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The interactions between the terrestrial biosphere, atmospheric chemistry, and climate involve complex feedbacks that have traditionally been modeled separately. We present a new framework that couples the Yale Interactive terrestrial Biosphere (YIBs) model, a dynamic plant-chemistry model, with the RegCM-Chem model. RegCM-Chem–YIBs integrates meteorological variables and atmospheric chemical composition from RegCM-Chem with land surface parameters from YIBs. The terrestrial carbon flux calculated by YIBs is fed back into RegCM-Chem interactively, thereby representing the interactions between fine particulate matter (PM 2.5), ozone (O 3), and carbon dioxide (CO 2). For testing purposes, we carry out a 1-year simulation (2016) at a 30 km horizontal resolution over East Asia with RegCM-Chem–YIBs. The model accurately captures the spatio-temporal distribution of climate, chemical composition, and ecological parameters. In particular, the estimated O 3 and PM 2.5 are consistent with ground observations, with correlation coefficients (R) of 0.74 and 0.65, respectively. The simulated CO 2 concentration is consistent with observations from six sites (R ranged from 0.89 to 0.97) and exhibits a similar spatial pattern when compared with carbon assimilation products. RegCM-Chem–YIBs produces reasonably good gross primary productivity (GPP) and net primary productivity (NPP), showing seasonal and spatial distributions consistent with satellite observations, and mean biases (MBs) of 0.13 and 0.05 kg C m -2 yr -1. This study illustrates that RegCM-Chem–YIBs is a valuable tool to investigate coupled interactions between the terrestrial carbon cycle, atmospheric chemistry, and climate change at a higher resolution on a regional scale. [ABSTRACT FROM AUTHOR]

This study explores the differences in performance and results by various versions of the ISORROPIA thermodynamic module implemented within the ECHAM/MESSy Atmospheric Chemistry (EMAC) model. Three different versions of the module were used, ISORROPIA II v1, ISORROPIA II v2.3, and ISORROPIA-lite. First, ISORROPIA II v2.3 replaced ISORROPIA II v1 in EMAC to improve pH predictions close to neutral conditions. The newly developed ISORROPIA-lite has been added to EMAC alongside ISORROPIA II v2.3. ISORROPIA-lite is more computationally efficient and assumes that atmospheric aerosols exist always as supersaturated aqueous (metastable) solutions, while ISORROPIA II includes the option to allow for the formation of solid salts at low RH conditions (stable state). The predictions of EMAC by employing all three aerosol thermodynamic models were compared to each other and evaluated against surface measurements from three regional observational networks in the polluted Northern Hemisphere (Interagency Monitoring of Protected Visual Environments (IMPROVE), European Monitoring and Evaluation Programme (EMEP), and Acid Deposition Monitoring Network of East Asia (EANET)). The differences between ISORROPIA II v2.3 and ISORROPIA-lite were minimal in all comparisons with the normalized mean absolute difference for the concentrations of all major aerosol components being less than 11 % even when different phase state assumptions were used. The most notable differences were lower aerosol concentrations predicted by ISORROPIA-lite in regions with relative humidity in the range of 20 % to 60 % compared to the predictions of ISORROPIA II v2.3 in stable mode. The comparison against observations yielded satisfactory agreement especially over the USA and Europe but higher deviations over East Asia, where the overprediction of EMAC for nitrate was as high as 4 µ g m -3 (∼20%). The mean annual aerosol pH predicted by ISORROPIA-lite was on average less than a unit lower than ISORROPIA II v2.3 in stable mode, mainly for coarse-mode aerosols over the Middle East. The use of ISORROPIA-lite accelerated EMAC by nearly 5 % compared to the use of ISORROPIA II v2.3 even if the aerosol thermodynamic calculations consume a relatively small fraction of the EMAC computational time. ISORROPIA-lite can therefore be a reliable and computationally efficient alternative to the previous thermodynamic module in EMAC. [ABSTRACT FROM AUTHOR]

The interactions between the terrestrial biosphere, atmospheric chemistry, and climate involve complex feedbacks that have traditionally been modeled separately. We present a new framework that couples the Yale Interactive terrestrial Biosphere (YIBs), a dynamic plant-chemistry model, with the RegCM-Chem model. RegCM-Chem-YIBs integrates meteorological variables and atmospheric chemical composition from RegCM-Chem with land surface parameters from YIBs. The terrestrial carbon flux calculated by YIBs, are fed back into RegCM-Chem interactively, thereby representing the interactions between fine particulate matter (PM2.5), ozone (O3), and carbon dioxide (CO2). For testing purposes, we carry out a one-year simulation (2016) at a 30 km horizontal resolution over East Asia with RegCM-Chem-YIBs. The model accurately captures the spa-tio-temporal distribution of climate, chemical composition, and ecological parameters. In particular, the estimated O3 and PM2.5 are consistent with ground observations, with correlation coefficients (R) of 0.74 and 0.65, respec-tively. The simulated CO2 concentration is consistent with observations from six sites (R ranged from 0.89 to 0.97) and exhibits a similar spatial pattern when compared to carbon assimilation products. RegCM-Chem-YIBs produces reasonably good gross primary productivity (GPP) and net primary productivity (NPP), showing seasonal and spatial distributions consistent with satellite observations, and mean biases (MBs) of 0.13 and 0.05 kg C m-2 year-1. This study illustrates that the RegCM-Chem-YIBs is a valuable tool to investigate coupled interactions between the terrestrial carbon cycle, atmospheric chemistry, and climate change at a higher resolution in regional scale. [ABSTRACT FROM AUTHOR]

The reduction of fine particles (PM 2.5) and reactive N (N r) and S (S r) species is a key objective for air pollution control policies because of their major adverse effects on human health, ecosystem diversity, and climate. The sensitivity of global and regional N r , S r , and PM 2.5 to 20 % and 40 % individual and collective reductions in anthropogenic emissions of NH 3 , NO x , and SO x (with respect to a 2015 baseline) is investigated using the EMEP MSC-W (European Monitoring and Evaluation Programme Meteorological Synthesizing Centre – West) atmospheric chemistry transport model with WRF (Weather Research and Forecasting) meteorology. Regional comparisons reveal that the individual emissions reduction has multiple co-benefits and small disbenefits on different species, and those effects are highly geographically variable. A 40 % NH 3 emission reduction decreases regional average NH 3 concentrations by 47 %–49 % but only decreases NH 4+ by 18 % in Euro_Medi, 15 % in East Asia, 12 % in North America, and 4 % in South Asia. This order follows the regional ammonia richness. A disbenefit is the increased SO 2 concentrations in these regions (10 %–16 % for 40 % reductions) because reduced NH 3 levels decrease SO 2 deposition through altering atmospheric acidity. A 40 % NO x emission reduction reduces NO x concentrations in East Asia by 45 %, Euro_Medi and North America by ∼ 38 %, and South Asia by 22 %, whilst the regional order is reversed for fine NO 3- , which is related to enhanced O 3 levels in East Asia (and also, but by less, in Euro_Medi) and decreased O 3 levels in South Asia (and also, but by less, in North America). Consequently, the oxidation of NO x to NO 3- and of SO 2 to SO 42- is enhanced in East Asia but decreased in South Asia, which causes a less effective decrease in NO 3- and even an increase in SO 42- in East Asia but quite the opposite in South Asia. For regional policy making, it is thus vital to reduce three precursors together to minimize such adverse effects. A 40 % SO x emission reduction is slightly more effective in reducing SO 2 (42 %–45 %) than SO 42- (34 %–38 %), whilst the disbenefit is that it yields a ∼ 12 % increase in total NH 3 deposition in the four regions, which further threatens ecosystem diversity. This work also highlights important messages for policy makers concerning the mitigation of PM 2.5. More emissions controls focusing on NH 3 and NO x are necessary for regions with better air quality, such as northern Europe and eastern North America. In East Asia, the three individual reductions are equally effective, whilst in South Asia only SO x reduction is currently effective. The geographically varying non-one-to-one proportionality of chemical responses of N r , S r , and PM 2.5 to emissions reductions revealed by this work show the importance of both prioritizing emissions strategies in different regions and combining several precursor reductions together to maximize the policy effectiveness. [ABSTRACT FROM AUTHOR]

Quantification and attribution of long-term tropospheric ozone trends are critical for understanding the impact of human activity and climate change on atmospheric chemistry but are also challenged by the limited coverage of long-term ozone observations in the free troposphere where ozone has higher production efficiency and radiative potential compared to that at the surface. In this study, we examine observed tropospheric ozone trends, their attributions, and radiative impacts from 1995–2017 using aircraft observations from the In-service Aircraft for a Global Observing System database (IAGOS), ozonesondes, and a multi-decadal GEOS-Chem chemical model simulation. IAGOS observations above 11 regions in the Northern Hemisphere and 19 of 27 global ozonesonde sites have measured increases in tropospheric ozone (950–250 hPa) by 2.7 ± 1.7 and 1.9 ± 1.7 ppbv per decade on average, respectively, with particularly large increases in the lower troposphere (950–800 hPa) above East Asia, the Persian Gulf, India, northern South America, the Gulf of Guinea, and Malaysia/Indonesia by 2.8 to 10.6 ppbv per decade. The GEOS-Chem simulation driven by reanalysis meteorological fields and the most up-to-date year-specific anthropogenic emission inventory reproduces the overall pattern of observed tropospheric ozone trends, including the large ozone increases over the tropics of 2.1–2.9 ppbv per decade and above East Asia of 0.5–1.8 ppbv per decade and the weak tropospheric ozone trends above North America, Europe, and high latitudes in both hemispheres, but trends are underestimated compared to observations. GEOS-Chem estimates an increasing trend of 0.4 Tg yr -1 of the tropospheric ozone burden in 1995–2017. We suggest that uncertainties in the anthropogenic emission inventory in the early years of the simulation (e.g., 1995–1999) over developing regions may contribute to GEOS-Chem's underestimation of tropospheric ozone trends. GEOS-Chem sensitivity simulations show that changes in global anthropogenic emission patterns, including the equatorward redistribution of surface emissions and the rapid increases in aircraft emissions, are the dominant factors contributing to tropospheric ozone trends by 0.5 Tg yr -1. In particular, we highlight the disproportionately large, but previously underappreciated, contribution of aircraft emissions to tropospheric ozone trends by 0.3 Tg yr -1 , mainly due to aircraft emitting NO x in the mid-troposphere and upper troposphere where ozone production efficiency is high. Decreases in lower-stratospheric ozone and the stratosphere–troposphere flux in 1995–2017 contribute to an ozone decrease at mid-latitudes and high latitudes. We estimate the change in tropospheric ozone radiative impacts from 1995–1999 to 2013–2017 is +18.5 mW m -2 , with 43.5 mW m -2 contributed by anthropogenic emission changes (20.5 mW m -2 alone by aircraft emissions), highlighting that the equatorward redistribution of emissions to areas with strong convection and the increase in aircraft emissions are effective for increasing tropospheric ozone's greenhouse effect. [ABSTRACT FROM AUTHOR]

Relationships between oceanic emissions and air chemistry are intricate and still not fully understood. For regional air chemistry, a better understanding of marine halogen emission on the hydroxyl (OH) radical is crucial. The OH radical is a key species in atmospheric chemistry because it can oxidize almost all trace species in the atmosphere. In the marine atmosphere, OH levels could be significantly affected by the halogen species emitted from the ocean. However, due to the complicated interactions of halogens with OH through different pathways, it is not well understood how halogens influence OH and even what the sign of the net effect is. Therefore, in this study, we aim to quantify the impact of marine-emitted halogens (including Cl, Br, and I) through different pathways on OH in the high OH season by using the WRF-CMAQ model with process analysis and state-of-the-art halogen chemistry in East Asia and near the western Pacific. Results show a very complicated response of the OH production rate (P OH) to marine halogen emissions. The monthly P OH is generally decreased over the ocean by up to a maximum of about 10 %–15 % in the Philippine Sea, but it is increased in many nearshore areas by up to about 7 %–9 % in the Bohai Sea. In the coastal areas of southern China, the monthly P OH could also decrease 3 %–5 %, but hourly values can decrease over 30 % in the daytime. Analysis of the individual reactions using the integrated reaction rate shows that the net change in P OH is controlled by the competition of three main pathways (OH from O 3 photolysis, OH from HO 2 conversion, and OH from HO X , X=Cl , Br, I) through different halogen species. Sea spray aerosol (SSA) and inorganic iodine gases are the major species influencing the strengths of these three pathways and therefore have the most significant impacts on P OH. Both of these two types of species decrease P OH through physical processes, while generally increasing P OH through chemical processes. In the ocean atmosphere, inorganic iodine gases determine the basic pattern of Δ P OH through complicated iodine chemistry, which generally positively influences P OH near O 3 sources while negatively influencing it when O 3 experiences longer transport over the ocean. Over the continent, SSA is the controlling species, and the SSA extinction effect leads to the negative Δ P OH in southern China. Our results show that marine-emitted halogen species have notable impacts over the ocean and potential impacts on coastal atmospheric oxidation by species (SSA, inorganic iodine, and halocarbons), processes (chemistry, radiation, and deposition), and main pathways. The notable impacts of the marine-emitted halogen species on the atmospheric oxidation capacity have further implications for the lifetime of long-lived species such as CH 4 in the long term and the quantity of air pollutants such as O 3 in the episodic events in East Asia and in other circumstances (e.g., different domains, regions, and emission rates). [ABSTRACT FROM AUTHOR]

Ammonia (NH3) plays a central role in the chemistry of inorganic secondary aerosols in the atmosphere. The largest emission sector for NH3 is agriculture, where NH3 is volatilized from livestock wastes and fertilized soils. Although the NH3 volatilization from soils is driven by the soil temperature and moisture, many atmospheric chemistry models prescribe the emission using yearly emission inventories and climatological seasonal variations. Here we evaluate an alternative approach where the NH3 emissions from agriculture are simulated interactively using the process model FANv2 (Flow of Agricultural Nitrogen, version 2) coupled to the Community Atmospheric Model with Chemistry (CAM-chem). We run a set of 6-year global simulations using the NH3 emission from FANv2 and three global emission inventories (EDGAR, CEDS and HTAP) and evaluate the model performance using a global set of multi-component (atmospheric NH3 and NH4+ , and NH4+ wet deposition) in situ observations. Over East Asia, Europe and North America, the simulations with different emissions perform similarly when compared with the observed geographical patterns. The seasonal distributions of NH3 emissions differ between the inventories, and the comparison to observations suggests that both FANv2 and the inventories would benefit from more realistic timing of fertilizer applications. The largest differences between the simulations occur over data-scarce regions. In Africa, the emissions simulated by FANv2 are 200 %–300 % higher than in the inventories, and the available in situ observations from western and central Africa, as well as NH3 retrievals from the Infrared Atmospheric Sounding Interferometer (IASI) instrument, are consistent with the higher NH3 emissions as simulated by FANv2. Overall, in simulating ammonia and ammonium concentrations over regions with detailed regional emission inventories, the inventories based on these details (HTAP, CEDS) capture the atmospheric concentrations and their seasonal variability the best. However these inventories cannot capture the impact of meteorological variability on the emissions, nor can these inventories couple the emissions to the biogeochemical cycles and their changes with climate drivers. Finally, we show with sensitivity experiments that the simulated time-averaged nitrate concentration in air is sensitive to the temporal resolution of the NH3 emissions. Over the CASTNET monitoring network covering the US, resolving the NH3 emissions hourly instead monthly reduced the positive model bias from approximately 80 % to 60 % of the observed yearly mean nitrate concentration. This suggests that some of the commonly reported overestimation of aerosol nitrate over the US may be related to unresolved temporal variability in the NH3 emissions. [ABSTRACT FROM AUTHOR]

Air quality simulations in which the global chemical transport model CHASER and the regional chemical transport model WRF/chem are coupled have been developed to consider the dynamic transport of chemical species across the boundaries of the domain of the regional chemical transport model. The simulation captures the overall seasonal variations of surface ozone, but overestimates its concentration over Japanese populated areas by approximately 20 ppb from summer to early winter. It is deduced that ozone formation around Northeast China and Japan in summer is overestimated in the simulation. On the other hand, the simulation well reproduces the interannual variability and the long-term trend of observed surface ozone over Japan. Sensitivity experiments have been performed to investigate the influence of the variation in inflow to East Asia on the interannual variability and the long-term trend of surface ozone over Japan during 1996-2005. The inflow defined in this paper includes the recirculation of species with sources within the East Asian region as well as the transport of species with sources out of the East Asian region. Results of sensitivity experiments suggest that inflow to East Asia accounts for approximately 30% of the increasing trend of surface ozone, whereas it has much less influence on the interannual variability of observed surface ozone compared to meteorological processes within East Asia. [ABSTRACT FROM AUTHOR]

Many efforts have been devoted to quantifying the impact of intercontinental transport on global air quality by using global chemical transport models with horizontal resolutions of hundreds of kilometers in recent decades. In this study, a global online air quality source–receptor model (GNAQPMS-SM) is designed to effectively compute the contributions of various regions to ambient pollutant concentrations. The newly developed model is able to quantify source–receptor (S-R) relationships in one simulation without introducing errors by nonlinear chemistry. We calculate the surface and planetary boundary layer (PBL) S-R relationships in 19 regions over the whole globe for ozone (O 3), black carbon (BC), and non-sea-salt sulfate (nss-sulfate) by conducting a high-resolution (0.5 ∘ × 0.5 ∘) simulation for the year 2018. The model exhibits a realistic capacity in reproducing the spatial distributions and seasonal variations of tropospheric O 3 , carbon monoxide, and aerosols at global and regional scales – Europe (EUR), North America (NAM), and East Asia (EA). The correlation coefficient (R) and normalized mean bias (NMB) for seasonal O 3 at global background and urban–rural sites ranged from 0.49 to 0.87 and - 2 % to 14.97 %, respectively. For aerosols, the R and NMB in EUR, NAM, and EA mostly exceed 0.6 and are within ± 15 %. These statistical parameters based on this global simulation can match those of regional models in key regions. The simulated tropospheric nitrogen dioxide and aerosol optical depths are generally in agreement with satellite observations. The model overestimates ozone concentrations in the upper troposphere and stratosphere in the tropics, midlatitude, and polar regions of the Southern Hemisphere due to the use of a simplified stratospheric ozone scheme and/or biases in estimated stratosphere–troposphere exchange dynamics. We find that surface O 3 can travel a long distance and contributes a non-negligible fraction to downwind regions. Non-local source transport explains approximately 35 %–60 % of surface O 3 in EA, South Asia (SAS), EUR, and NAM. The O 3 exported from EUR can also be transported across the Arctic Ocean to the North Pacific and contributes nearly 5 %–7.5 % to the North Pacific. BC is directly linked to local emissions, and each BC source region mainly contributes to itself and surrounding regions. For nss-sulfate, contributions of long-range transport account for 15 %–30 % within the PBL in EA, SAS, EUR, and NAM. Our estimated international transport of BC and nss-sulfate is lower than that from the Hemispheric Transport of Air Pollution (HTAP) assessment report in 2010, but most surface O 3 results are within the range. This difference may be related to the different simulation years, emission inventories, vertical and horizontal resolutions, and S-R revealing methods. Additional emission sensitivity simulation shows a negative O 3 response in receptor region EA in January from EA. The difference between two methods in estimated S-R relationships of nss-sulfate and O 3 are mainly due to ignoring the nonlinearity of pollutants during chemical processes. The S-R relationship of aerosols within EA subcontinent is also assessed. The model that we developed creates a link between the scientific community and policymakers. Finally, the results are discussed in the context of future model development and analysis opportunities. [ABSTRACT FROM AUTHOR]

Atmospheric pollution has many profound effects on human health, ecosystems, and the climate. Of concern are high concentrations and deposition of reactive nitrogen (N r) species, especially of reduced N (gaseous NH3 , particulate NH4+). Atmospheric chemistry and transport models (ACTMs) are crucial to understanding sources and impacts of N r chemistry and its potential mitigation. Here we undertake the first evaluation of the global version of the EMEP MSC-W ACTM driven by WRF meteorology (1∘×1∘ resolution), with a focus on surface concentrations and wet deposition of N and S species relevant to investigation of atmospheric N r and secondary inorganic aerosol (SIA). The model–measurement comparison is conducted both spatially and temporally, covering 10 monitoring networks worldwide. Model simulations for 2010 compared use of both HTAP and ECLIPSE E (ECLIPSE annual total with EDGAR monthly profile) emissions inventories; those for 2015 used ECLIPSE E only. Simulations of primary pollutants are somewhat sensitive to the choice of inventory in places where regional differences in primary emissions between the two inventories are apparent (e.g. China) but are much less sensitive for secondary components. For example, the difference in modelled global annual mean surface NH3 concentration using the two 2010 inventories is 18 % (HTAP: 0.26 µgm-3 ; ECLIPSE E : 0.31 µgm-3) but is only 3.5 % for NH4+ (HTAP: 0.316 µgm-3 ; ECLIPSE E : 0.305 µgm-3). Comparisons of 2010 and 2015 surface concentrations between the model and measurements demonstrate that the model captures the overall spatial and seasonal variations well for the major inorganic pollutants NH3 , NO2 , SO2 , HNO3 , NH4+ , NO3- , and SO42- and their wet deposition in East Asia, Southeast Asia, Europe, and North America. The model shows better correlations with annual average measurements for networks in Southeast Asia (mean R for seven species: R7‾=0.73), Europe (R7‾=0.67), and North America (R7‾=0.63) than in East Asia (R5‾=0.35) (data for 2015), which suggests potential issues with the measurements in the latter network. Temporally, both model and measurements agree on higher NH3 concentrations in spring and summer and lower concentrations in winter. The model slightly underestimates annual total precipitation measurements (by 13 %–45 %) but agrees well with the spatial variations in precipitation in all four world regions (0.65–0.94 R range). High correlations between measured and modelled NH4+ precipitation concentrations are also observed in all regions except East Asia. For annual total wet deposition of reduced N, the greatest consistency is in North America (0.75–0.82 R range), followed by Southeast Asia (R=0.68) and Europe (R=0.61). Model–measurement bias varies between species in different networks; for example, bias for NH4+ and NO3- is largest in Europe and North America and smallest in East Asia and Southeast Asia. The greater uniformity in spatial correlations than in biases suggests that the major driver of model–measurement discrepancies (aside from differing spatial representativeness and uncertainties and biases in measurements) are shortcomings in absolute emissions rather than in modelling the atmospheric processes. The comprehensive evaluations presented in this study support the application of this model framework for global analysis of current and potential future budgets and deposition of N r and SIA. [ABSTRACT FROM AUTHOR]

Aromatics contribute a significant fraction to organic compounds in the troposphere and are mainly emitted by anthropogenic activities and biomass burning. Their oxidation in lab experiments is known to lead to the formation of ozone and aerosol precursors. However, their overall impact on tropospheric composition is uncertain as it depends on transport, multiphase chemistry, and removal processes of the oxidation intermediates. Representation of aromatics in global atmospheric models has been either neglected or highly simplified. Here, we present an assessment of their impact on gas-phase chemistry, using the general circulation model EMAC (ECHAM5/MESSy Atmospheric Chemistry). We employ a comprehensive kinetic model to represent the oxidation of the following monocyclic aromatics: benzene, toluene, xylenes, phenol, styrene, ethylbenzene, trimethylbenzenes, benzaldehyde, and lumped higher aromatics that contain more than nine C atoms. Significant regional changes are identified for several species. For instance, glyoxal increases by 130 % in Europe and 260 % in East Asia, respectively. Large increases in HCHO are also predicted in these regions. In general, the influence of aromatics is particularly evident in areas with high concentrations of NOx , with increases up to 12 % in O3 and 17 % in OH. On a global scale, the estimated net changes of trace gas levels are minor when aromatic compounds are included in our model. For instance, the tropospheric burden of CO increases by about 6 %, while the burdens of OH , O3 , and NOx (NO+NO2) decrease between 3 % and 9 %. The global mean changes are small, partially because of compensating effects between high- and low- NOx regions. The largest change is predicted for the important aerosol precursor glyoxal, which increases globally by 36 %. In contrast to other studies, the net change in tropospheric ozone is predicted to be negative, -3 % globally. This change is larger in the Northern Hemisphere where global models usually show positive biases. We find that the reaction with phenoxy radicals is a significant loss for ozone, on the order of 200–300 Tg yr -1 , which is similar to the estimated ozone loss due to bromine chemistry. Although the net global impact of aromatics is limited, our results indicate that aromatics can strongly influence tropospheric chemistry on a regional scale, most significantly in East Asia. An analysis of the main model uncertainties related to oxidation and emissions suggests that the impact of aromatics may even be significantly larger. [ABSTRACT FROM AUTHOR]

Cloud water acidity affects the atmospheric chemistry of sulfate and organic aerosol formation, halogen radical cycling, and trace metal speciation. Precipitation acidity including post-depositional inputs adversely affects soil and freshwater ecosystems. Here, we use the GEOS-Chem model of atmospheric chemistry to simulate the global distributions of cloud water and precipitation acidity as well as the total acid inputs to ecosystems from wet deposition. The model accounts for strong acids (H2SO4 , HNO3 , and HCl), weak acids (HCOOH, CH3COOH , CO2 , and SO2), and weak bases (NH3 as well as dust and sea salt aerosol alkalinity). We compile a global data set of cloud water pH measurements for comparison with the model. The global mean observed cloud water pH is 5.2±0.9 , compared to 5.0±0.8 in the model, with a range from 3 to 8 depending on the region. The lowest values are over East Asia, and the highest values are over deserts. Cloud water pH over East Asia is low because of large acid inputs (H2SO4 and HNO3), despite NH3 and dust neutralizing 70 % of these inputs. Cloud water pH is typically 4–5 over the US and Europe. Carboxylic acids account for less than 25 % of cloud water H+ in the Northern Hemisphere on an annual basis but 25 %–50 % in the Southern Hemisphere and over 50 % in the southern tropical continents, where they push the cloud water pH below 4.5. Anthropogenic emissions of SO2 and NOx (precursors of H2SO4 and HNO3) are decreasing at northern midlatitudes, but the effect on cloud water pH is strongly buffered by NH4+ and carboxylic acids. The global mean precipitation pH is 5.5 in GEOS-Chem, which is higher than the cloud water pH because of dilution and below-cloud scavenging of NH3 and dust. GEOS-Chem successfully reproduces the annual mean precipitation pH observations in North America, Europe, and eastern Asia. Carboxylic acids, which are undetected in routine observations due to biodegradation, lower the annual mean precipitation pH in these areas by 0.2 units. The acid wet deposition flux to terrestrial ecosystems taking into account the acidifying potential of NO3- and NH4+ in N-saturated ecosystems exceeds 50 meqm-2a-1 in East Asia and the Americas, which would affect sensitive ecosystems. NH4+ is the dominant acidifying species in wet deposition, contributing 41 % of the global acid flux to continents under N-saturated conditions. [ABSTRACT FROM AUTHOR]

In this study, a full description and comprehensive evaluation of a global–regional nested model, the Aerosol and Atmospheric Chemistry Model of the Institute of Atmospheric Physics (IAP-AACM), is presented for the first time. Not only are the global budgets and distribution explored, but comparisons of the nested simulation over China against multiple datasets are investigated, which benefit from access to Chinese air quality monitoring data from 2013 to the present and the "Model Inter-Comparison Study for Asia" project. The model results and analysis can help reduce uncertainties and aid with understanding model diversity with respect to assessing global and regional aerosol effects on climate and human health, especially over East Asia and areas affected by East Asia. For the global simulation, the 1-year simulation for 2014 shows that the IAP-AACM is within the range of other models. Overall, it reasonably reproduced spatial distributions and seasonal variations of trace gases and aerosols in both surface concentrations and column burdens (mostly within a factor of 2). The model captured spatial variation for carbon monoxide well with a slight underestimation over ocean, which implicates the uncertainty of the ocean source. The simulation also matched the seasonal cycle of ozone well except for the continents in the Northern Hemisphere, which was partly due to the lack of stratospheric–tropospheric exchange. For aerosols, the simulation of fine-mode particulate matter (PM 2.5) matched observations well. The simulation of primary aerosols (normalized mean biases, NMBs, are within ±0.64) is better than that of secondary aerosols (NMB values are greater than 1.0 in some regions). For the nested regional simulation, the IAP-AACM shows the superiority of higher-resolution simulation using the nested domain over East Asia. The model reproduced variation of sulfur dioxide (SO2), nitrogen dioxide (NO2), and PM 2.5 accurately in typical cities, with correlation coefficients (R) above 0.5 and NMBs within ±0.5. Compared with the global simulation, the nested simulation exhibits an improved ability to capture the high temporal and spatial variability over China. In particular, the R values for SO2 , NO2 and PM 2.5 are increased by ∼0.15 , ∼0.2 , and ∼0.25 respectively in the nested grid. Based on the evaluation and analysis, future model improvements are suggested. [ABSTRACT FROM AUTHOR]

We analyzed long-term fine- and coarse-mode synergetic observations of nitrate and related aerosols (SO42-, NO3-, NH4+, Na+, Ca2+) at Fukuoka (33.52° N, 130.47° E) from August 2014 to October 2015. A Goddard Earth Observing System chemical transport model (GEOS-Chem) including dust and sea salt acid uptake processes was used to assess the observed seasonal variation and the impact of long-range transport (LRT) from the Asian continent. For fine aerosols (fSO42-, fNO3-, and fNH4+), numerical results explained the seasonal changes, and a sensitivity analysis excluding Japanese domestic emissions clarified the LRT fraction at Fukuoka (85% for fSO42-, 47% for fNO3-, 73% for fNH4+). Observational data confirmed that coarse NO3- (cNO3-) made up the largest proportion (i.e., 40-55%) of the total nitrate (defined as the sum of fNO3-, cNO3-, and HNO3) during the winter, while HNO3 gas constituted approximately 40% of the total nitrate in summer and fNO3- peaked during the winter. Large-scale dust-nitrate (mainly cNO3-) outflow from China to Fukuoka was confirmed during all dust events that occurred between January and June. The modeled cNO3- was in good agreement with observations between July and November (mainly coming from sea salt NO3-). During the winter, however, the model underestimated cNO3- levels compared to the observed levels. The reason for this underestimation was examined statistically using multiple regression analysis (MRA). We used cNa+, nss-cCa2+, and cNH4+ as independent variables to describe the observed cNO3- levels; these variables were considered representative of sea salt cNO3-, dust cNO3-, and cNO3- accompanied by cNH4+), respectively. The MRA results explained the observed seasonal changes in dust cNO3- and indicated that the dust-acid uptake scheme reproduced the observed dust-nitrate levels even in winter. The annual average contributions of each component were 43% (sea salt cNO3-), 19% (dust cNO3-), and 38% (cNH4+ term). The MRA dust-cNO3- component had a high value during the dust season, and the sea salt component made a large contribution throughout the year. During the winter, cNH4+ term made a large contribution. The model did not include aerosol microphysical processes (such as condensation and coagulation between the fine anthropogenic aerosols NO3- and SO42- and coarse particles), and our results suggest that inclusion of aerosol microphysical processes is critical when studying observed cNO3- formation, especially in winter. [ABSTRACT FROM AUTHOR]

The Community Multiscale Air Quality (CMAQ) model has been further developed in terms of simulating natural wind-blown dust in this study, with a series of modifications aimed at improving the model's capability to predict the emission, transport, and chemical reactions of dust. The default parameterization of initial threshold friction velocity constants are revised to correct the double counting of the impact of soil moisture in CMAQ by the reanalysis of field experiment data; source-dependent speciation profiles for dust emission are derived based on local measurements for the Gobi and Taklamakan deserts in East Asia; and dust heterogeneous chemistry is also implemented. The improved dust module in the CMAQ is applied over East Asia for March and April from 2006 to 2010. The model evaluation result shows that the simulation bias of PM10 and aerosol optical depth (AOD) is reduced, respectively, from -55.42 and -31.97% by the original CMAQ to -16.05 and -22.1% by the revised CMAQ. Comparison with observations at the nearby Gobi stations of Duolun and Yulin indicates that applying a source-dependent profile helps reduce simulation bias for trace metals. Implementing heterogeneous chemistry also results in better agreement with observations for sulfur dioxide (SO2), sulfate (SO2- 4 ), nitric acid (HNO3), nitrous oxides (NOx). The investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variation of dust. The model evaluation also indicates potential uncertainty within the excessive soil moisture used by meteorological simulation. The mass contribution of fine-mode particles in dust emission may be underestimated by 50%. The revised CMAQ model provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere. [ABSTRACT FROM AUTHOR]-3). The investigation of a severe dust storm episode from 19 to 21 March 2010 suggests that the revised CMAQ is capable of capturing the spatial distribution and temporal variation of dust. The model evaluation also indicates potential uncertainty within the excessive soil moisture used by meteorological simulation. The mass contribution of fine-mode particles in dust emission may be underestimated by 50%. The revised CMAQ model provides a useful tool for future studies to investigate the emission, transport, and impact of wind-blown dust over East Asia and elsewhere. [ABSTRACT FROM AUTHOR]

Understanding the exchange processes between the atmospheric boundary layer and the free troposphere is crucial for estimating hemispheric transport of air pollution. Most studies of hemispheric air pollution transport have taken a large-scale perspective using global chemical transport models with fairly coarse spatial and temporal resolutions. In support of United Nations Task Force on Hemispheric Transport of Air Pollution (TF HTAP; www.htap. org), this study employs two high-resolution atmospheric chemistry models (WRF-Chem and CMAQ; 36×36 km) driven with chemical boundary conditions from a global model (MOZART; 1.9×1.9°) to examine the role of finescale transport and chemistry processes in controlling pollution export and import over the Asian continent in spring (March 2001). Our analysis indicates the importance of rapid venting through deep convection that develops along the leading edge of frontal system convergence bands, which are not adequately resolved in either of two global models compared with TRACE-P aircraft observations during a frontal event. Both regional model simulations and observations show that frontal outflows of CO, O3 and PAN can extend to the upper troposphere (6-9 km). Pollution plumes in the global MOZART model are typically diluted and insufficiently lofted to higher altitudes where they can undergo more efficient transport in stronger winds. We use sensitivity simulations that perturb chemical boundary conditions in the CMAQ regional model to estimate that the O3 production over East Asia (EA) driven by PAN decomposition contributes 20% of the spatial averaged total O3 response to European (EU) emission perturbations in March, and occasionally contributes approximately 50% of the total O3 response in subsiding plumes at mountain observatories (at approximately 2 km altitude). The response to decomposing PAN of EU origin is strongly affected by the O3 formation chemical regimes, which vary with the model chemical mechanism and NOx/VOC emissions. Our highresolution models demonstrate a large spatial variability (by up to a factor of 6) in the response of local O3 to 20% reductions in EU anthropogenic O3 precursor emissions. The response in the highly populated Asian megacities is 40- 50% lower in our high-resolution models than the global model, suggesting that the source-receptor relationships inferred from the global coarse-resolution models likely overestimate health impacts associated with intercontinental O3 transport. Our results highlight the important roles of rapid convective transport, orographic forcing, urban photochemistry and heterogeneous boundary layer processes in controlling intercontinental transport; these processes may not be well resolved in the large-scale models. [ABSTRACT FROM AUTHOR]

The impact of the East Asia monsoon on the seasonal behavior of O3 in the boundary layer of Eastern China and the west Pacific region was analyzed for 2004-2006 by means of full-year nested chemical transport model simulations and continuous observational data obtained from three inland mountain sites in central and eastern China and three oceanic sites in the west Pacific region. The basic common features of O3 seasonal behaviors over all the monitoring sites are the pre- and post-monsoon peaks with a summer trough. Such bimodal seasonal patterns of O3 are predominant over the region with strong summer monsoon penetration, and become weaker or even disappear outside the monsoon region. The seasonal/geographical distribution of the pre-defined monsoon index indicated that the East Asia summer monsoon is responsible for the bimodal seasonal O3 pattern, and also partly account for the differences in the O3 seasonal variations between the inland mountain and oceanic sites. Over the inland mountain sites, the O3 concentration increased gradually from the beginning of the year, reached a maximum in June, decreased rapidly to the summer valley in July or August, and then peaked in September or October, thereafter decreased gradually again. Over the oceanic sites, O3 abundance showed a similar increasing trend beginning in January, but then decreased gradually from the end of March, followed by a wide trough with the minimum in July and August and a small peak in October or November. A sensitivity analysis performed by setting China-emission to zero revealed that the chemically produced O3 from China-emission contributed substantially to the O3 abundance, particularly the pre- and post-monsoon O3 peaks, over China mainland. We found that China-emission contributed more than 40% to total boundary layer O3 during summertime (60-70% in July) and accounted for about 40 ppb of each peak value over the inland region if without considering the effect of the nonlinear chemical productions. In contrast, over the oceanic region in the high monsoon index zone, the contribution of China-emission to total boundary layer O3 was always less than 20% (<10 ppb), and less than 10% in summer. [ABSTRACT FROM AUTHOR]