Three-dimensional Chemical Transport Model Research Articles

Satellite observations of stratospheric hydrogen fluoride and comparisons with SLIMCAT calculations

Abstract. The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). Many of these fluorine-containing species deplete stratospheric ozone and are regulated by the Montreal Protocol. Once in the atmosphere they slowly degrade, ultimately leading to the formation of hydrogen fluoride (HF), the dominant reservoir of stratospheric fluorine due to its extreme stability. Monitoring the growth of stratospheric HF is therefore an important marker for the success of the Montreal Protocol. We report the comparison of global distributions and trends of HF measured in the Earth's atmosphere by the satellite remote-sensing instruments ACE-FTS (Atmospheric Chemistry Experiment Fourier transform spectrometer), which has been recording atmospheric spectra since 2004, and HALOE (HALogen Occultation Experiment), which recorded atmospheric spectra between 1991 and 2005, with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the agreement between observation and model is good, although the ACE-FTS measurements are biased high by ∼ 10 % relative to HALOE. The observed global HF trends reveal a substantial slowing down in the rate of increase of HF since the 1990s: 4.97 ± 0.12 % year−1 (1991–1997; HALOE), 1.12 ± 0.08 % year−1 (1998–2005; HALOE), and 0.52 ± 0.03 % year−1 (2004–2012; ACE-FTS). In comparison, SLIMCAT calculates trends of 4.01, 1.10, and 0.48 % year−1, respectively, for the same periods; the agreement is very good for all but the earlier of the two HALOE periods. Furthermore, the observations reveal variations in the HF trends with latitude and altitude; for example, between 2004 and 2012 HF actually decreased in the Southern Hemisphere below ∼ 35 km. An additional SLIMCAT simulation with repeating meteorology for the year 2000 produces much cleaner trends in HF with minimal variations with latitude and altitude. Therefore, the variations with latitude and altitude in the observed HF trends are due to variability in stratospheric dynamics on the timescale of a few years. Overall, the agreement between observation and model points towards the ongoing success of the Montreal Protocol and the usefulness of HF as a metric for stratospheric fluorine.

Implementation of state-of-the-art ternary new-particle formation scheme to the regional chemical transport model PMCAMx-UF in Europe

Abstract. The particle formation scheme within PMCAMx-UF, a three-dimensional chemical transport model, was updated with particle formation rates for the ternary H2SO4–NH3–H2O pathway simulated by the Atmospheric Cluster Dynamics Code (ACDC) using quantum chemical input data. The model was applied over Europe for May 2008, during which the EUCAARI-LONGREX (European Aerosol Cloud Climate and Air Quality Interactions–Long-Range Experiment) campaign was carried out, providing aircraft vertical profiles of aerosol number concentrations. The updated model reproduces the observed number concentrations of particles larger than 4 nm within 1 order of magnitude throughout the atmospheric column. This agreement is encouraging considering the fact that no semi-empirical fitting was needed to obtain realistic particle formation rates. The cloud adjustment scheme for modifying the photolysis rate profiles within PMCAMx-UF was also updated with the TUV (Tropospheric Ultraviolet and Visible) radiative-transfer model. Results show that, although the effect of the new cloud adjustment scheme on total number concentrations is small, enhanced new-particle formation is predicted near cloudy regions. This is due to the enhanced radiation above and in the vicinity of the clouds, which in turn leads to higher production of sulfuric acid. The sensitivity of the results to including emissions from natural sources is also discussed.

Microscale air quality impacts of distributed power generation facilities

ABSTRACTThe electric system is experiencing rapid growth in the adoption of a mix of distributed renewable and fossil fuel sources, along with increasing amounts of off-grid generation. New operational regimes may have unforeseen consequences for air quality. A three-dimensional microscale chemical transport model (CTM) driven by an urban wind model was used to assess gaseous air pollutant and particulate matter (PM) impacts within ~10 km of fossil-fueled distributed power generation (DG) facilities during the early afternoon of a typical summer day in Houston, TX. Three types of DG scenarios were considered in the presence of motor vehicle emissions and a realistic urban canopy: (1) a 25-MW natural gas turbine operating at steady state in either simple cycle or combined heating and power (CHP) mode; (2) a 25-MW simple cycle gas turbine undergoing a cold startup with either moderate or enhanced formaldehyde emissions; and (3) a data center generating 10 MW of emergency power with either diesel or natural gas-fired backup generators (BUGs) without pollution controls. Simulations of criteria pollutants (NO2, CO, O3, PM) and the toxic pollutant, formaldehyde (HCHO), were conducted assuming a 2-hr operational time period. In all cases, NOx titration dominated ozone production near the source. The turbine scenarios did not result in ambient concentration enhancements significantly exceeding 1 ppbv for gaseous pollutants or over 1 µg/m3 for PM after 2 hr of emission, assuming realistic plume rise. In the case of the datacenter with diesel BUGs, ambient NO2 concentrations were enhanced by 10–50 ppbv within 2 km downwind of the source, while maximum PM impacts in the immediate vicinity of the datacenter were less than 5 µg/m3.Implications: Plausible scenarios of distributed fossil generation consistent with the electricity grid’s transformation to a more flexible and modernized system suggest that a substantial amount of deployment would be required to significantly affect air quality on a localized scale. In particular, natural gas turbines typically used in distributed generation may have minor effects. Large banks of diesel backup generators such as those used by data centers, on the other hand, may require pollution controls or conversion to natural gas-fired reciprocal internal combustion engines to decrease nitrogen dioxide pollution.

A modelling study of the atmospheric chemistry of DMS using the global model, STOCHEM-CRI

The tropospheric chemistry of dimethylsulfide (DMS) is investigated using a global three-dimensional chemical transport model, STOCHEM with the CRIv2-R5 chemistry scheme. The tropospheric distribution of DMS and its removal at the surface by OH abstraction, OH addition, NO3 oxidation, and BrO oxidation is modelled. The study shows that the lifetime and global burden of DMS is ca. 1.2 days and 98 Gg S, respectively. Inclusion of BrO oxidation resulted in a reduction of the lifetime (1.0 day) and global burden (83 Gg S) of DMS showing that this reaction is important in the DMS budget. The percentage contribution of BrO oxidation to the total removal of DMS is found to be only 7.9% that is considered a lower limit because the study does not include an inorganic source of bromine from sea-salt. BrO oxidation contributed significantly in the high latitudes of the southern hemisphere (SH). Inclusion of DMS removal by Cl2 showed that potentially a large amount of DMS is removed via this reaction specifically in the remote SH oceans, depending on the flux of Cl2 from the Southern Ocean. Model DMS levels are evaluated against measurement data from six different sites around the globe. The model predicted the correct seasonal cycle for DMS at all locations and correlated well with measurement data for most of the periods.

Global modeling of the C1–C3 alkyl nitrates using STOCHEM-CRI

The atmospheric global budget and distribution of C1–C3 alkyl nitrates have been investigated using a global three-dimensional chemistry transport model, STOCHEM-CRI. Alkyl nitrates (RONO2) are significant NOx reservoir species and the more detailed VOC oxidation mechanism (CRI v2-R5) leads to greater photochemical production. RONO2 are significant sources of NOx in regions remote from NOx sources. The study shows that the global burden and the atmospheric life-time of C1–C3 alkyl nitrates are 113 Gg and 9–10 days, respectively, which are in excellent agreement with estimates established by previous studies. The abundance of alkyl nitrates have been found to be higher in the continental atmosphere, with CH3ONO2 mixing ratios up to 20 ppt over the Amazon rainforest. Up to 15, 10, 2, and 5 ppt of modelled CH3ONO2, C2H5ONO2, n-C3H7ONO2 and i-C3H7ONO2 have been found in the northern hemisphere over regions with large anthropogenic emissions of NOx and VOCs. The combination of atmospheric production and long-range transport led to high alkyl nitrate levels at high latitudes. The model performance for C1–C3 alkyl nitrates was established using observations from nine flights and nine field campaigns. The comparison shows a tendency towards model under-prediction of the observations, particularly in the southern hemispheric marine boundary layer, possibly due to the absence of oceanic production mechanisms and air-sea exchange processes in the model. The discrepancies between model and observed seasonal cycles, especially of CH3ONO2, in both hemispheres are discussed.

Verifying Fossil-Fuel Carbon Dioxide Emissions Forecasted by an Artificial Neural Network with the GEOS-Chem Model

In this study, the authors developed an en- semble of Elman neural networks to forecast the spatial and temporal distribution of fossil-fuel emissions (ff) in 2009. The authors built and trained 29 Elman neural net- works based on the monthly average grid emission data (1979-2008) from different geographical regions. A three-dimensional global chemical transport model, God- dard Earth Observing System (GEOS)-Chem, was applied to verify the effectiveness of the networks. The results showed that the networks captured the annual increasing trend and interannual variation of ff well. The difference between the simulations with the original and predicted ff ranged from −1 ppmv to 1 ppmv globally. Meanwhile, the authors evaluated the observed and simulated north-south gradient of the atmospheric CO2 concentrations near the surface. The two simulated gradients appeared to have a similar changing pattern to the observations, with a slightly higher background CO2 concentration, ~ 1 ppmv. The results indicate that the Elman neural network is a useful tool for better understanding the spatial and tem- poral distribution of the atmospheric CO2 concentration and ff.

Evaluation of the ability of the EC tracer method to estimate secondary organic carbon

The elemental carbon (EC) tracer method has often been used to estimate the primary and secondary organic aerosol (OA) fractions using field measurements of organic carbon (OC) and EC. In this observation-based approach, EC is used as a tracer for primary OC (POC), which allows for the estimation of secondary OC (SOC). The accuracy of this approach is evaluated using concentrations generated by PMCAMx, a three-dimensional chemical transport model that simulates the complex processes leading to SOC formation (including evaporation and chemical processing of POC and chemical aging of semivolatile and intermediate volatility organics). The ratio of primary organic to elemental carbon [OC/EC]p is estimated in various locations in the Eastern United States, and is then used to calculate the primary and secondary OC concentrations. To estimate the [OC/EC]p from simulated concentrations, we use both a traditional approach and the high EC edge method, in which only values with the highest EC/OC ratio are used. Both methods perform best on a daily-averaged basis, because of the variability of the [OC/EC]p ratio during the day. The SOC estimated by the EC tracer methods corresponds to the biogenic and anthropogenic SOC formed during the oxidation of volatile organic compounds. On the other hand, the estimated POC corresponds to the sum of the fresh POC, the SOC from oxidation of the evaporated POC and the intermediate volatility organic compounds, and the OC from long-distance transport. With this correspondence, the traditional EC tracer method tends to overpredict primary OC and underpredict secondary OC for the selected urban areas in the eastern United States. The high EC edge method performs better, especially in areas where the primary contribution to OC is smaller. Despite the weaknesses of models like the one used here, the conclusions about the accuracy of observation-based methods like the EC-tracer approach should be relatively robust due to the internal consistency of the data and the approach.

Effects of olive tree branches burning emissions on PM2.5 concentrations

An olive tree branches burning emission inventory for Greece is developed based on recently measured emission factors and the spatial distribution of olive trees. A three-dimensional chemical transport model (CTM), PMCAMx, is used to estimate the corresponding impact on PM2.5 concentrations during a typical winter period. Assuming that burning of olive tree branches takes place only during days with low wind speed and without precipitation, the contribution of olive tree branches burning emissions on PM2.5 levels is more significant during the most polluted days. Increases of hourly PM2.5 exceeding 50% and locally reaching up to 150% in Crete are predicted during the most polluted periods. On a monthly-average basis, the corresponding emissions are predicted to increase PM2.5 levels up to 1.5 μg m−3 (20%) in Crete and Peloponnese, where the largest fraction of olive trees is located, and by 0.4 μg m−3 (5%) on average over Greece. OA and EC levels increase by 20% and 13% respectively on average over Greece, and up to 70% in Crete. The magnitude of the effect is quite sensitive to burning practices. Assuming that burning of olive tree branches takes place during all days results in a smaller effect of burning on PM2.5 levels (9% increase instead of 20%). These results suggest that this type of agricultural waste burning is a major source of particulate pollution in the Mediterranean countries where this practice is prevalent during winter.

Energetic particle induced intra-seasonal variability of ozone inside the Antarctic polar vortex observed in satellite data

Abstract. Measurements from 2002 to 2011 by three independent satellite instruments, namely MIPAS, SABER, and SMR on board the ENVISAT, TIMED, and Odin satellites are used to investigate the intra-seasonal variability of stratospheric and mesospheric O3 volume mixing ratio (vmr) inside the Antarctic polar vortex due to solar and geomagnetic activity. In this study, we individually analysed the relative O3 vmr variations between maximum and minimum conditions of a number of solar and geomagnetic indices (F10.7 cm solar radio flux, Ap index, ≥ 2 MeV electron flux). The indices are 26-day averages centred at 1 April, 1 May, and 1 June while O3 is based on 26-day running means from 1 April to 1 November at altitudes from 20 to 70 km. During solar quiet time from 2005 to 2010, the composite of all three instruments reveals an apparent negative O3 signal associated to the geomagnetic activity (Ap index) around 1 April, on average reaching amplitudes between −5 and −10% of the respective O3 background. The O3 response exceeds the significance level of 95% and propagates downwards throughout the polar winter from the stratopause down to ~ 25 km. These observed results are in good qualitative agreement with the O3 vmr pattern simulated with a three-dimensional chemistry-transport model, which includes particle impact ionisation.

Atmospheric fate of methyl vinyl ketone: peroxy radical reactions with NO and HO2.

First generation product yields from the OH-initiated oxidation of methyl vinyl ketone (3-buten-2-one, MVK) under both low and high NO conditions are reported. In the low NO chemistry, three distinct reaction channels are identified leading to the formation of (1) OH, glycolaldehyde, and acetyl peroxy R2a , (2) a hydroperoxide R2b , and (3) an α-diketone R2c . The α-diketone likely results from HOx-neutral chemistry previously only known to occur in reactions of HO2 with halogenated peroxy radicals. Quantum chemical calculations demonstrate that all channels are kinetically accessible at 298 K. In the high NO chemistry, glycolaldehyde is produced with a yield of 74 ± 6.0%. Two alkyl nitrates are formed with a combined yield of 4.0 ± 0.6%. We revise a three-dimensional chemical transport model to assess what impact these modifications in the MVK mechanism have on simulations of atmospheric oxidative chemistry. The calculated OH mixing ratio over the Amazon increases by 6%, suggesting that the low NO chemistry makes a non-negligible contribution toward sustaining the atmospheric radical pool.

Consistency of tropospheric ozone observations made by different platforms and techniques in the global databases

A large quantity of tropospheric ozone observations are conducted all over the world using different platforms and techniques for different purposes and goals. These observations are commonly used to derive seasonal cycles, interannual variations and long-term trends of ozone in the troposphere. In addition, they are used for comparison with three-dimensional chemistry-transport models to evaluate their performance and hence to test our current understanding of the tropospheric ozone variability. It is still challenging to provide robust tropospheric ozone trends throughout the world because of the great variability of ozone, its complex photochemical reactions, the rarity of long-term records, the diversity of measurement techniques and platforms, and the issues with data quality. In this work, we evaluated, with emphasis on the lower troposphere, the consistency of tropospheric ozone observations made by means of multiple platforms, including surface sites, sondes and regular aircraft, that are publicly available in the global databases, but excluding space-borne platforms. Concomitant observations were examined on an hourly basis (except for ±3 hours for sonde versus aircraft) for pairs of locations at less than 100-km distance. Generally, we found good agreement between sonde and surface observations. We also found that there was no need to apply any correction factor to ozonesonde observations except for Brewer–Mast sondes at Hohenpeissenberg. Because of a larger distance between the site pairs, the correlations found between the aircraft and surface measurements were poorer than those between sonde and surface measurements. However, a relatively simple wind segregation improved the agreement between the aircraft versus surface measurements. We found also that due to diurnal cycles, the sonde launching at a fixed local time led to positive or negative biases against the surface observations, suggesting that great attention should be paid to local time and diurnal variations when using ozonesonde in the analysis of seasonal cycles, long-term trends and interannual variations of lower tropospheric ozone. The comparison of surface data at Mt. Happo to regular aircraft data over Tokyo/Narita showed a relatively reasonable agreement, ensuring regionally representative ozone data sets in this region for trend analysis.

Satellite observations of stratospheric carbonyl fluoride

Abstract. The vast majority of emissions of fluorine-containing molecules are anthropogenic in nature, e.g. chlorofluorocarbons (CFCs), hydrochlorofluorocarbons (HCFCs), and hydrofluorocarbons (HFCs). These molecules slowly degrade in the atmosphere, leading to the formation of HF, COF2, and COClF, which are the main fluorine-containing species in the stratosphere. Ultimately both COF2 and COClF further degrade to form HF, an almost permanent reservoir of stratospheric fluorine due to its extreme stability. Carbonyl fluoride (COF2) is the second-most abundant stratospheric "inorganic" fluorine reservoir, with main sources being the atmospheric degradation of CFC-12 (CCl2F2), HCFC-22 (CHF2Cl), and CFC-113 (CF2ClCFCl2). This work reports the first global distributions of carbonyl fluoride in the Earth's atmosphere using infrared satellite remote-sensing measurements by the Atmospheric Chemistry Experiment Fourier transform spectrometer (ACE-FTS), which has been recording atmospheric spectra since 2004, and the Michelson Interferometer for Passive Atmospheric Sounding (MIPAS) instrument, which recorded thermal emission atmospheric spectra between 2002 and 2012. The observations reveal a high degree of seasonal and latitudinal variability over the course of a year. These have been compared with the output of SLIMCAT, a state-of-the-art three-dimensional chemical transport model. In general the observations agree well with each other, although MIPAS is biased high by as much as ~30%, and compare well with SLIMCAT. Between January 2004 and September 2010 COF2 grew most rapidly at altitudes above ~25 km in the southern latitudes and at altitudes below ~25 km in the northern latitudes, whereas it declined most rapidly in the tropics. These variations are attributed to changes in stratospheric dynamics over the observation period. The overall COF2 global trend over this period is calculated as 0.85 ± 0.34 (MIPAS), 0.30 ± 0.44 (ACE), and 0.88% year−1 (SLIMCAT).

Linking climate and air quality over Europe: effects of meteorology on PM<sub>2.5</sub> concentrations

Abstract. The effects of various meteorological parameters such as temperature, wind speed, absolute humidity, precipitation and mixing height on PM2.5 concentrations over Europe were examined using a three-dimensional chemical transport model, PMCAMx-2008. Our simulations covered three periods, representative of different seasons (summer, winter, and fall). PM2.5 appears to be more sensitive to temperature changes compared to the other meteorological parameters in all seasons. PM2.5 generally decreases as temperature increases, although the predicted changes vary significantly in space and time, ranging from −700 ng m−3 K−1 (−8% K−1) to 300 ng m−3 K−1 (7% K−1). The predicted decreases of PM2.5 are mainly due to evaporation of ammonium nitrate, while the higher biogenic emissions and the accelerated gas-phase reaction rates increase the production of organic aerosol (OA) and sulfate, having the opposite effect on PM2.5. The predicted responses of PM2.5 to absolute humidity are also quite variable, ranging from −130 ng m−3 %−1 (−1.6% %−1) to 160 ng m−3 %−1 (1.6% %−1) dominated mainly by changes in inorganic PM2.5 species. An increase in absolute humidity favors the partitioning of nitrate to the aerosol phase and increases the average PM2.5 during summer and fall. Decreases in sulfate and sea salt levels govern the average PM2.5 response to humidity during winter. A decrease of wind speed (keeping the emissions constant) increases all PM2.5 species (on average 40 ng m−3 %−1) due to changes in dispersion and dry deposition. The wind speed effects on sea salt emissions are significant for PM2.5 concentrations over water and in coastal areas. Increases in precipitation have a negative effect on PM2.5 (decreases up to 110 ng m−3 %−1) in all periods due to increases in wet deposition of PM2.5 species and their gas precursors. Changes in mixing height have the smallest effects (up to 35 ng m−3 %−1) on PM2.5 . Regarding the relative importance of each of the meteorological parameters in a changed future climate, the projected changes in precipitation are expected to have the largest impact on PM2.5 levels during all periods (changes up to 2 μg m−3 in the fall). The expected effects in future PM2.5 levels due to wind speed changes are similar in all seasons and quite close to those resulting from future precipitation changes (up to 1.4 μg m−3). The expected increases in absolute humidity in the future can lead to large changes in PM2.5 levels (increases up to 2 μg m−3) mainly in the fall due to changes in particulate nitrate levels. Despite the high sensitivity of PM2.5 levels to temperature, the small expected increases of temperature in the future will lead to modest PM2.5 changes and will not dominate the overall change.

Reassessing the photochemical production of methanol from peroxy radical self and cross reactions using the STOCHEM-CRI global chemistry and transport model

Methanol (CH3OH) is an oxygenated volatile organic compound (VOC) and one of the most abundant species present in the troposphere. The mass of CH3OH in the atmospheric reservoir, its annual mass flux from sources to sinks, and its global budget have been investigated using STOCHEM-CRI, a global three-dimensional chemistry transport model. Our study shows that the global burden of methanol is 5 Tg. The atmospheric life-time of CH3OH is found to be 6.1 days which falls within the range of previous modelling studies. The impact of peroxy radicals on the photochemical production of CH3OH has been studied and suggests that NMVOCs (non-methane Volatile Organic Compounds) are an important source of both peroxy radicals and CH3OH. The photochemical production routes of CH3OH are found to be 48 Tg/yr, which are higher than the previous studies and contributes significantly to the total global methanol sources of 287 Tg/yr. An additional CH3OH production of 8.2 Tg/yr from the reaction of methyl peroxy radicals (CH3O2) with hydroxyl radicals (OH) could be a significant additional source of CH3OH particularly over the tropical oceans which would lead to a revision of the global sources and life cycle of CH3OH.

No equatorial divide for a cleansing radical

A constraint on the global distribution of the elusive hydroxyl radical takes us a step closer towards understanding the complex, interdependent factors that control the levels of this atmospheric cleanser. See Letter p.219 The hydroxyl radical is an important atmospheric oxidant, but our knowledge of its global distribution remains imprecise, with estimates for the ratio of Northern Hemisphere to Southern Hemisphere hydroxyl radical concentration varying from 0.85 to 1.4. These authors use a three-dimensional chemistry-transport model that has been well validated for interhemispheric transport using sulphur hexafluoride measurements, to obtain an interhemispheric hydroxyl radical ratio of 0.97±0.12. This information can help improve our understanding of the fate of atmospheric pollutants and greenhouse gases.

Global and regional emissions estimates for N<sub>2</sub>O

Abstract. We present a comprehensive estimate of nitrous oxide (N2O) emissions using observations and models from 1995 to 2008. High-frequency records of tropospheric N2O are available from measurements at Cape Grim, Tasmania; Cape Matatula, American Samoa; Ragged Point, Barbados; Mace Head, Ireland; and at Trinidad Head, California using the Advanced Global Atmospheric Gases Experiment (AGAGE) instrumentation and calibrations. The Global Monitoring Division of the National Oceanic and Atmospheric Administration/Earth System Research Laboratory (NOAA/ESRL) has also collected discrete air samples in flasks and in situ measurements from remote sites across the globe and analyzed them for a suite of species including N2O. In addition to these major networks, we include in situ and aircraft measurements from the National Institute of Environmental Studies (NIES) and flask measurements from the Tohoku University and Commonwealth Scientific and Industrial Research Organization (CSIRO) networks. All measurements show increasing atmospheric mole fractions of N2O, with a varying growth rate of 0.1–0.7% per year, resulting in a 7.4% increase in the background atmospheric mole fraction between 1979 and 2011. Using existing emission inventories as well as bottom-up process modeling results, we first create globally gridded a priori N2O emissions over the 37 years since 1975. We then use the three-dimensional chemical transport model, Model for Ozone and Related Chemical Tracers version 4 (MOZART v4), and a Bayesian inverse method to estimate global as well as regional annual emissions for five source sectors from 13 regions in the world. This is the first time that all of these measurements from multiple networks have been combined to determine emissions. Our inversion indicates that global and regional N2O emissions have an increasing trend between 1995 and 2008. Despite large uncertainties, a significant increase is seen from the Asian agricultural sector in recent years, most likely due to an increase in the use of nitrogenous fertilizers, as has been suggested by previous studies.

Observed and simulated features of the CO2 diurnal cycle in the boundary layer at Beijing and Hefei, China

The mechanism of the CO2 diurnal cycle is a basis for investigating the carbon budget and its impacts on climate and environment change. Regional diurnal variations in CO2 concentration based on observations and modeling have been studied widely. However, few studies have focused on the pattern of the CO2 diurnal cycle in China. In this study, a three-dimensional global chemical transport model, Goddard Earth Observing System (GEOS)-Chem, was applied to simulate the CO2 concentration and its variation over China from 2004 to 2012. Meanwhile, we also analyzed the CO2 concentration as observed by two eddy covariance flux observation towers, one located in Beijing (39°58′N, 116°22′E) and one in Hefei (31°55′N, 117°10′E), using LI-COR 7500A infrared gas analyzers. Observations showed the amplitude of the CO2 diurnal cycle at Hefei to be larger than at Beijing, due to stronger ecological activities. GEOS-Chem successfully captured the main aspects of the diurnal cycle of the CO2 concentration in the boundary layer observed at both Beijing and Hefei. However, some discrepancies between the model and observations did exist; specifically, the model tended to underestimate the amplitude of the CO2 diurnal cycle. The data also showed that traffic emissions significantly enhanced the CO2 concentration in the boundary layer.

Particle number concentrations over Europe in 2030: the role of emissions and new particle formation

Abstract. The aerosol particle number concentration is a key parameter when estimating impacts of aerosol particles on climate and human health. We use a three-dimensional chemical transport model with detailed microphysics, PMCAMx-UF, to simulate particle number concentrations over Europe in the year 2030, by applying emission scenarios for trace gases and primary aerosols. The scenarios are based on expected changes in anthropogenic emissions of sulfur dioxide, ammonia, nitrogen oxides, and primary aerosol particles with a diameter less than 2.5 μm (PM2.5) focusing on a photochemically active period, and the implications for other seasons are discussed. For the baseline scenario, which represents a best estimate of the evolution of anthropogenic emissions in Europe, PMCAMx-UF predicts that the total particle number concentration (Ntot) will decrease by 30–70% between 2008 and 2030. The number concentration of particles larger than 100 nm (N100), a proxy for cloud condensation nuclei (CCN) concentration, is predicted to decrease by 40–70% during the same period. The predicted decrease in Ntot is mainly a result of reduced new particle formation due to the expected reduction in SO2 emissions, whereas the predicted decrease in N100 is a result of both decreasing condensational growth and reduced primary aerosol emissions. For larger emission reductions, PMCAMx-UF predicts reductions of 60–80% in both Ntot and N100 over Europe. Sensitivity tests reveal that a reduction in SO2 emissions is far more efficient than any other emission reduction investigated, in reducing Ntot. For N100, emission reductions of both SO2 and PM2.5 contribute significantly to the reduced concentration, even though SO2 plays the dominant role once more. The impact of SO2 for both new particle formation and growth over Europe may be expected to be somewhat higher during the simulated period with high photochemical activity than during times of the year with less incoming solar radiation. The predicted reductions in both Ntot and N100 between 2008 and 2030 in this study will likely reduce both the aerosol direct and indirect effects, and limit the damaging effects of aerosol particles on human health in Europe.

Sensitivity analysis of source regions to PM2.5 concentration at Fukue Island, Japan

The authors analyze the sensitivities of source regions in East Asia to PM2.5 (particulate matter with an aerodynamic diameter of ≤2.5 µm) concentration at Fukue Island located in the western part of Japan by using a regional chemical transport model with emission sensitivity simulations for the year 2010. The temporal variations in PM2.5 concentration are generally reproduced, but the absolute concentration is underestimated by the model. Chemical composition of PM2.5 in the model is compared with filter sampling data in spring; simulated sulfate, ammonium, and elemental carbon are consistent with observations, but mass concentration of particulate organic matters is underestimated. The relative contribution from each source region shows the seasonal variation, especially in summer. The contribution from central north China (105°E–124°E, 34°N–42°N) accounts for 50–60% of PM2.5 at Fukue Island except in summer; it significantly decreases in summer (18%). Central south China (105°E–123°E, 26°N–34°N) has the relative contribution of 15–30%. The contribution from the Korean Peninsula is estimated at about 10% except in summer. The domestic contribution accounts for about 7% in spring and autumn and increases to 19% in summer. We also estimate the relative contribution to daily average concentration in high PM2.5 days (>35 μg m−3). Central north China has a significant contribution of 60–70% except in summer. The relative contribution from central south China is estimated at 46% in summer and about 30% in the other seasons. The contributions from central north and south China on high PM2.5 days are generally larger than those of their seasonal mean contributions. The domestic contribution is smaller than the seasonal mean value in every season; it is less than 10% even in summer. These model results suggest that foreign anthropogenic sources have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.Implications: The contribution from several source regions in East Asia to PM2.5 concentration at Fukue Island, a remote island located in the western part of Japan and close to the Asian continent, is estimated using a three-dimensional chemical transport model. The model results suggest that PM2.5 that is attributed to foreign anthropogenic sources have a larger contribution than that of domestic pollution and have a substantial impact on attainment of the atmospheric environmental standard of Japan at Fukue Island.

Dust vertical profile impact on global radiative forcing estimation using a coupled chemical-transport–radiative-transfer model

Abstract. Atmospheric mineral dust particles exert significant direct radiative forcings and are important drivers of climate and climate change. We used the GEOS-Chem global three-dimensional chemical transport model (CTM) coupled with the Fu-Liou-Gu (FLG) radiative transfer model (RTM) to investigate the dust radiative forcing and heating rate based on different vertical profiles for April 2006. We attempt to actually quantify the sensitivities of radiative forcing to dust vertical profiles, especially the discrepancies between using realistic and climatological vertical profiles. In these calculations, dust emissions were constrained by observations of aerosol optical depth (AOD). The coupled calculations utilizing a more realistic dust vertical profile simulated by GEOS-Chem minimize the physical inconsistencies between 3-D CTM aerosol fields and the RTM. The use of GEOS-Chem simulated vertical profile of dust extinction, as opposed to the FLG prescribed vertical profile, leads to greater and more spatially heterogeneous changes in the estimated radiative forcing and heating rate produced by dust. Both changes can be attributed to a different vertical structure between dust and non-dust source regions. Values of the dust vertically resolved AOD per grid level (VRAOD) are much larger in the middle troposphere, though smaller at the surface when the GEOS-Chem simulated vertical profile is used, which leads to a much stronger heating rate in the middle troposphere. Compared to the FLG vertical profile, the use of GEOS-Chem vertical profile reduces the solar radiative forcing at the top of atmosphere (TOA) by approximately 0.2–0.25 W m−2 over the African and Asian dust source regions. While the Infrared (IR) radiative forcing decreases 0.2 W m−2 over African dust belt, it increases 0.06 W m−2 over the Asian dust belt when the GEOS-Chem vertical profile is used. Differences in the solar radiative forcing at the surface between the use of the GEOS-Chem and FLG vertical profiles are most significant over the Gobi desert with a value of about 1.1 W m−2. The radiative forcing effect of dust particles is more pronounced at the surface over the Sahara and Gobi deserts by using FLG vertical profile, while it is less significant over the downwind area of Eastern Asia.