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The Superconducting Submillimeter-Wave Limb-Emission Sounder (SMILES) on board the International Space Station observed ozone in the stratosphere with high precision from October 2009 to April 2010. Although SMILES measurements only cover latitudes from 38° S to 65° N, the combination of data assimilation methods and an isentropic advection model allows us to quantify the ozone depletion in the 2009/2010 Arctic polar winter by making use of the instability of the polar vortex in the northern hemisphere. Ozone data from both SMILES and Odin/SMR (Sub-Millimetre Radiometer) for the winter were assimilated into the Dynamical Isentropic Assimilation Model for OdiN Data (DIAMOND). DIAMOND is an off-line wind-driven transport model on isentropic surfaces. Wind data from the operational analyses of the European Centre for Medium- Range Weather Forecasts (ECMWF) were used to drive the model. In this study, particular attention is paid to the cross isentropic transport of the tracer in order to accurately assess the ozone loss. The assimilated SMILES ozone fields agree well with the limitation of noise induced variability within the SMR fields despite the limited latitude coverage of the SMILES observations. Ozone depletion has been derived by comparing the ozone field acquired by sequential assimilation with a passively transported ozone field initialized on 1 December 2009. Significant ozone loss was found in different periods and altitudes from using both SMILES and SMR data: The initial depletion occurred at the end of January below 550 K with an accumulated loss of 0.6–1.0 ppmv (approximately 20%) by 1 April. The ensuing loss started from the end of February between 575 K and 650 K. Our estimation shows that 0.8–1.3 ppmv (20–25 %) of O<sub>3</sub> has been removed at the 600 K isentropic level by 1 April in volume mixing ratio (VMR).
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In order to improve our understanding of air quality in Southeast Asia, the anthropogenic emissions inventory must be well represented. In this work, we apply different anthropogenic emission inventories in the Weather Research and Forecasting Model with Chemistry (WRF-Chem) version 3.3 using Model for Ozone and Related Chemical Tracers (MOZART) gas-phase chemistry and Global Ozone Chemistry Aerosol Radiation and Transport (GOCART) aerosols to examine the differences in predicted carbon monoxide (CO) and ozone (O<sub>3</sub>) surface mixing ratios for Southeast Asia in March and December 2008. The anthropogenic emission inventories include the Reanalysis of the TROpospheric chemical composition (RETRO), the Intercontinental Chemical Transport Experiment-Phase B (INTEX-B), the MACCity emissions (adapted from the Monitoring Atmospheric Composition and Climate and megacity Zoom for the Environment projects), the Southeast Asia Composition, Cloud, Climate Coupling Regional Study (SEAC4RS) emissions, and a combination of MACCity and SEAC4RS emissions. Biomass-burning emissions are from the Fire Inventory from the National Center for Atmospheric Research (NCAR) (FINNv1) model. WRF-Chem reasonably predicts the 2 m temperature, 10 m wind, and precipitation. In general, surface CO is underpredicted by WRF-Chem while surface O<sub>3</sub> is overpredicted. The NO<sub>2</sub> tropospheric column predicted by WRF-Chem has the same magnitude as observations, but tends to underpredict the NO<sub>2</sub> column over the equatorial ocean and near Indonesia. Simulations using different anthropogenic emissions produce only a slight variability of O<sub>3</sub> and CO mixing ratios, while biomass-burning emissions add more variability. The different anthropogenic emissions differ by up to 30% in CO emissions, but O<sub>3</sub> and CO mixing ratios averaged over the land areas of the model domain differ by ~4.5% and ~8%, respectively, among the simulations. Biomass-burning emissions create a substantial increase for both O<sub>3</sub> and CO by ~29% and ~16%, respectively, when comparing the March biomass-burning period to the December period with low biomass-burning emissions. The simulations show that none of the anthropogenic emission inventories are better than the others for predicting O<sub>3</sub> surface mixing ratios. However, the simulations with different anthropogenic emission inventories do differ in their predictions of CO surface mixing ratios producing variations of ~30% for March and 10–20% for December at Thai surface monitoring sites.
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Recently, methacrylic acid epoxide (MAE) has been proposed as a precursor to an important class of isoprene-derived compounds found in secondary organic aerosol (SOA): 2-methylglyceric acid (2-MG) and a set of oligomers, nitric acid esters, and sulfuric acid esters related to 2-MG. However, the specific chemical mechanisms by which MAE could form these compounds have not been previously studied with experimental methods. In order to determine the relevance of these processes to atmospheric aerosol, MAE and 2-MG have been synthesized and a series of bulk solution-phase experiments aimed at studying the reactivity of MAE using nuclear magnetic resonance (NMR) spectroscopy have been performed. The present results indicate that the acid-catalyzed MAE reaction is more than 600 times slower than a similar reaction of an important isoprene-derived epoxide, but is still expected to be kinetically feasible in the atmosphere on more acidic SOA. The specific mechanism by which MAE leads to oligomers was identified, and the reactions of MAE with a number of atmospherically relevant nucleophiles were also investigated. Because the nucleophilic strengths of water, sulfate, alcohols (including 2-MG), and acids (including MAE and 2-MG) in their reactions with MAE were found to be of similar magnitudes, it is expected that a diverse variety of MAE + nucleophile product species may be formed on ambient SOA. Thus, the results indicate that epoxide chain reaction oligomerization will be limited by the presence of high concentrations of non-epoxide nucleophiles (such as water); this finding is consistent with previous environmental chamber investigations of the relative humidity dependence of 2-MG-derived oligomerization processes and suggests that extensive oligomerization may not be likely on ambient SOA because of other competitive MAE reaction mechanisms.
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Increases in observed atmospheric concentrations of the long-lived greenhouse gas nitrous oxide (N<sub>2</sub>O) have been well documented. However, information on event-related instantaneous emissions during fertilizer applications is lacking. With the development of fast-response N<sub>2</sub>O analyzers, the eddy covariance (EC) technique can be used to gather instantaneous measurements of N<sub>2</sub>O concentrations to quantify the exchange of nitrogen between the soil and atmosphere. The objectives of this study were to evaluate the performance of a new EC system, to measure the N<sub>2</sub>O flux with the system, and finally to examine relationships of the N<sub>2</sub>O flux with soil temperature, soil moisture, precipitation, and fertilization events. An EC system was assembled with a sonic anemometer and a fast-response N<sub>2</sub>O analyzer (quantum cascade laser spectrometer) and applied in a cornfield in Nolensville, Tennessee during the 2012 corn growing season (4 April–8 August). Fertilizer amounts totaling 217 kg N ha<sup>−1</sup> were applied to the experimental site. Results showed that this N<sub>2</sub>O EC system provided reliable N<sub>2</sub>O flux measurements. The cumulative emitted N<sub>2</sub>O amount for the entire growing season was 6.87 kg N<sub>2</sub>O-N ha<sup>−1</sup>. Seasonal fluxes were highly dependent on soil moisture rather than soil temperature. This study was one of the few experiments that continuously measured instantaneous, high-frequency N<sub>2</sub>O emissions in crop fields over a growing season of more than 100 days.
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We assess the potential of the water-soluble fraction of atmospheric fine aerosols in the southeastern United States to generate reactive oxygen species (ROS) and identify major ROS-associated emission sources. ROS-generation potential of particles was quantified by the dithiothreitol (DTT) assay and involved analysis of fine particulate matter (PM) extracted from high-volume quartz filters (23 h integrated samples) collected at various sites in different environmental settings in the southeast, including three urban-Atlanta sites, in addition to a rural site. Paired sampling was conducted with one fixed site in Atlanta (Jefferson Street), representative of the urban environment, with the others rotating among different sites, for ~250 days between June 2012 and September 2013 (<i>N</i>=483). A simple linear regression between the DTT activity and aerosol chemical components revealed strong associations between PM ROS-generation potential and secondary organic aerosol (WSOC – water-soluble organic carbon) in summer, and biomass burning markers in winter. Redox-active metals were also somewhat correlated with the DTT activity, but mostly at urban and roadside sites. Positive matrix factorization (PMF) was applied to apportion the relative contribution of various sources to the ROS-generation potential of water-soluble PM<sub>2.5</sub> in urban Atlanta. PMF showed that vehicular emissions contribute uniformly throughout the year (12–25%), while secondary oxidation processes dominated the DTT activity in summer (46%) and biomass burning in winter (47%). Road dust was significant only during drier periods (~12% in summer and fall). Source apportionment by chemical mass balance (CMB) was reasonably consistent with PMF, but with higher contribution from vehicular emissions (32%). Given the spatially large data set of PM sampled over an extended period, the study reconciles the results from previous work that showed only region- or season-specific aerosol components or sources contributing to PM ROS activity, possibly due to smaller sample sizes. The ubiquitous nature of the major sources of PM-associated ROS suggests widespread population exposures to aerosol components that have the ability to catalyze the production of oxidants in vivo.
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For the investigation of megacity emission plume characteristics mobile aerosol and trace gas measurements were carried out in the greater Paris region in July 2009 and January–February 2010 within the EU FP7 MEGAPOLI project (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation). The deployed instruments measured physical and chemical properties of sub-micron aerosol particles, gas phase constituents of relevance for urban air pollution studies and meteorological parameters. The emission plume was identified based on fresh pollutant (e.g., particle-bound polycyclic aromatic hydrocarbons, black carbon, CO<sub>2</sub> and NO<sub>x</sub>) concentration changes in combination with wind direction data. The classification into megacity influenced and background air masses allowed a characterization of the emission plume during summer and winter environmental conditions. On average, a clear increase of fresh pollutant concentrations in plume compared to background air masses was found for both seasons. For example, an average increase of 190% (+ 8.8 ng m<sup>−3</sup>) in summer and of 130% (+ 18.1 ng m<sup>−3</sup>) in winter was found for particle-bound polycyclic aromatic hydrocarbons in plume air masses. The aerosol particle size distribution in plume air masses was influenced by nucleation and growth due to coagulation and condensation in summer, while in winter only the latter process (i.e., particle growth) seemed to be initiated by urban pollution. The observed distribution of fresh pollutants in the emission plume – its cross sectional Gaussian-like profile and the exponential decrease of pollutant concentrations with increasing distance to the megacity – are in agreement with model results. Differences between model and measurements were found for plume center location, plume width and axial plume extent. In general, dilution was identified as the dominant process determining the axial variations within the Paris emission plume. For in-depth analysis of transformation processes occurring in the advected plume, simultaneous measurements at a suburban measurement site and a stationary site outside the metropolitan area using the mobile laboratory have proven to be most useful. Organic aerosol oxidation was observed in summer, while in winter transformation processes seemed to occur at a slower rate.
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A parcel and a one-dimensional model are used to investigate the temperature dependence of ice crystal number density. The number of ice crystals initially formed in a cold cirrus cloud is very sensitive to the nucleation mechanism and the detailed history of cooling rates during nucleation. A possible small spread in the homogeneous freezing threshold due to varying particle composition is identified as a sensitive nucleation parameter. In a parcel model, the slow growth rate of ice crystals at low temperatures inherently leads to a strong increase in ice number density at low temperatures. This temperature dependence is not observed. The model temperature dependence occurs for a wide range of assumptions and for either homogeneous or, less strongly, heterogeneous freezing. However, the parcel model also shows that random temperature fluctuations result in an extremely wide range of ice number densities. A one-dimensional model is used to show that the rare temperature trajectories resulting in the lowest number densities are disproportionately important. Low number density ice crystals sediment and influence a large volume of air. When such fall streaks are included, the ice number becomes less sensitive to the details of nucleation than it is in a parcel model. The one-dimensional simulations have a more realistic temperature dependence than the parcel mode. The one-dimensional model also produces layers with vertical dimensions of meters even if the temperature forcing has a much broader vertical wavelength. Unlike warm clouds, cirrus clouds are frequently surrounded by supersaturated air. Sedimentation through supersaturated air increases the importance of any process that produces small numbers of ice crystals. This paper emphasizes the relatively rare temperature trajectories that produce the fewest crystals. Other processes are heterogeneous nucleation, sedimentation from the very bottom of clouds, annealing of disordered to hexagonal ice, and entrainment.
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We report a study of changes in air quality due to emission reductions using the chemical transport model CAMx. The model domain includes all of Europe with a nested domain over Switzerland. The model simulations were performed with emissions for 1990 (the reference year for the Gothenburg Protocol), 2005 (the reference year for the revised Gothenburg Protocol), 2006 (for model validation) and 2020 (the target year for the revised Gothenburg Protocol) using three emission scenarios prepared by IIASA/GAINS. Changes in ozone, particulate matter and nitrogen deposition are the central theme of the study. <br><br> The modelled relative changes in the annual average PM<sub>2.5</sub> concentrations between 1990 and 2005 look reasonable based on various PM<sub>10</sub> and PM<sub>2.5</sub> observations in the past. The results obtained in this study suggest that annual mean concentrations of PM<sub>2.5</sub> decreased by about 20–50% in Europe. Simulations using the baseline scenario (BL 2020) suggest that PM<sub>2.5</sub> concentrations in 2020 will be about 30% lower than those in 2005. The largest predicted decrease in PM<sub>2.5</sub>, based on the MTFR (maximum technically feasible reduction) scenario, was about 60% and was located mainly in the eastern part of Europe. <br><br> In the case of ozone, both model results and measurements show an increase in the mean ozone mixing ratios between 1990 and 2005. The observations, however, suggest a larger increase, indicating the importance of background ozone levels. Although emission reductions caused a decrease in peak ozone values, average ozone levels in polluted regions increased due to reduced titration with nitric oxide (NO). This caused a change in the frequency distribution of ozone. Model simulations using emission scenarios for 2020 suggest that annual average ozone mixing ratios will continue to increase. Changes in the levels of the damage indicators AOT40 for forests and SOMO35 are reported as well. <br><br> The model results suggest that nitrogen deposition has decreased by 10–30% in the eastern part of Europe since 1990, while it has increased by about 20% in the Iberian Peninsula. The decrease is mainly due to the deposition of oxidized nitrogen species, whereas deposition of reduced nitrogen compounds increased. In Switzerland, nitrogen deposition is larger in the northern part of the Alps, where ammonia emissions are the highest. Applying the baseline scenario, we found that the deposition of oxidized nitrogen compounds will have decreased by a further 40% by 2020, whereas deposition of reduced species will continue to increase. This will lead to a 10–20% decrease in the total nitrogen deposition in most of the model domain, with a 10% increase in the eastern part of Europe.
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Observations and simple theoretical arguments suggest that the Northern Hemisphere (NH) stratospheric polar vortex is stronger in winters following major volcanic eruptions. However, recent studies show that climate models forced by prescribed volcanic aerosol fields fail to reproduce this effect. We investigate the impact of volcanic aerosol forcing on stratospheric dynamics, including the strength of the NH polar vortex, in ensemble simulations with the Max Planck Institute Earth System Model. The model is forced by four different prescribed forcing sets representing the radiative properties of stratospheric aerosol following the 1991 eruption of Mt. Pinatubo: two forcing sets are based on observations, and are commonly used in climate model simulations, and two forcing sets are constructed based on coupled aerosol–climate model simulations. For all forcings, we find that simulated temperature and zonal wind anomalies in the NH high latitudes are not directly impacted by anomalous volcanic aerosol heating. Instead, high-latitude effects result from enhancements in stratospheric residual circulation, which in turn result, at least in part, from enhanced stratospheric wave activity. High-latitude effects are therefore much less robust than would be expected if they were the direct result of aerosol heating. Both observation-based forcing sets result in insignificant changes in vortex strength. For the model-based forcing sets, the vortex response is found to be sensitive to the structure of the forcing, with one forcing set leading to significant strengthening of the polar vortex in rough agreement with observation-based expectations. Differences in the dynamical response to the forcing sets imply that reproducing the polar vortex responses to past eruptions, or predicting the response to future eruptions, depends on accurate representation of the space–time structure of the volcanic aerosol forcing.
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We analyzed the measurements of ozone (O<sub>3</sub>) and its precursors made at rural/suburban sites downwind of four large Chinese cities – Beijing, Shanghai, Guangzhou and Lanzhou, to elucidate their pollution characteristics, regional transport, in situ production, and impacts of heterogeneous processes. The same measurement techniques and observation-based model were used to minimize uncertainties in comparison of the results due to difference in methodologies. All four cities suffered from serious O<sub>3</sub> pollution but showed different precursor distributions. The model-calculated in situ O<sub>3</sub> production rates were compared with the observed change rates to infer the relative contributions of on-site photochemistry and transport. At the rural site downwind of Beijing, export of the well-processed urban plumes contributed to the extremely high O<sub>3</sub> levels (up to an hourly value of 286 ppbv), while the O<sub>3</sub> pollution observed at suburban sites of Shanghai, Guangzhou and Lanzhou was dominated by intense in situ production. The O<sub>3</sub> production was in a volatile organic compound (VOC)-limited regime in both Shanghai and Guangzhou, and a NO<sub>x</sub>-limited regime in Lanzhou. The key VOC precursors are aromatics and alkenes in Shanghai, and aromatics in Guangzhou. The potential impacts on O<sub>3</sub> production of several heterogeneous processes, namely, hydrolysis of dinitrogen pentoxide (N<sub>2</sub>O<sub>5</sub>), uptake of hydro peroxy radical (HO<sub>2</sub>) on particles and surface reactions of NO<sub>2</sub> forming nitrous acid (HONO), were assessed. The analyses indicate the varying and considerable impacts of these processes in different areas of China depending on the atmospheric abundances of aerosol and NO<sub>x</sub>, and suggest the urgent need to better understand these processes and represent them in photochemical models.
