the long-term trends of tropospheric NO2, HCHO, and HCHO/NO2 ratios to diagnose ozone sensitivity to changes in NOx and volatile organic compound using the Ozone Monitoring Instrument (OMI). Using an adaptive-degree polynomial filter, we identify extremums of time series of NO2 to determine when and how NO2 change. Due to the regulations in China, trends which were predominantly upward turned downward. The years undergoing these changes primarily happened in 2011 and 2012. OMI column densities, however, suggest that NOx sources in South Korea, the Pearl River Delta (PRD), Taiwan, and Japan have not consistently decreased. Specifically, as Chinese exports of NO2 started subsiding, increasing trends in NO2 columns over several Korean cities, including Seoul, become evident. To quantify the changes in NOx emissions from summertime 2010 to 2014, we conduct a 3D-Var inverse modeling using a regional model with MIX-Asia inventory and estimate NOx emissions (in 2010 and 2014) for the PRD (1.6 and 1.5 Gg/d), the Yangtze River Delta (3.9 and 3.0 Gg/d), north China (15.6 and 14.3 Gg/d), South Korea (1.6 and 1.5 Gg/d), and Japan (2.7 and 2.6 Gg/d). OMI HCHO shows upward trends in East Asia resulting from anthropogenic effects; however, the magnitudes are negative in the PRD, Japan, North Korea, and Taiwan. OMI HCHO/NO2 ratios reveal that while South Korea, Japan, and the south of China have undergone toward more NOx-sensitive regime, areas around the Bohai Sea have become more NOx saturated.

This study examines the effects of different foreign anthropogenic emissions inventories on predicted ozone concentrations in the Seoul Metropolitan Area (SMA), South Korea, and estimates changes in ozone due to emissions reductions. We ran the Community Multi-Scale Air Quality (CMAQ) model using the High-Order Decoupled Direct Method with three inventories of foreign anthropogenic emissions: (1) the Intercontinental Chemical Transport Experiment, Phase B (INTEX-B) 2006; (2) the Comprehensive Regional Emissions inventory for Atmospheric Transport Experiment (CREATE) 2010; and (3) the Model Inter-Comparison Study (MICS)-Asia 2010. All three inventories have different spatial distributions of emissions, yielding different modeled ozone concentrations. However, the ozone concentrations modeled for the SMA differ less than those modeled for large, foreign cities in the modeling domain. The simulations using INTEX-B 2006 and CREATE 2010 suggested greater reduction in ozone with NOx control than with VOCs control. All simulations show that (1) simultaneous reduction in NOx and VOCs leads to less ozone reduction than the sum of ozone reductions for individual NOx and VOCs controls and (2) ozone reductions are stronger for high ozone days than for low ozone days. Comparing the modeled reductions in the relative sense yields smaller differences between high and low ozone days than comparing the modeled reductions in the absolute sense. With a 20% reduction in only NOx emissions, the differences in MDA1O3 among the three inventories were between 0.3 and 0.7 ppb. Because air-quality planning often leads to defined tonnage reductions, we examined the model’s response to such a defined emissions reduction. Using the NOx reduction in China estimated by Zhao et al. (2013), we estimated that the differences in MDA1O3 among the three inventories were between 1.50 and 1.78 ppb. Based on these results, we recommend using different foreign anthropogenic emissions inventories to test future scenarios for air-quality control

Spatial and temporal variations of mercury, including dry and wet deposition fluxes, were assessed over Northeast Asia, targeting the Yellow Sea, using meteorology and chemistry models. Four modeling periods, each representative of one of the four seasons, were selected. Modeling results captured general patterns and behaviors, and fell within similar ranges with respect to observations. However, temporal variations of mercury were not closely matched, possibly owing to the effects of localized emissions. Modeling results indicated that dry deposition is correlated with wind speed, while wet deposition is correlated with precipitation amount. Overall, the wet deposition flux of 66 ng/m2-day was about twice as large as the dry deposition flux of 32 ng/m2-day, when averaged over the four modeling periods. Dry deposition occurred predominantly in the form of reactive gaseous mercury (RGM). In contrast, RGM accounted for only about two-thirds of wet deposition, while particulate mercury accounted for the remainder.

To address the limitations of titanium dioxide (TiO2) and expand the applicability of the photocatalytic activity of TiO2,WSe2 and silica, an eco-friendly, self-assembled method for combining a silica precursor with a WSe2-graphene-TiO2 composite with cetyltrimethylammonium bromide (CTAB) as surface active agents is proposed. Firstly, for the main target, the photocatalytic degradation of organic dye solutions with different initial pH levels and catalyst dosages under visible light irradiation was surveyed. The as-synthesized sample exhibited highly efficient photocatalytic effects for the treatment of the SO dye solution in the optimal conditions of this study, which included a solution with a pH level of 11 and 0.05-gram dosage of the catalyst. Secondly, previous photocatalytic hydrogen production studies reported markedly better outcomes with SiO2/WSe2-graphene-TiO2 than with the binary WSe2-graphene and ternary WSe2-graphene-TiO2 composites under ambient conditions with and without 20% methanol sacrificing reagents. The SiO2/WSe2-graphene-TiO2 composite is promising to become a potential candidate for photocatalytic performance that performs excellently as well as offer an efficient heterosystem for hydrogen production.

We have developed the Integrated Climate and Air Quality Modeling System (ICAMS) through the one-way nesting of global–regional models to examine the changes in the surface ozone concentrations over East Asia under future climate scenarios. Model simulations have been conducted for the present period of 1996–2005 to evaluate the performance of ICAMS. The simulated surface ozone concentrations reproduced the observed monthly mean concentrations at sites in East Asia with high R2 values (0.4–0.9), indicating a successful simulation to capture both spatial and temporal variability. We then performed several model simulations with the six IPCC SRES scenarios (A2, A1B, A1FI, A1T, B1, and B2) for the next three periods, 2016–2025 (the 2020s), 2046–2055 (the 2050s), and 2091–2100 (the 2090s). The model results show that the projected changes of the annual daily mean maximum eight-hour (DM8H) surface ozone concentrations in summertime for East Asia are in the range of 2–8 ppb, −3 to 8 ppb, and −7 to 9 ppb for the 2020s, the 2050s, and the 2090s, respectively, and are primarily determined based on the emission changes of NOx and NMVOC. The maximum increases in the annual DM8H surface ozone and high-ozone events occur in the 2020s for all scenarios except for A2, implying that the air quality over East Asia is likely to get worse in the near future period (the 2020s) than in the far future periods (the 2050s and the 2090s). The changes in the future environment based on IPCC SRES scenarios would also influence the change in the occurrences of high-concentrations events more greatly than that of the annual DM8H surface ozone concentrations. Sensitivity simulations show that the emissions increase is the key factor in determining future regional surface ozone concentrations in the case of a developing country, China, whereas a developed country, Japan would be influenced more greatly by effects of the regional climate change than the increase in emissions.

We investigate ozone air quality changes in 2050 caused by global changes in climate and anthropogenic emissions of ozone precursors by using a global chemical transport model driven by meteorological fields from a general circulation model. We use projected emissions based on the Representative Concentration Pathway (RCP) scenarios and conduct model simulations to quantify the effects of climate and emission changes on future air quality, focusing on ozone in surface air. Our model results show that annual mean concentrations of surface ozone will be lower in 2050 relative to 2000 by −3.3, −3.7, and −4.2 ppbv under RCP6.0, RCP4.5, and RCP2.6, respectively. In contrast, the RCP8.5 projection results in a slight increase of 2.1 ppbv caused by a methane increase. The ozone reductions are driven primarily by decreases in NOx emission, which dominate the climate penalty on ozone driven by temperature increases. We also estimate the effect of 21st century climate change on ozone air quality, assuming no changes in anthropogenic emissions of ozone precursors in the future. We further use a statistical method to analyze the results in order to quantify the effect of each meteorological variable change on ozone concentration in summer. Temperature increase is found to result in ozone increases of up to 2.2 ppbv over land. Ozone over the oceans, however, is largely reduced with specific humidity increase, particularly in the Northern Hemisphere, where the ozone concentration decreases by 0.8 ppbv. We find that future increases in natural NOx emissions from lightning and soil make an important contribution to the formation of nitric acid and might seriously offset future decreases in nitrogen deposition caused by anthropogenic NOx emission reduction.

We use a 3-D regional atmospheric chemistry transport model (WRF-Chem) to examine ozone dry deposition in East Asia, which is an important but uncertain research area because of insufficient observation and numerical studies focusing on East Asia. Here we compare two widely used dry deposition parameterization schemes, the Wesely and M3DRY schemes, which are used in the WRF-Chem and Community Multiscale Air Quality (CMAQ) models, respectively. Simulated ozone dry deposition velocities with the two schemes under identical meteorological conditions show considerable differences (a factor of 2) owing to surface resistance parameterization discrepancies. Resulting ozone concentrations differ by up to 10 ppbv for a monthly mean in May when the peak ozone typically occurs in East Asia. An evaluation of the simulated dry deposition velocities shows that the Wesely scheme calculates values with more pronounced diurnal variation than the M3DRY and results in a good agreement with the observations. However, we find significant changes in simulated ozone concentrations using the Wesely scheme but with different surface type data sets, indicating the high sensitivity of ozone deposition calculations to the input data. The need is high for observations to constrain the dry deposition parameterization and its input data to improve the use of air quality models for East Asia.

Ozone concentrations in East Asia were simulated using the Community Multi-scale Air Quality (CMAQ) model, and its source contributions were estimated by multiple source–receptor modeling techniques. To study relationships between ozone concentrations and precursor emission sources, three approaches were applied to four months (January, April, July, and October 2009) to represent seasonal characteristics and compare results, with a particular focus on South Korea. Brute force (BF) is a traditional sensitivity analysis method used to estimate model output response to an input change. The high-order decoupled direct method (HDDM), a computational method, is an efficient and accurate alternative to the BF method for sensitivity. The Ozone and Particulate Precursor Tagging Methodology (OPTM) provides contribution information quantified by tracking emissions from selected sources throughout the simulation period. The approaches generally show that most of the receptor regions were substantially influenced by emissions from central China, which is the largest anthropogenic emissions source region in East Asia. Local emissions were still major contributors, especially South Korea and Japan during July 2009. On the other hand, a case study of maximum 8-h ozone concentrations derived from CMAQ–OPTM on April 9 in South Korea shows that the NOx and VOCs emissions from China contributed approximately 82% and 91%, respectively, to maximum 8-h ozone in Region 4 (South Korea) without boundary inflow, which indicates that Chinese emissions are the dominant contributor in this episode. A comparison study of the three approaches shows that HDDM tends to estimate biogenic source contributions lower than that from OPTM in China but similar to OPTM in South Korea and Japan. When comparing the BF method and HDDM, the sensitivity results show a reasonably good agreement during a given period. The location- and time-dependent maximum 8-h ozone isopleths over South Korea as a receptor region created by HDDM suggest that most ozone was being transported from central China, whereas almost no ozone was formed locally during April 2009, and local conditions were heavily VOC limited. On the other hand, local emissions were the dominant contributor during July 2009, and every source region showed a NOx-limited regime, which indicates that ozone concentrations in South Korea strongly depend on NOx emissions during this month.

Significant differences were found between two particulate sulfate size-distributions measured using a MOUDI impactor at Gosan, Jeju Island, Korea, and simulated via the Lagrangian photochemical model under a condition of aerosol internal mixing between mineral dust and urban pollution particles. It was suspected that these differences might have resulted from: (1) the assumption of aerosol internal mixing and (2) the uses of identical reaction probabilities (γ) of the gaseous sulfate precursors (SO2 and H2SO4) onto both urban pollution particles and mineral dust in the Lagrangian photochemical model simulations. In this study; therefore, some cases of aerosol external mixing between urban-derived pollution aerosols and mineral dust were investigated, with different magnitudes of γ for the gas-phase sulfate precursors onto the two different condensing media. The model simulations under the external mixing condition, with different magnitudes of the reaction probabilities (γi,urban and γi,dust) onto urban pollution particles and mineral dust, successfully reproduced the size-dependent particulate sulfate formation measured at the Gosan station. Further attempts were made to approximate the magnitudes of γSO2,urban and γH2SO4,dust under external mixing state conditions with the fixed γSO2,dust and γH2SO2,urban values of 10−4 and 1.0. The best-estimates of γSO2,urban and γH2SO4,dust found in this study were in the orders of 10−4–10−5 and 10−2–10−3, respectively.

Elevated levels of formaldehyde (HCHO) along the ship corridors have been observed by satellite sensors, such as ESA/ERS-2 GOME (Global Ozone Monitoring Experiment), and were also simulated by global 3-D chemistry-transport models. In this study, three likely sources of the elevated HCHO levels in the ship plumes as well as their contributions to the elevated HCHO levels (budget) were investigated using a newly-developed ship-plume photochemical/dynamic model: (1) primary HCHO emission from ships; (2) secondary HCHO production via the atmospheric oxidation of non-methane volatile organic compounds (NMVOCs) emitted from ships; and (3) atmospheric oxidation of CH4 within the ship plumes. For this ship-plume modelling study, the ITCT 2K2 (Intercontinental Transport and Chemical Transformation 2002) ship-plume experiment, which was carried out about 100 km off the coast of California on 8 May 2002 (11:00 local standard time), was chosen as a base study case because it is the best defined in terms of (1) meteorological data, (2) in-plume chemical composition, and (3) background chemical composition. From multiple ship-plume model simulations for the ITCT 2K2 ship-plume experiment case, CH4 oxidation by elevated levels of in-plume OH radicals was found to be the main factor responsible for the elevated levels of HCHO in the ITCT 2K2 ship-plume. More than ~88% of the HCHO for the ITCT 2K2 ship-plume is produced by this atmospheric chemical process, except in the areas close to the ship stacks where the main source of the elevated HCHO levels would be primary HCHO from the ships (due to the deactivation of CH4 oxidation from the depletion of in-plume OH radicals). Because of active CH4 oxidation by OH radicals, the instantaneous chemical lifetime of CH4 (τCH4) decreased to ~0.45 yr inside the ship plume, which is in contrast to τCH4 of ~1.1 yr in the background (up to ~41% decrease) for the ITCT 2K2 ship-plume case. A variety of likely ship-plume situations at three different latitudinal locations within the global ship corridors was also studied to determine the enhancements in the HCHO levels in the marine boundary layer (MBL) influenced by ship emissions. It was found that the ship-plume HCHO levels could be 19.9–424.9 pptv higher than the background HCHO levels depending on the latitudinal locations of the ship plumes (i.e., intensity of solar radiation and temperature), MBL stability and NOx emission rates. On the other hand, NMVOC emissions from ships were not found to be a primary source of photochemical HCHO production inside ship plumes due to their rapid and individual dilution. However, the diluted NMVOCs would contribute to the HCHO productions in the background air.

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.

In this study, background concentration sites of Deokjeok and Gosan, which were deemed suitable for monitoring the impact of long-range transported air pollutants, were selected. An investigation of the source types of pollutants, their locations, and relative quantitative contributions to the particulate concentrations at both sites using appropriate methodologies to make initial estimations was conducted. Episodic measurements of PM2.5, PM10, and size distribution, along with its ion and carbon components were performed from 2005 to 2007, and a comprehensive analysis of the results was conducted utilizing back trajectory analysis. As for frequency of wind direction, it was quite apparent that the two sites are heavily influenced by air masses originating from the eastern and northern regions of China. For PM2.5 and PM10, the mass concentrations from north and east China were higher than other cases, originating from the ocean. In the northerly-wind case, meteorological properties for Deokjeok and Gosan and the influence of carbon emissions from northwest Korea resulted in a changing of air mass properties during transport. As was the case with mass concentration, the highest contribution for ionic and carbon components of PM2.5 and PM10 for both sites appeared for the westerly wind case. A specially high relative contribution, greater than 1.4 times, was apparent in the secondary aerosol case because of a large influence of long-range transported pollutants from east China. Carbon components exhibited different behaviors for the northerly and westerly wind cases compared with secondary aerosol. The major reason for this discrepancy appears to be the carbon emissions from northwest Korea.

In this study, NO2 columns from the US EPA Models-3/CMAQ model simulations carried out using the 2001 ACE-ASIA (Asia Pacific Regional Aerosol Characterization Experiment) emission inventory over East Asia were compared with the GOME-derived NO2 columns. There were large discrepancies between the CMAQ-predicted and GOME-derived NO2 columns in the fall and winter seasons. In particular, while the CMAQ-predicted NO2 columns produced larger values than the GOME-derived NO2 columns over South Korea for all four seasons, the CMAQ-predicted NO2 columns produced smaller values than the GOME-derived NO2 columns over North China for all seasons with the exception of summer (summer anomaly). It is believed that there might be some error in the NOx emission estimates as well as uncertainty in the NOx chemical loss rates over North China and South Korea. Regarding the latter, this study further focused on the biogenic VOC (BVOC) emissions that were strongly coupled with NOx chemistry during summer in East Asia. This study also investigated whether the CMAQ-modeled NO2/NOx ratios with the possibly overestimated isoprene emissions were higher than those with reduced isoprene emissions. Although changes in both the NOx chemical loss rates and NO2/NOx ratios from CMAQ-modeling with the different isoprene emissions affected the CMAQ-modeled NO2 levels, the effects were found to be limited, mainly due to the low absolute levels of NO2 in summer. Seasonal variations of the NOx emission fluxes over East Asia were further investigated by a set of sensitivity runs of the CMAQ model. Although the results still exhibited the summer anomaly possibly due to the uncertainties in both NOx-related chemistry in the CMAQ model and the GOME measurements, it is believed that consideration of both the seasonal variations in NOx emissions and the correct BVOC emissions in East Asia are critical. Overall, it is estimated that the NOx emissions are underestimated by ~57.3% in North China and overestimated by ~46.1% in South Korea over an entire year. In order to confirm the uncertainty in NOx emissions, the NOx emissions over South Korea and China were further investigated using the ACE-ASIA, REAS (Regional Emission inventory in ASia), and CAPSS (Clean Air Policy Support System) emission inventories. The comparison between the CMAQ-calculated and GOME-derived NO2 columns indicated that both the ACE-ASIA and REAS inventories have some uncertainty in NOx emissions over North China and South Korea, which can also lead to some errors in modeling the formation of ozone and secondary aerosols in South Korea and North China.

The purpose of this study is to understand the impact that temperature and relative humidity have on the volatilization loss of particulate nitrate from Teflon filters during measurements of ambient fine particles . Fine particles were measured using an annular denuder system (ADS) at four representive areas in Seoul. The measurements were made during 28 different days at 24-hr sampling intervals from February 14 to October 15, 1997. In this study, nitrate losses. calculated by the ratio of nitrate on the nylon filter to their sum in both Teflon and nylon titters, varied seasonally in the following order: summer (45.5%) > spring (23.8%) > fall (20.6%) > winter (19.7%). The results showed strong correlations with temperature, but we did not observe any significant effects of relative humidity. However, we observed that both temperature and relative humidity influenced the ambient gas/particle nitrate ratio in a different case study using a denuder.

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.

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.

Long-range transport of pollutants influenced by anthropogenic and natural emission sources in East Asia is investigated by using backward trajectory analysis along the NASA TRACE-P flight tracks and a numerical simulation with the three-dimensional chemical transport model (STEM-2k1). Observation-based regional distributions of trace gases are reconstructed using the observations obtained by measurements on board the DC-8 and P3-B aircrafts. Systematic features of the spatial distribution for each species are identified. It is found that the observed concentrations of CO and some NMHCs, and the ratios between these species, are highly associated with the source distribution features and their regional characteristics. Reconstructed fields of the observed and modeled ethane/CO and ethane/propane are found to reproduce well the estimated emission ratios in East Asia. We also investigated the time rate of change of the concentration of species and their ratio along the trajectory. From this analysis the propane/ethane and propane/acetylene ratios are shown to preserve their emission ratios during regional transport. However systematic differences in the propane vs. acetylene/CO relationships are found between the model and observation values. This analysis suggests that further efforts are needed to improve the estimates of biomass burning emissions in SE Asia. The results presented in this paper also suggest ways to further extend the capabilities to derive observation-based inventories.

The relationship between SO 2 emissions and the effective particle radius of low-level water clouds ( r e ) over China was investigated to determine anthropogenic effects on clouds. Sulfur dioxide emission values were obtained from a statistical inventory, and r e origins were retrieved by satellite remote sensing on a 0.5° grid. Comparisons between annual mean SO 2 emissions and r e showed generally decreasing r e values, explained by the Twomey effect. The existence of the Twomey effect is supported by comparisons with simulated aerosol optical depths. Results further suggest that clouds over land show sensitivity to the Twomey effect as well as clouds over the ocean.

An intercomparison study involving eight long-range transport models for sulfur deposition in East Asia has been initiated. The participating models included Eulerian and Lagrangian frameworks, with a wide variety of vertical resolutions and numerical approaches. Results from this study, in which models used common data sets for emissions, meteorology, and dry, wet and chemical conversion rates, are reported and discussed. Model results for sulfur dioxide and sulfate concentrations, wet deposition amounts, for the period January and May 1993, are compared with observed quantities at 18 surface sites in East Asia. At many sites the ensemble of models is found to have high skill in predicting observed quantities. At other sites all models show poor predictive capabilities. Source–receptor relationships estimated by the models are also compared. The models show a high degree of consistency in identifying the main source–receptor relationships, as well as in the relative contributions of wet/dry pathways for removal. But at some locations estimated deposition amounts can vary by a factor or 5. The influence of model structure and parameters on model performance is discussed. The main factors determining the deposition fields are the emissions and underlying meteorological fields. Model structure in terms of vertical resolution is found to be more important than the parameterizations used for chemical conversion and removal, as these processes are highly coupled and often work in compensating directions.

Uncertainties in calculated impacts of climate forecasts on future regional air quality are investigated using downscaled MM5 meteorological fields from the NASA GISS and MIT IGSM global models and the CMAQ model in 2050 in the continental US. Differences between three future scenarios: high-extreme, low-extreme and base case, are used for quantifying effects of climate uncertainty on regional air quality. GISS, with the IPCC A1B scenario, is used for the base case simulations. IGSM results, in the form of probabilistic distributions, are used to perturb the base case climate to provide the high- and low-extreme scenarios. Impacts of the extreme climate scenarios on concentrations of summertime fourth-highest daily maximum 8-h average ozone are predicted to be up to 10 ppbV (about one-seventh of the current US ozone standard of 75 ppbV) in urban areas of the Northeast, Midwest and Texas due to impacts of meteorological changes, especially temperature and humidity, on the photochemistry of tropospheric ozone formation and increases in biogenic VOC emissions, though the differences in average peak ozone concentrations are about 1–2 ppbV on a regional basis. Differences between the extreme and base scenarios in annualized PM2.5 levels are very location dependent and predicted to range between −1.0 and +1.5 μg m−3. Future annualized PM2.5 is less sensitive to the extreme climate scenarios than summertime peak ozone since precipitation scavenging is only slightly affected by the extreme climate scenarios examined. Relative abundances of biogenic VOC and anthropogenic NOx lead to the areas that are most responsive to climate change. Overall, planned controls for decreasing regional ozone and PM2.5 levels will continue to be effective in the future under the extreme climate scenarios. However, the impact of climate uncertainties may be substantial in some urban areas and should be included in assessing future regional air quality and emission control requirements., United States. Environmental Protection Agency (Science To Achieve Results (STAR) grant No. RD83096001), United States. Environmental Protection Agency (Science To Achieve Results (STAR) grant No. RD82897602), United States. Environmental Protection Agency (Science To Achieve Results (STAR) grant No. RD83107601), East Tennessee State University

Responses of ozone and PM2.5 to emission changes are coupled because of interactions between their precursors. Here we show the interdependencies of ozone and PM2.5 responses to emission changes in 2001 and 2050, with the future case accounting for both currently planned emission controls and climate change. Current responses of ozone and PM2.5 to emissions are quantified and linked on a daily basis for five cities in the continental United States: Atlanta, Chicago, Houston, Los Angeles, and NewYork. Reductions in anthropogenic NO(x) emissions decrease 24-h average PM2.5 levels but may either increase or decrease daily maximum 8-h average ozone levels. Regional ozone maxima for all the cities are more sensitive to NO(x) reductions than at the city center, particularly in New York and Chicago. Planned controls of anthropogenic NO(x) emissions lead to more positive responses to NO(x) reductions in the future. Sensitivities of ozone and PM2.5 to anthropogenic VOC emissions are predicted to decrease between 2001 and 2050. Ammonium nitrate formation is predicted to be less ammonia-sensitive in 2050 than 2001 while the opposite is true for ammonium sulfate. Sensitivity of PM2.5 to SO2 and NO(x) emissions changes little between 2001 and 2050. Both ammonium sulfate and ammonium nitrate are predicted to decrease in sensitivity to SO2 and NO(x) emissions between 2001 and 2050. The complexities, linkages, and daily changes in the pollutant responses to emission changes suggest that strategies developed to meet specific air quality standards should consider other air quality impacts as well.

[1] Potential impacts of global climate change and emissions on the total nitrogen and sulfur deposition over the US are investigated. Three future years' annual average deposition rates (i.e., 2049–2051) are compared with historic ones (i.e., 2000–2002) accounting for existing US and individual State's emission regulations and strategies. Impacts of global climate change alone on regional nitrogen and sulfur deposition are small compared to impacts from emission control-related reductions for the projections used in this study. The combined effect of climate change and emission reductions is a decrease in the annual average nitrogen and sulfur deposition over the US. Reduced nitrogen species dominate oxidized nitrogen deposition in the future. Spatial distribution plots for both components show lower deposition rates in the future mainly in the middle and eastern States where reductions in NOx and SO2 emissions are more pronounced.

[1] Mercury tracer model simulations are performed to support the analysis of the total gas phase mercury (TGM) observations on 15 flights of the NSF/NCAR C-130 aircraft during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign conducted during April 2001. Ninety-seven percent of the observed mercury concentrations are greater than 1.2 ng/m3. The mean value of the observations is 1.9 ng/m3. No simple relationships between Hg-CO and Hg-total sulfur are found; however, strong correlations are observed in individual flight segments. Backward trajectory analysis is used to help characterize regional of Hg/CO ratios, and these are compared with emission-based ratios from the various sectors. Model predictions using new Hg emission estimates are presented and compared to the observations. Under the condition of a mercury background level of 1.2 ng/m3 the tracer model underestimates the observations when the flights were over the Yellow Sea but is consistent with the observations when the flights were over the Japan Sea. Further analysis suggests that Hg emissions are underestimated in north central China and the eastern coastal areas of China. Model sensitivity studies indicate that the emissions of China may be underestimated by 80–200%.

[1] Measurements from the Transport and Chemical Evolution over the Pacific (TRACE-P) and Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) field experiments obtained during the period of March–April 2001 are used to evaluate the impact of megacity emissions on regional air quality in east Asia. A classification method built upon back trajectory analysis and sensitivity runs using the Sulfur Transport and Emissions Model 2001 (STEM-2K1) regional chemical transport model are used to identify the aircraft observations that were influenced by megacity emissions. More than 30% of measurement points are classified as urban points, with a significant number of plumes found to have originated from Shanghai, Qingdao, Beijing, Taiyuan, Tianjin and Guiyang, Seoul, and Pusan. These data are then analyzed, and chemical characteristics of these megacities are compared. Emission estimates for the megacities are also presented and discussed in the context of expected similarities and differences in the chemical signals in the ambient air impacted by these cities. Comparisons of the observation-based ratios with emission-based estimates are presented and provide a means to test for the consistency of the emission estimates. The observation-based ratios are shown to be generally consistent with the emissions ratios. The megacity emissions are used in the STEM-2K1 model to study the effects of these emissions on criteria and photochemical species in the region. Over large portions of the Japan Sea, Yellow Sea, western Pacific Ocean, and the Bay of Bengal, megacity emissions contribute in excess of 10% of the near-surface ambient levels of O3, CO, SO2, H2SO4, HCHO, and NOz. The megacity emissions are also used to study ozone levels in Asia under a scenario where all cities evolve their emissions in a manner such that they end up with the same VOC/NOx emission ratio as that for Tokyo. Monthly mean ozone levels are found to increase by at least 5%.

[1] We evaluate the TRACE-P emission inventories for gaseous and particulate pollutants from East Asia using chemical measurements made at a rural site in China during the China-MAP Field Intensive in conjunction with a coupled regional climate/chemical transport modeling system. Time-dependent, three-dimensional fields for trace gas and particulate matter concentrations over East Asia are simulated by an updated version of the Regional Acid Deposition Model (RADM) driven by the TRACE-P emission inventories along with meteorology fields calculated by the NCAR Regional Climate Model (RegCM) for the month of November 1999. Model-calculated SO2 is in good agreement with measurements, while CO and particulate carbon (PC) are significantly smaller, and particulate sulfate (SO4� ) is somewhat smaller. Our calculations suggest that increases in the TRACE-P emission inventory of CO by � 50% and PC by 60–90% would bring the model-calculated CO, PC, and particulate sulfate concentration into agreement with the China-MAP observations. If these increases were spread uniformly throughout China and the year, it would require that there be additional emissions in China of CO and PC of 60 Tg yr � 1 and 2.5–4 Tg yr � 1 , respectively. Further analysis of high resolution gas species measurements suggests that the missing CO emissions are likely to be associated with SO2 emissions from coal burning. This in turn suggests that coal-burning facilities in China are operating at significantly lower efficiencies than currently assumed. INDEX TERMS: 0322 Atmospheric Composition and Structure: Constituent sources and sinks; 0345 Atmospheric Composition and Structure: Pollution—urban and regional (0305); 0365 Atmospheric Composition and Structure: Troposphere—composition and chemistry; 0368 Atmospheric Composition and Structure: Troposphere—constituent transport and chemistry; KEYWORDS: anthropogenic emissions, East Asia, regional modeling

[ 1] Regional modeling analysis for the Intercontinental Transport and Chemical Transformation 2002 (ITCT 2K2) experiment over the eastern Pacific and U. S. West Coast is performed using a multiscale modeling system, including the regional tracer model Chemical Weather Forecasting System (CFORS), the Sulfur Transport and Emissions Model 2003 (STEM-2K3) regional chemical transport model, and an off-line coupling with the Model of Ozone and Related Chemical Tracers ( MOZART) global chemical transport model. CO regional tracers calculated online in the CFORS model are used to identify aircraft measurement periods with Asian influences. Asian-influenced air masses measured by the National Oceanic and Atmospheric Administration (NOAA) WP-3 aircraft in this experiment are found to have lower DeltaAcetone/DeltaCO, DeltaMethanol/DeltaCO, and DeltaPropane/DeltaEthyne ratios than air masses influenced by U. S. emissions, reflecting differences in regional emission signals. The Asian air masses in the eastern Pacific are found to usually be well aged (> 5 days), to be highly diffused, and to have low NOy levels. Chemical budget analysis is performed for two flights, and the O-3 net chemical budgets are found to be negative ( net destructive) in the places dominated by Asian influences or clear sites and positive in polluted American air masses. During the trans-Pacific transport, part of gaseous HNO3 was converted to nitrate particle, and this conversion was attributed to NOy decline. Without the aerosol consideration, the model tends to overestimate HNO3 background concentration along the coast region. At the measurement site of Trinidad Head, northern California, high-concentration pollutants are usually associated with calm wind scenarios, implying that the accumulation of local pollutants leads to the high concentration. Seasonal variations are also discussed from April to May for this site. A high-resolution nesting simulation with 12-km horizontal resolution is used to study the WP-3 flight over Los Angeles and surrounding areas. This nested simulation significantly improved the predictions for emitted and secondary generated species. The difference of photochemical behavior between the coarse (60-km) and nesting simulations is discussed and compared with the observation.

In this paper, aerosol composition and size distributions in east Asia are simulated using a comprehensive chemical transport model. Three-dimensional aerosol simulations for the TRACE-P and ACE-Asia periods are performed and used to help interpret actual observations. The regional chemical transport model, STEM-2K3, which includes the on-line gas-aerosol thermodynamic module SCAPE II, and explicitly considers chemical aging of dust, is used in the analysis. The model is found to represent many of the important observed features. The Asian outflow during March and April of 2001 is heavily polluted with high aerosol loadings. Under conditions of low dust loading, SO_2 condensation and gas phase ammonia distribution determine the nitrate size and gas-aerosol distributions along air mass trajectories, a situation that is analyzed in detail for two TRACE-P flights. Dust is predicted to alter the partitioning of the semivolatile components between the gas and aerosol phases as well as the size distributions of the secondary aerosol constituents. Calcium in the dust affects the gas-aerosol equilibrium by shifting the equilibrium balance to an anion-limited status, which benefits the uptake of sulfate and nitrate, but reduces the amount of aerosol ammonium. Surface reactions on dust provide an additional mechanism to produce aerosol nitrate and sulfate. The size distribution of dust is shown to be a critical factor in determining the size distribution of secondary aerosols. As much of the dust mass is found in the supermicron mode (70–90%), appreciable amounts of sulfate and nitrate are found in the supermicron particles. For sulfate the observations and the analysis indicate that 10–30% of sulfate is in the supermicron fraction during dust events; in the case of nitrate, more than 80% is found in the supermicron fraction.

[1] An extensive set of carbonyl sulfide (OCS) and carbon disulfide (CS2) observations were made as part of the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) project, which took place in the early spring 2001. TRACE-P sampling focused on the western Pacific region but in total included the geographic region 110°E to 290°E longitude, 5°N to 50°N latitude, and 0–12 km altitude. Substantial OCS and CS2 enhancements were observed for a great many air masses of Chinese and Japanese origin during TRACE-P. Over the western Pacific, mean mixing ratios of long-lived OCS and shorter-lived CS2 showed a gradual decrease by about 10% and a factor of 5–10, respectively, from the surface to 8–10 km altitude, presumably because land-based sources dominated their distribution during February through April 2001. The highest mean OCS and CS2 levels (580 and 20 pptv, respectively, based on 2.5° × 2.5° latitude bins) were observed below 2 km near the coast of Asia, at latitudes between 25°N and 35°N, where urban Asian outflow was strongest. Ratios of OCS versus CO for continental SE Asia were much lower compared to Chinese and Japanese signatures and were strongly associated with biomass burning/biofuel emissions. We present a new inventory of anthropogenic Asian emissions (including biomass burning) for OCS and CS2 and compare it to emission estimates based on regional relationships of OCS and CS2 to CO and CO2. The OCS and CS2 results for the two methods compare well for continental SE Asia and Japan plus Korea and also for Chinese CS2 emissions. However, it appears that the inventory underestimates Chinese emissions of OCS by about 30–100%. This difference may be related to the fact that we did not include natural sources such as wetland emissions in our inventory, although the contributions from such sources are believed to be at a seasonal low during the study period. Uncertainties in OCS emissions from Chinese coal burning, which are poorly characterized, likely contribute to the discrepancy.

[1] A comprehensive regional-scale chemical transport model, Sulfur Transport and Emissions Model 2001 (STEM-2K1), is employed to study dust outflows and their influence on regional chemistry in the high-dust Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) period, from 4–14 April 2001. In this period, dust storms are initialized in the Taklamagan and Gobi deserts because of cold air outbreaks, are transported eastward, and are often intensified by dust emitted from exposed soils as the front moves off the continent. Simulated dust agrees well with surface weather observations, satellite images, and the measurements of the C-130 aircraft. The C-130 aircraft observations of chemical constituents of the aerosol are analyzed for dust-rich and low-dust periods. In the submicron aerosol, dust-rich air masses have elevated ratios of ΔCa/ΔMg, ΔNH4+/ΔSO42−, and ΔNO3−/ΔCO (Δ represents the difference between observed and background concentrations). The impacts of heterogeneous reactions on dust involving O3, NO2, SO2, and HNO3 are studied by incorporating these reactions into the analysis. These reactions have significant influence on regional chemistry. For example, the low O3 concentrations in C-130 flight 6 can be explained only by the influence of heterogeneous reactions. In the near-surface layer, the modeled heterogeneous reactions indicated that O3, SO2, NO2, and HNO3 are decreased by up to 20%, 55%, 20%, and 95%, respectively, when averaged over this period. In addition, NO, HONO, and daytime OH can increase by 20%, 30%, and 4%, respectively, over polluted regions. When dust encounters fresh pollutants, these heterogeneous reactions can lead to a series of complex responses of the photochemical system. In addition, these reactions can alter the chemical-size distribution of the aerosol. Under heavy dust loadings, these reactions can lead to >20% of the sulfate and >70% of the nitrate being associated with the coarse fraction. The radiative influence of dust can also affect the photochemical system. For example, OH levels can decrease by 20% near surface. The dust radiative influence is shown to be weaker than the heterogeneous influence for most species.

[1] We report on mercury in the atmosphere of east Asia (Japan, Korea, and China) as measured from sea level to ∼7000 m during 16 research flights in the National Science Foundation (NSF)/National Center for Atmospheric Research (NCAR) C-130 aircraft during the Asian Pacific Regional Aerosol Characterization Experiment (ACE-Asia) campaign (http://saga.pmel.noaa.gov/aceasia/). The air at all altitudes contained concentrations of atmospheric mercury above the global background. The atmosphere was highly stratified with plumes originating from massive dust storms carried out of China, from local industrial pollution, from volcanoes, and, less well defined, from biomass burning. Most often the air masses were mixtures, e.g., dust layers contained anthropogenic emissions or volcanic plumes were embedded in anthropogenic pollution; thus the total data set showed no significant correlations of gaseous mercury with the most common anthropogenic pollutants in the area (CO and SO2), but good correlations were observed for identifiable plumes. Highest mixing ratios for gaseous elemental mercury (GEM) were found in industrial plumes exiting China (∼6.3 ng/m3), Korea (∼3 ng/m3), and Japan (∼3 ng/m3). The core of the plume from Miyake Jima volcano contained ∼3.7 ng/m3 of GEM. Crustal mercury was also present, emitted and subsequently deposited during the outbreak of the spring dust storms. Some of the nondust aerosols contained soluble mercury in highly variable ratios with the gas-phase mercury contained in the same plume. Preliminary estimates for the export from China are 5–15 t of crustal mercury during the dust storms, ∼150 t/yr of gas-phase mercury from biomass/biofuel combustion, and ∼600 t/yr from industrial sources, mostly from coal combustion. Gaseous mercury is a useful tracer for industrial, volcanic, and biomass-burning sources, but in most cases, robust plume identification required one or more cotracers. Because of the inertness of GEM and the ease of its measurement it is well suited for the tracking of long-range transport.

[1] Measurements obtained during the NASA Transport and Chemical Evolution over the Pacific (TRACE-P) experiment are used in conjunction with regional modeling analysis to evaluate emission estimates for Asia. A comparison between the modeled values and the observations is one method to evaluate emissions. Based on such analysis it is concluded that the inventory performs well for the light alkanes, CO, ethyne, SO2, and NOx. Furthermore, based on model skill in predicting important photochemical species such as O3, HCHO, OH, HO2, and HNO3, it is found that the emissions inventories are of sufficient quality to support preliminary studies of ozone production. These are important finding in light of the fact that emission estimates for many species (such as speciated NMHCs and BC) for this region have only recently been estimated and are highly uncertain. Using a classification of the measurements built upon trajectory analysis, we compare observed species distributions and ratios of species to those modeled and to ratios estimated from the emissions inventory. It is shown that this technique can reconstruct a spatial distribution of propane/benzene that looks remarkably similar to that calculated from the emissions inventory. A major discrepancy between modeled and observed behavior is found in the Yellow Sea, where modeled values are systematically underpredicted. The integrated analysis suggests that this may be related to an underestimation of emissions from the domestic sector. The emission is further tested by comparing observed and measured species ratios in identified megacity plumes. Many of the model derived ratios (e.g., BC/CO, SOx/C2H2) fall within ∼25% of those observed and all fall outside of a factor of 2.5.

[1] Data obtained during the TRACE-P experiment is used to evaluate how well the CFORS/STEM-2K1 regional-scale chemical transport model is able to represent the aircraft observations. Thirty-one calculated trace gas and aerosol parameters are presented and compared to the in situ data. The regional model is shown to accurately predict many of the important features observed. The mean values of all the model parameters in the lowest 1 km are predicted within ±30% of the observed values. The correlation coefficients (R) for the meteorological parameters are found to be higher than those for the trace species. For example, for temperature, R > 0.98. Among the trace species, ethane, propane, and ozone show the highest values (0.8 < R < 0.9), followed by CO, SO2, and NOy. NO and NO2 had the lowest values (R < 0.4). Analyses of pollutant transport into the Yellow Sea by frontal events are presented and illustrate the complex nature of outflow. Biomass burning from SE Asia is transported in the warm conveyor belt at altitudes above ∼2 km and at latitudes below 30N. Outflow of pollution emitted along the east coast of China in the postfrontal regions is typically confined to the lower ∼2 km and results in high concentrations with plume-like features in the Yellow Sea. During these situations the model underpredicts CO and black carbon (among other species). An analysis of ozone production in this region is also presented. In and around the highly industrialized regions of East Asia, where fossil fuel usage dominates, ozone is NMHC-limited. South of ∼30–35N, ozone production is NOx-limited, reflecting the high NMHC/NOx ratios due to the large contributions to the emissions from biomass burning, biogenics sources, and biofuel usage in central China and SE Asia.