Recent laboratory studies indicated that a photo‐induced heterogeneous reaction of ozone on the surface of aerosol containing humic like substances (HULIS) has the potential to affect the ozone ...budget in biomass burning plumes. To evaluate atmospheric significance of such heterogeneous light induced ozone loss, this process has been taken into account in the simulation of the extreme air pollution episode in the Moscow region during the 2010 mega fire event in western Russia. Results of the numerical experiments performed with the CHIMERE chemistry transport model indicate that photo induced removal of ozone could lead to significant (reaching several tens of percent) episodic decrease of the ozone concentration. The simulations also show that while wildfires provide reactive surface for the considered reaction, they strongly inhibit the photo‐induced heterogeneous ozone loss by attenuating actinic fluxes through the “shielding” aerosol effect. The present results are calling for additional experimental and modelling studies.
Key Points
Photo induced ozone loss on biomass burning aerosol is a significant process
Aerosol is a self‐inhibiting agent of the heterogeneous light induced ozone loss
Uncertainties in reactivity of biomass burning aerosol call for new studies
Well documented adverse health effects of airborne particulate matter (PM) stimulate intensive research aimed at understanding and forecasting its behaviour. Forecasting of PM levels is commonly ...performed with either statistical or deterministic chemistry-transport models (CTM). In this study, we investigate advantages of combining deterministic and statistical approaches for PM10 forecasting over Europe one day ahead. The proposed procedure involves statistical postprocessing of deterministic forecasts by using PM10 monitoring data. A series of experiments is performed using a state-of-the-art CTM (CHIMERE) and statistical models based on linear regressions. It is found that performance of both CTM simulations and "pure" statistical models is inferior to that of the combined models. In particular, the root mean squared error of the deterministic forecasts can be reduced, on the average, by up to 45 percent (specifically, from 12.8 to 6.9I14g/m3 at urban sites in summer) and the coefficient of determination can be almost doubled. Importantly, it is found that the combined models for rural sites in summer and for urban and suburban sites in both summer and winter are representative, on the average, not only for a given monitoring site used for their training, but also of territories of similar type of environment (rural, suburban or urban) within several hundreds of kilometers away.
Ammonia (NH3), whose main source in the troposphere is agriculture, is an important gaseous precursor of atmospheric particulate matter (PM). We derived daily ammonia emissions using NH3 total ...columns measured from the Infrared Atmospheric Sounding Interferometer (IASI) on board Metop‐A, at a relatively high spatial resolution (grid cell of 0.5° × 0.5°). During the European spring haze episodes of 24–31 March 2012 and 8–15 March 2014, IASI reveals NH3 total column magnitudes highlighting higher NH3 emissions over central Europe (especially over Germany, Czech Republic, and eastern France) from the ones provided by the European reference European Monitoring and Evaluation Programme inventory. These ammonia emissions exhibit in addition a large day‐to‐day variability, certainly due to spreading practices. The increase of NH3 emissions in the model, that reaches +300% locally, leads to an increase of both NH3 and PM2.5 surface concentrations and allows for a better comparison with independent measurements (in terms of bias, root‐mean‐square error, and correlation). This study suggests that there are good prospects for better quantifying NH3 emissions by atmospheric inversions.
Key Points
Strong potential of IASI for deducing NH3 daily emissions
High NH3 emissions revealed over central Europe
Strong impact of NH3 emissions on pollution particle formation
First partial tropospheric ozone columns (0–6 km) derived from radiances observed by the IASI instrument aboard the MetOp‐A platform over Europe during summer 2007 are presented. They were retrieved ...using an altitude‐dependent regularization method. Comparison with measurements from balloon sondes shows excellent agreement. Space‐borne observations show large lower tropospheric ozone amounts over South‐Eastern Europe during the heat wave period, which are also displayed by simulations with a regional chemistry‐transport model CHIMERE.
This study describes and evaluates the newly developed European scale Eulerian chemistry transport model CHIMERE-continental. The model is designed for seasonal simulations and real time forecasts ...without the use of super-computers. For the purpose of model evaluation simulated ozone mixing ratios for the period between 1 May 1998 and 30 September 1998 are compared to observational data from 115 European surface sites. In order to facilitate the interpretation of future forecasts a statistic is established to estimate the reliability of a simulated pollution level. Besides this, the comparison is done by means of time series, scatter plots, a spectral analysis and the calculation of RMS-errors and biases of the model results corresponding to each observation site. It turns out that the mean RMS-error of the simulated daily maximum ozone mixing ratio for the sites considered
a priori as well suited for a model comparison is about
10
ppb
. For the same period but a reduced number of sites observed concentrations of NO
2 and ethene are compared to simulated values. Difficulties encountered with the representativeness of observations when trying to evaluate a mesoscale air pollution model are discussed.
Ambient particle number size distributions were measured in Paris, France, during summer (1-31 July 2009) and winter (15 January to 15 February 2010) at three fixed ground sites and using two mobile ...laboratories and one airplane. The campaigns were part of the Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation (MEGAPOLI) project. New particle formation (NPF) was observed only during summer on approximately 50 % of the campaign days, assisted by the low condensation sink (about 10.7 plus or minus 5.9 10-3 s-1). NPF events inside the Paris plume were also observed at 600 m altitude onboard an aircraft simultaneously with regional events identified on the ground. Increased particle number concentrations were measured aloft also outside of the Paris plume at the same altitude, and were attributed to NPF. The Paris plume was identified, based on increased particle number and black carbon concentration, up to 200 km away from the Paris center during summer. The number concentration of particles with diameters exceeding 2.5 nm measured on the surface at the Paris center was on average 6.9 plus or minus 8.7 104 and 12.1 plus or minus 8.6 104 cm-3 during summer and winter, respectively, and was found to decrease exponentially with distance from Paris. However, further than 30 km from the city center, the particle number concentration at the surface was similar during both campaigns. During summer, one suburban site in the NE was not significantly affected by Paris emissions due to higher background number concentrations, while the particle number concentration at the second suburban site in the SW increased by a factor of 3 when it was downwind of Paris.
In this study we present airborne observations of aerosol and trace gases obtained over the sea in the western Mediterranean basin during the TRAQA (TRansport and Air QuAlity) and SAFMED (Secondary ...Aerosol Formation in the MEDiterranean) campaigns in summer 2012 and 2013. A total of 23 vertical profiles were measured up to 5000 m above sea level over an extended area (40-45 degree N and 2 degree W-12 degree E) including the Gulf of Genoa, southern France, the Gulf of Lion, and the Spanish coast. During TRAQA and SAFMED the study area experienced a wide range of meteorological conditions which favoured pollution export from different sources located around the basin. Also, several events of dust outflows were measured during the campaigns. Observations from the present study show that continental pollution largely affects the western Mediterranean both close to coastal regions and in the open sea as far as ~ 250 km from the coastline. The measured aerosol scattering coefficient varies between ~ 20 and 120 Mm-1, while carbon monoxide (CO) and ozone (O3) mixing ratios are in the range of 60-165 and 30-85 ppbv, respectively. Pollution reaches 3000-4000 m in altitude and presents a very complex and highly stratified structure characterized by fresh and aged layers both in the boundary layer and in the free troposphere. Within pollution plumes the measured particle concentration in the Aitken (0.004-0.1 mu m) and accumulation (0.1-1.0 mu m) modes is between ~ 30 and 5000-6000 scm-3 (standard cm-3), which is comparable to the aerosol concentration measured in continental areas under pollution conditions. Additionally, our measurements indicate the presence of highly concentrated Aitken layers (10 000-15 000 scm-3) observed both close to the surface and in the free troposphere, possibly linked to the influence of new particle formation (NPF) episodes over the basin.
Hourly concentrations of inorganic salts (ions) and carbonaceous material in fine aerosols (aerodynamic diameter, A.D. <2.5 μm) have been determined experimentally from fast measurements performed ...for a 3-week period in spring 2007 in Paris (France). The sum of these two chemical components (ions and carbonaceous aerosols) has shown to account for most of the fine aerosol mass (PM2.5). This time-resolved dataset allowed investigating the factors controlling the levels of PM2.5 in Paris and showed that polluted periods with PM2.5 > 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.
An innovative approach using mobile lidar measurements was implemented to test the performances of chemistry-transport models in simulating mass concentrations (PM10 ) predicted by ...chemistry-transport models. A ground-based mobile lidar (GBML) was deployed around Paris onboard a van during the MEGAPOLI (Megacities: Emissions, urban, regional and Global Atmospheric POLlution and climate effects, and Integrated tools for assessment and mitigation) summer experiment in July 2009. The measurements performed with this Rayleigh-Mie lidar are converted into PM10 profiles using optical-to-mass relationships previously established from in situ measurements performed around Paris for urban and peri-urban aerosols. The method is described here and applied to the 10 measurements days (MD). MD of 1, 15, 16 and 26 July 2009, corresponding to different levels of pollution and atmospheric conditions, are analyzed here in more details. Lidar-derived PM10 are compared with results of simulations from POLYPHEMUS and CHIMERE chemistry-transport models (CTM) and with ground-based observations from the AIRPARIF network. GBML-derived and AIRPARIF in situ measurements have been found to be in good agreement with a mean Root Mean Square Error RMSE (and a Mean Absolute Percentage Error MAPE) of 7.2 μg m-3 (26.0%) and 8.8 μg m-3 (25.2%) with relationships assuming peri-urban and urban-type particles, respectively. The comparisons between CTMs and lidar at ~200 m height have shown that CTMs tend to underestimate wet PM10 concentrations as revealed by the mean wet PM10 observed during the 10 MD of 22.4, 20.0 and 17.5 μg m-3 for lidar with peri-urban relationship, and POLYPHEMUS and CHIMERE models, respectively. This leads to a RMSE (and a MAPE) of 6.4 μg m-3 (29.6%) and 6.4 μg m-3 (27.6%) when considering POLYPHEMUS and CHIMERE CTMs, respectively. Wet integrated PM10 computed (between the ground and 1 km above the ground level) from lidar, POLYPHEMUS and CHIMERE results have been compared and have shown similar results with a RMSE (and MAPE) of 6.3 mg m-2 (30.1%) and 5.2 mg m-2 (22.3%) with POLYPHEMUS and CHIMERE when comparing with lidar-derived PM10 with periurban relationship. The values are of the same order of magnitude than other comparisons realized in previous studies. The discrepancies observed between models and measured PM10 can be explained by difficulties to accurately model the background conditions, the positions and strengths of the plume, the vertical turbulent diffusion (as well as the limited vertical model resolutions) and chemical processes as the formation of secondary aerosols. The major advantage of using vertically resolved lidar observations in addition to surface concentrations is to overcome the problem of limited spatial representativity of surface measurements. Even for the case of a well-mixed boundary layer, vertical mixing is not complete, especially in the surface layer and near source regions. Also a bad estimation of the mixing layer height would introduce errors in simulated surface concentrations, which can be detected using lidar measurements. In addition, horizontal spatial representativity is larger for altitude integrated measurements than for surface measurements, because horizontal inhomogeneities occurring near surface sources are dampened.
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.
PDF
