ALBERT

Description: Hourly concentrations of inorganic salts (ions) and carbonaceous material in fine aerosols (aerodynamic diameter, A.D.

Description: Simulations with the chemistry transport model CHIMERE are compared to measurements performed during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) summer campaign in the Greater Paris region in July 2009. The volatility-basis-set approach (VBS) is implemented into this model, taking into account the volatility of primary organic aerosol (POA) and the chemical aging of semi-volatile organic species. Organic aerosol is the main focus and is simulated with three different configurations with a modified treatment of POA volatility and modified secondary organic aerosol (SOA) formation schemes. In addition, two types of emission inventories are used as model input in order to test the uncertainty related to the emissions. Predictions of basic meteorological parameters and primary and secondary pollutant concentrations are evaluated, and four pollution regimes are defined according to the air mass origin. Primary pollutants are generally overestimated, while ozone is consistent with observations. Sulfate is generally overestimated, while ammonium and nitrate levels are well simulated with the refined emission data set. As expected, the simulation with non-volatile POA and a single-step SOA formation mechanism largely overestimates POA and underestimates SOA. Simulation of organic aerosol with the VBS approach taking into account the aging of semi-volatile organic compounds (SVOC) shows the best correlation with measurements. High-concentration events observed mostly after long-range transport are well reproduced by the model. Depending on the emission inventory used, simulated POA levels are either reasonable or underestimated, while SOA levels tend to be overestimated. Several uncertainties related to the VBS scheme (POA volatility, SOA yields, the aging parameterization), to emission input data, and to simulated OH levels can be responsible for this behavior. Despite these uncertainties, the implementation of the VBS scheme into the CHIMERE model allowed for much more realistic organic aerosol simulations for Paris during summertime. The advection of SOA from outside Paris is mostly responsible for the highest OA concentration levels. During advection of polluted air masses from northeast (Benelux and Central Europe), simulations indicate high levels of both anthropogenic and biogenic SOA fractions, while biogenic SOA dominates during periods with advection from Southern France and Spain.

Description: Hourly concentrations of inorganic salts (ions) and carbonaceous material in fine aerosols (aerodynamic diameter, A.D. 15 μg m−3 were characterized by air masses of continental (North-Western Europe) origin and chemical composition made by 75% of ions. By contrast, periods with clean marine air masses have shown the lowest PM2.5 concentrations (typically of about 10 μg m−3); carbonaceous aerosols contributing for most of this mass (typically 75%). In order to better discriminate between local and continental contributions to the observed chemical composition and concentrations of PM2.5 over Paris, a comparative study was performed between this time-resolved dataset and the outputs of a chemistry transport model (CHIMERE), showing a relatively good capability of the model to reproduce the time-limited intense maxima observed in the field for PM2.5 and ion species. Different model scenarios were then investigated switching off local and European (North-Western and Central) emissions. Results of these scenarios have clearly shown that most of the ions observed over Paris during polluted periods, were either transported or formed in-situ from gas precursors transported from Northern Europe. On the opposite, long-range transport from Europe appeared to weakly contribute to the levels of carbonaceous aerosols observed over Paris. The model failed to properly account for the concentration levels and variability of secondary organic aerosols (SOA) determined experimentally by the EC-tracer method. The abundance of SOA (relatively to organic aerosol, OA) was as much as 75%, showing a weak dependence on air masses origin. Elevated SOA/OA ratios were also observed for air masses having residence time above ground of less than 10 h, suggesting intense emissions and/or photochemical processes leading to rapid formation of secondary organic aerosols.

Description: Results of the chemistry transport model CHIMERE are compared with the measurements performed during the MEGAPOLI summer campaign in the Greater Paris Region in July, 2009. The Volatility-Basis-Set approach (VBS) is implemented into this model, taking into account the volatility of primary organic aerosol (POA) and the chemical aging of semi-volatile organic species. Organic aerosol is the main focus and is simulated with three different configurations related to the volatility of POA and the scheme of secondary organic aerosol (SOA) formation. In addition, two types of emission inventories are used as model input in order to test the uncertainty related to the emissions. Predictions of basic meteorological parameters and primary and secondary pollutant concentrations are evaluated and four pollution regimes according to the air mass origin are defined. Primary pollutants are generally overestimated, while ozone is consistent with observations. Sulfate is generally overestimated, while ammonium and nitrate levels are well simulated with the refined emission data set. As expected, the simulation with non-volatile POA and a single-step SOA formation mechanism largely overestimates POA and underestimates SOA. Simulation of organic aerosol with the VBS approach taking into account the aging of semi-volatile organic compounds (SVOC) shows the best correlation with measurements. All observed high concentration events are reproduced by the model mostly after long range transport, indicating that long range transport of SOA to Paris is well reproduced. Depending on the emission inventory used, simulated POA levels are either reasonable or underestimated, while SOA levels tend to be overestimated. Several uncertainties related to the VBS scheme (POA volatility, SOA yields, the aging parameterization), to emission input data, and to simulated OH levels can be responsible for this behavior. Despite these uncertainties, the implementation of the VBS scheme into the CHIMERE model allowed for much more realistic organic aerosol simulations for Paris during summer time. The advection of SOA from outside Paris is mostly responsible for the highest OA concentration levels. During advection of polluted air masses from north-east (Benelux and Central Europe), simulations indicate high levels of both anthropogenic and biogenic SOA fractions, while biogenic SOA dominates during days with advection from Southern France and Spain.

Description: Aerosol simulations in chemistry transport models (CTMs) still suffer from numerous uncertainties, and diagnostic evaluations are required to point out major error sources. This paper presents an original approach to evaluate CTMs based on local and imported contributions in a large megacity rather than urban background concentrations. The study is applied to the CHIMERE model in the Paris region (France) and considers the fine particulate matter (PM2.5) and its main chemical constituents (elemental and organic carbon, nitrate, sulfate and ammonium), for which daily measurements are available during a whole year at various stations (PARTICULES project). Back-trajectory data are used to locate the upwind station, from which the concentration is identified as the import, the local production being deduced from the urban concentration by subtraction. Uncertainties on these contributions are quantified. Small biases in urban background PM2.5 simulations (bias of +16%) hide significant error compensations between local and advected contributions, as well as in PM2.5 chemical compounds. In particular, winter time organic matter (OM) imports appear strongly underestimated while local OM and elemental carbon (EC) production is overestimated all along the year. Erroneous continental wood burning emissions and missing secondary organic aerosol (SOA) pathways may explain errors on advected OM, while the carbonaceous compounds is likely to be related to errors in emissions and dynamics. A statistically significant local formation of nitrate is also highlighted from observations, but missed by the model. Together with the overestimation of nitrate imports, it leads to a bias of +51% on the local PM2.5 contribution. Such an evaluation finally gives more detailed insights on major gaps in current CTMs on which future efforts are needed.

Description: Ozone and PM2.5 concentrations over the city of Paris are modeled with the CHIMERE air-quality model at 4 km × 4 km horizontal resolution for two future emission scenarios. High-resolution (1 km × 1 km) emission projection until 2020 for the greater Paris region is developed by local experts (AIRPARIF) and is further extended to year 2050 based on regional scale emission projections developed by the Global Energy Assessment. Model evaluation is performed based on a 10 yr control simulation. Ozone is in very good agreement with measurements while PM2.5 is underestimated by 20% over the urban area mainly due to a large wet bias in wintertime precipitation. A significant increase of maximum ozone relative to present time levels over Paris is modeled under the "business as usual" scenario (+7 ppb) while a more optimistic mitigation scenario leads to moderate ozone decrease (−3.5 ppb) in year 2050. These results are substantially different to previous regional scale projections where 2050 ozone is found to decrease under both future scenarios. A sensitivity analysis showed that this difference is due to the fact that ozone formation over Paris at the current, urban scale study, is driven by VOC-limited chemistry, whereas at the regional scale ozone formation occurs under NOx-sensitive conditions. This explains why the sharp NOx reductions implemented in the future scenarios have a different effect on ozone projections at different scales. In rural areas projections at both scales yield similar results showing that the longer time-scale processes of emission transport and ozone formation are less sensitive to model resolution. PM2.5 concentrations decrease by 78% and 89% under "business as usual" and "mitigation" scenarios respectively compared to present time period. The reduction is much more prominent over the urban part of the domain due to the effective reductions of road transport and residential emissions resulting in the smoothing of the large urban increment modelled in the control simulation.

Description: While previous research helped to identify and prioritize the sources of error in air-quality modeling due to anthropogenic emissions and spatial scale effects our knowledge is limited on how these uncertainties affect climate forced air-quality assessments. Using as reference a 10 yr model simulation over the greater Paris (France) area at 4 km resolution and anthropogenic emissions from a 1 km resolution bottom-up inventory, through several tests we estimate the sensitivity of modeled ozone and PM2.5 concentrations to different potentially influential factors with a particular interest over the urban areas. These factors include the model horizontal and vertical resolution, the meteorological input from a climate model and its resolution, the use of a top-down emission inventory, the resolution of the emissions input and the post-processing coefficients used to derive the temporal, vertical and chemical split of emissions. We show that urban ozone displays moderate sensitivity to the resolution of emissions (~8%), the post-processing method (6.5%) and model resolution (~5) while annual PM2.5 levels are particularly sensitive to changes in their primary emissions (~32%) and the resolution of the emission inventory (~24%) while model horizontal and vertical resolution are of little effect. In addition we use the results of these sensitivities to explain and quantify the discrepancy between a coarse (~50 km) and a fine (4 km) resolution simulation over the urban area. We show that the ozone bias of the coarse run (+9 ppb) is reduced by ~40% by adopting a higher resolution emission inventory, by 25% by using a post-processing technique based on the local inventory (same improvement is obtained by increasing model horizontal resolution) and by 10% by adopting the annual emission totals of the local inventory. The bias on PM2.5 follows a more complex pattern with the positive bias associated to the coarse run (+3.6 μg m3) increasing or decreasing depending on the type of the refinement. We conclude that in the case of fine particles the coarse simulation cannot selectively incorporate local scale features in order to reduce model error.

Description: Secondary inorganic compounds represent a major fraction of fine aerosol in the Paris megacity. The thermodynamics behind their formation is now relatively well constrained, but due to sparse direct measurements of their precursors (in particular NH3 and HNO3), uncertainties remain on their concentrations and variability as well as the formation regime of ammonium nitrate (in terms of limited species, among NH3 and HNO3) in urban environments such as Paris. This study presents the first urban background measurements of both inorganic aerosol compounds and their gaseous precursors during several months within the city of Paris. Intense agriculture-related NH3 episodes are observed in spring/summer while HNO3 concentrations remain relatively low, even during summer, which leads to a NH3-rich regime in Paris. The local formation of ammonium nitrate within the city appears low, despite high NOx emissions. The dataset is also used to evaluate the CHIMERE chemistry-transport model (CTM). Interestingly, the rather good results obtained on ammonium nitrates hide significant errors on gaseous precursors (e.g. mean bias of −75 and +195 % for NH3 and HNO3, respectively). It thus leads to a mis-representation of the nitrate formation regime through a highly underestimated Gas Ratio metric (introduced by Ansari and Pandis, 1998) and a much higher sensitivity of nitrate concentrations to ammonia changes. Several uncertainty sources are investigated, pointing out the importance of better assessing both NH3 emissions and OH concentrations in the future. These results finally remind the caution required in the use of CTMs for emission scenario analysis, highlighting the importance of prior diagnostic and dynamic evaluations.

Description: Within the framework of air quality studies at the megacity scale, highly time-resolved volatile organic compounds (C2–C8) measurements were performed in downtown Paris (urban background sites) from January to November 2010. This unique dataset included non-methane hydrocarbons (NMHCs) and aromatic/oxygenated species (OVOCs) measured by a GC-FID (Gas Chromatograph with a Flame Ionization Detector) and a PTR-MS (Proton Transfer Reaction – Mass Spectrometer), respectively. The current study presents the seasonal variability of atmospheric VOCs being monitored in the French megacity and their various associated emission sources. Clear seasonal and diurnal patterns differed from one VOC to another as the result of their different origins and the influence of environmental parameters (solar radiation, temperature). Source Apportionment (SA) was comprehensively conducted using a multivariate mathematical receptor modeling. The United States Environmental Protection Agency's Positive Matrix Factorization tool (US EPA, PMF) was used to apportion and quantify ambient VOC concentrations into six different sources. The modeled source profiles were identified from near-field observations (measurements from three distinct emission sources: inside a highway tunnel, at a fireplace and from a domestic gas flue, with hence a specific focus on road-traffic, wood burning activities and natural gas emissions) and hydrocarbon profiles reported in the literature. The reconstructed VOC sources were cross-validated using independent tracers such as inorganic gases (NO, NO2, CO), black carbon (BC) and meteorological data (temperature). The largest contributors to the predicted VOC concentrations were traffic-related activities (including motor vehicle exhaust, 15 % of the total mass on the annual average, and gasoline evaporation, 10 %), with the remaining emissions from natural gas and background (23 %), solvents use (20 %), wood burning (18 %) and a biogenic source (15 %). An important finding of this work is the significant contribution from wood burning, especially in winter, where it could represent up to ~ 50 % of the total mass of VOCs. Biogenic emissions also surprisingly contributed up to ~ 30 % in summer (due to the dominating weight of OVOCs in this source). Finally, the mixed natural gas and background source exhibited a high contribution in spring (35 %, when continental air influences were observed) and in autumn (23 %, for home heating consumption).

Description: Aerosol simulations in chemistry transport models (CTMs) still suffer from numerous uncertainties, and diagnostic evaluations are required to point out major error sources. This paper presents an original approach to evaluate CTMs based on local and imported contributions in a large megacity rather than urban background concentrations. The study is applied to the CHIMERE model in the Paris region (France) and considers the fine particulate matter (PM2.5) and its main chemical constituents (elemental and organic carbon, nitrate, sulfate and ammonium), for which daily measurements are available during a whole year at various stations (PARTICULES project). Back-trajectory data are used to locate the upwind station, from which the concentration is identified as the import, the local production being deduced from the urban concentration by subtraction. Uncertainties on these contributions are quantified. Small biases in urban background PM2.5 simulations (bias of +16%) hide significant error compensations between local and advected contributions, as well as in PM2.5 chemical compounds. In particular, wintertime OM imports appear strongly underestimated while local OM and EC production are overestimated all along the year. Erroneous continental woodburning emissions and missing SOA pathways may explain errors on advected OM, while carbonaceous compounds overestimation is likely to be related to errors in emissions and dynamics. A statistically significant local formation of nitrate is also highlighted from observations, but missed by the model. Together with the overestimation of nitrate imports, it leads to a bias of +51% on the local PM2.5 contribution. Such an evaluation finally gives more detailed insights on major gaps in current CTMs on which future efforts are needed.