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Fungal spore organic aerosol emissions have been recognised as a significant source of particulate matter as PM10; however, they are not widely considered in current air quality models. In this work, we have implemented the parameterisation of fungal spore organic aerosol (OA) emissions introduced by Heald and Spracklen (2009) (H&S) and further modified by Hoose et al. (2010) in the CHIMERE regional chemistry-transport model. This simple parameterisation is based on two variables, leaf area index (LAI) and specific humidity. We have validated the geographical and temporal representativeness of this parameterisation on a large scale by using yearly polyol observations and primary biogenic organic aerosol factors from positive matrix factorisation (PMF) analysis at 11 French measurement sites. For a group of sites in northern and eastern France, the seasonal variation of fungal spore emissions, displaying large summer and small winter values, is correctly depicted. However, the H&S parameterisation fails to capture fungal spore concentrations for a smaller group of Mediterranean sites with less data availability in terms of both absolute values and seasonal variability, leading to strong negative biases, especially during the autumn and winter seasons. Two years of CHIMERE simulations with the H&S parameterisation have shown a significant contribution of fungal spore OA to PM10 mass, which is lower than 10 % during winter and reaches up to 20 % during summer in high-emission zones, especially over large forested areas. In terms of contributions to organic matter (OM) concentrations, the simulated fungal spore contribution in autumn is as high as 40 % and reaches at most 30 % of the OM for the other seasons. As a conclusion, the fungal spore OA contribution to the total OM concentrations is shown to be substantial enough to be considered a major PM10 fraction and should then be included in state-of-the-art chemistry-transport models.

Since 2018, the TROPOspheric Monitoring Instrument (TROPOMI) on board the Sentinel-5 Precursor (S5P) has provided unprecedented images of nitrogen dioxide (NO2) tropospheric columns at a relatively high spatial resolution with a daily revisit. This study aims at assessing the potential of TROPOMI–PAL data to estimate the national to urban NOx emissions in France from 2019 to 2021, using the variational mode of the recent Community Inversion Framework (CIF) coupled to the CHIMERE regional transport model at a spatial resolution of 10 km × 10 km. The seasonal to inter-annual variations in the French NOx emissions are analyzed. Special attention is paid to the current capability to quantify strong anomalies in the NOx emissions at intra-annual scales, such as the ones due to the COVID-19 pandemic, by using TROPOMI NO2 observations. At the annual scale, the inversions suggest a decrease in the average emissions over 2019–2021 of −3 % compared to the national budget from the Copernicus Atmosphere Monitoring Service regional inventory (CAMS-REG) for the year 2016, which is used as a prior estimate of the national-scale emissions for each year by the Bayesian inversion framework. This is lower than the decrease of −14 % from 2016 to the average over 2019–2021 in the estimates of the French Technical Reference Center for Air Pollution and Climate Change (CITEPA). The lower decrease in the inversion results may be linked in large part to the limited level of constraint brought by the TROPOMI data, due to the observation coverage and the ratio between the current level of errors in the observation and the chemistry-transport model, and to the NO2 signal from the French anthropogenic sources. Focusing on local analysis and selecting the days during which the TROPOMI coverage is good over a specific local source, we compute the reductions in the anthropogenic NOx emission estimates by the inversions from spring 2019 to spring 2020. These reductions are particularly pronounced for the largest French urban areas with high emission levels (e.g., −26 % from April 2019 to April 2020 in the Paris urban area), reflecting reductions in the intensity of vehicle traffic reported during the lockdown period. However, the system does not show large emission decreases for some of the largest cities in France (such as Bordeaux, Nice and Toulouse), even though they were also impacted by the lockdown measures. Despite the current limitations for the monitoring of emissions at the national scale, or for some of the largest cities in France, these results open positive perspectives regarding the ability to support the validation or improvement of inventories with satellite observations, at least at the local level. This leads to discussions on the need for a stepwise improvement of the inversion configuration for a better extraction and extrapolation in space and time of the information from the satellite observations.

A new version of the CHIMERE model is presented. This version contains both computational and physico-chemical changes. The computational changes make it easy to choose the variables to be extracted as a result, including values of maximum sub-hourly concentrations. Performance tests show that the model is 1.5 to 2 times faster than the previous version for the same setup. Processes such as turbulence, transport schemes and dry deposition have been modified and updated. Optimization was also performed for the management of emissions such as anthropogenic and mineral dust. The impact of fires on wind speed, soil properties and leaf area index (LAI) was added. Pollen emissions, transport and deposition were added for birch, ragweed, olive and grass. The model is validated with a simulation covering Europe with a 60 km × 60 km resolution and the entire year of 2019. Results are compared to various measurements, and statistical scores show that the model provides better results than the previous versions.

Meteorological and chemical modelling at the regional scale often involve the nudging of the modelled meteorology towards reanalysis fields and meteo-chemical coupling to properly consider the interactions between aerosols, clouds and radiation. Both types of processes can change the meteorology, but not for the same reasons and not necessarily in the same way. To assess the possible interactions between nudging and online coupling, several simulations are carried out with the WRF–CHIMERE (Weather Research and Forecasting) model in its offline and online configurations. Through comparison with measurements, we show that the use of nudging significantly improves the model performances. We also show that coupling changes the results much less than nudging. Finally, we show that when nudging is used, it limits the variability in the results due to coupling.

The aerosol optical depth (AOD) is a derived measurement useful to investigate the aerosol load and its distribution at different spatio-temporal scales. In this work we use long-term (2000–2021) MAIAC (Multi-Angle Implementation of Atmospheric Correction) retrievals with 1 km resolution to investigate the climatological AOD variability and trends at different scales in Europe: a continental (30–60∘ N, 20∘ W–40∘ E), a regional (100 × 100 km2) and an urban–local scale (3 × 3 km2). The AOD climatology at the continental scale shows the highest values during summer (JJA) and the lowest during winter (DJF) seasons. Regional and urban–local scales are investigated for 21 cities in Europe, including capitals and large urban agglomerations. Analyses show AOD average (550 nm) values between 0.06 and 0.16 at the urban–local scale while also displaying a strong north–south gradient. This gradient corresponds to a similar one in the European background, with higher AOD being located over the Po Valley, the Mediterranean Basin and eastern Europe. Average enhancements of the local with respect to regional AOD of 57 %, 55 %, 39 % and 32 % are found for large metropolitan centers such as Barcelona, Lisbon, Paris and Athens, respectively, suggesting a non-negligible enhancement of the aerosol burden through local emissions. Negative average deviations are observed for other cities, such as Amsterdam (−17 %) and Brussels (−6 %), indicating higher regional background signal and suggesting a heterogeneous aerosol spatial distribution that conceals the urban–local signal. Finally, negative statistically significant AOD trends for the entire European continent are observed. A stronger decrease rate at the regional scale with respect to the local scale occurs for most of the cities under investigation.

The atypical huge forest fires observed in France during the summer of 2022 are modeled using the CHIMERE model. The impact of these emissions is quantified on ozone, aerosols and aerosol optical depth (AOD). The fires also influence the surface by destroying the vegetation and creating new erodible surfaces. This increases the mineral dust emissions but also reduces the leaf area index (LAI), and then it decreases the biogenic emissions and the dry deposition of gases such as ozone. Results show that the fires induce numerous increases in surface ozone and particulate matter (PM) concentrations close to the sources but also in downwind remote sites such as the Paris area. During the period of the most intense fires in July, the impact of concentrations is mainly due to emissions themselves, and later, in August, ozone and PM concentrations continue to increase but this time due to changes in the burned surfaces.

Organic aerosol (OA) still remains one of the most difficult components of the atmospheric aerosols to simulate, given the multitude of its precursors, the uncertainty in its formation pathways, and the lack of measurements of its detailed composition. The LANDEX (LANDes Experiment) project, during its intensive field campaign in summer 2017, gives us the opportunity to compare biogenic secondary OA (BSOA) and its precursors and oxidants obtained within and above the Landes forest canopy to simulations performed with CHIMERE, a state-of-the-art regional chemistry transport model. The Landes forest is situated in the southwestern part of France and is one of the largest anthropized forests in Europe (1×106 ha). The majority of the forest is comprised of maritime pine trees, which are strong terpenoid emitters, providing a large potential for BSOA formation. In order to simulate OA buildup in this area, a specific model configuration setup adapted to the local peculiarities was necessary. As the forest is nonhomogeneous, with interstitial agricultural fields, high-resolution 1 km simulations over the forest area were performed. Biogenic volatile organic compound (BVOC) emissions were predicted by MEGAN, but specific land cover information needed to be used and was thus chosen from the comparison of several high-resolution land cover databases. Moreover, the tree species distribution needed to be updated for the specific conditions of the Landes forest. In order to understand the canopy effect in the forest, canopy effects on vertical diffusivity, winds, and radiation were implemented in the model in a simplified way. The refined simulations show a redistribution of BVOCs with a decrease in isoprene and an increase in terpenoid emissions with respect to the standard case, both of which are in line with observations. Corresponding changes to simulated BSOA sources are tracked. Very low nighttime ozone, sometimes near zero, remains overestimated in all simulations. This has implications for the nighttime oxidant budget, including NO3. Despite careful treatment of physical conditions, simulated BSOA is overestimated in the most refined simulation. Simulations are also compared to air quality sites surrounding the Landes forest, reporting a more realistic simulation in these stations in the most refined test case. Finally, the importance of the sea breeze system, which also impacts species concentrations inside the forest, is made evident.

Volcanic activity is an important source of atmospheric sulfur dioxide (SO2), which, after conversion into sulfuric acid, induces impacts on rain acidity, human health, meteorology and the radiative balance of the atmosphere, among others. This work focuses on the conversion of SO2 into sulfates (SO4(p)2-, S(+VI)) in the mid-tropospheric volcanic plume emitted by the explosive eruption of Mount Etna (Italy) on 12 April 2012, using the CHIMERE chemistry transport model. As the volcanic plume location and composition depend on several often poorly constrained parameters, using a chemistry transport model allows us to study the sensitivity of SO2 oxidation to multiple aspects, such as volcanic water emissions, transition metal emissions, plume diffusion and plume altitude. Our results show that two pathways contribute to sulfate production in the mid-troposphere: (1) the oxidation of SO2 by OH in the gaseous phase (70 %) and (2) aqueous oxidation by O2 catalysed by Mn2+ and Fe3+ ions (25 %). Oxidation in the aqueous phase is the faster process, but liquid water is scarce in the mid-troposphere; therefore, the relative share of gaseous oxidation can be important. After 1 d in the mid-troposphere, about 0.5 % of the volcanic SO2 was converted to sulfates via the gaseous process. Because of the nonlinear dependency of the kinetics in the aqueous phase on the amount of volcanic water emitted and on the availability of transition metals in the aqueous phase, several experiments have been designed to determine the prominence of different parameters. Our simulations show that, during the short time that liquid water remains in the plume, around 0.4 % of sulfates manage to quickly enter the liquid phase. Sensitivity tests regarding the advection scheme have shown that this scheme must be chosen wisely, as dispersion will impact both of the oxidation pathways explained above.

We present a comprehensive study integrating satellite observations of ozone pollution, in situ measurements, and chemistry-transport model simulations for quantifying the role of anthropogenic emission reductions during the COVID-19 lockdown in spring 2020 over Europe. Satellite observations are derived from the IASI+GOME2 (Infrared Atmospheric Sounding Interferometer + Global Ozone Monitoring Experiment 2) multispectral synergism, which provides better sensitivity to near-surface ozone pollution. These observations are mainly analysed in terms of differences between the average on 1–15 April 2020, when the strictest lockdown restrictions took place, and the same period in 2019. They show clear enhancements of near-surface ozone in central Europe and northern Italy, as well as some other hotspots, which are typically characterized by volatile organic compound (VOC)-limited chemical regimes. An overall reduction of ozone is observed elsewhere, where ozone chemistry is limited by the abundance of NOx. The spatial distribution of positive and negative ozone concentration anomalies observed from space is in relatively good quantitative agreement with surface in situ measurements over the continent (a correlation coefficient of 0.55, a root-mean-squared difference of 11 ppb, and the same standard deviation and range of variability). An average difference of ∼ 8 ppb between the two observational datasets is observed, which can partly be explained by the fact the satellite approach retrieves partial columns of ozone with a peak sensitivity above the surface (near 2 km of altitude over land and averaging kernels reaching the middle troposphere over ocean). For assessing the impact of the reduction of anthropogenic emissions during the lockdown, we adjust the satellite and in situ surface observations for subtracting the influence of meteorological conditions in 2020 and 2019. This adjustment is derived from the chemistry-transport model simulations using the meteorological fields of each year and identical emission inventories. Using adjustments adapted for the altitude and sensitivity of each observation, both datasets show consistent estimates of the influence of lockdown emission reduction. They both show lockdown-associated ozone enhancements in hotspots over central Europe and northern Italy, with a reduced amplitude with respect to the total changes observed between the 2 years and an overall reduction elsewhere over Europe and the ocean. Satellite observations additionally provide the ozone anomalies in the regions remote from in situ sensors, an enhancement over the Mediterranean likely associated with maritime traffic emissions, and a marked large-scale reduction of ozone elsewhere over ocean (particularly over the North Sea), in consistency with previous assessments done with ozone sonde measurements in the free troposphere. These observational assessments are compared with model-only estimations, using the CHIMERE chemistry-transport model. Whereas a general qualitative consistency of positive and negative ozone anomalies is observed with respect to observational estimates, significant changes are seen in their amplitudes. Models underestimate the range of variability of the ozone changes by at least a factor 2 with respect to the two observational datasets, both for enhancements and decreases of ozone. Moreover, a significant ozone decrease observed at a large hemispheric scale is not simulated since the modelling domain is the European continent. As simulations only consider the troposphere, the influence from stratospheric ozone is also missing. Sensitivity analyses also show an important role of vertical mixing of atmospheric constituents, which depends on the meteorological fields used in the simulation and significantly modify the amplitude of the changes of ozone pollution during the lockdown.

During the West African summer monsoon, pollutants emitted in urbanized coastal areas modify cloud cover and precipitation patterns. The Dynamics-Aerosol-Chemistry-Cloud Interactions in West Africa (DACCIWA) field campaign provided numerous aircraft-based and ground-based observations, which are used here to evaluate two experiments made with the coupled WRF–CHIMERE model, integrating both the direct and indirect aerosol effect on meteorology. During one well-documented week (1–7 July 2016), the impacts of anthropogenic aerosols on the diurnal cycle of low-level clouds and precipitation are analyzed in detail using high and moderate intensity of anthropogenic emissions in the experiments. Over the continent and close to major anthropogenic emission sources, the breakup time of low-level clouds is delayed by 1 hour, and the daily precipitation rate decreased by 7.5 % with the enhanced anthropogenic emission experiment (with high aerosol load). Despite the small modifications on daily average of low-level cloud cover (+2.6 %) with high aerosol load compared to moderate, there is an increase by more than 20 % from 14:00 to 22:00 UTC on hourly average. Moreover, modifications of the modeled low-level cloud and precipitation rate occur far from the major anthropogenic emission sources, to the south over the ocean and to the north up to 11∘ N. The present study adds evidence to recent findings that enhanced pollution levels in West Africa may reduce precipitation.

The CHIMERE chemistry-transport model v2020r1 replaces the v2017r5 version and provides numerous novelties. The most important of these is the online coupling with the Weather Research and Forecasting (WRF) meteorological model via the OASIS3 – Model Coupling Toolkit (MCT) external coupler. The model can still be used in offline mode; the online mode enables us to take into account the direct and indirect effects of aerosols on meteorology. This coupling also enables using the meteorological parameters with sub-hourly time steps. Some new parameterizations are implemented to increase the model performance and the user's choices: dimethyl sulfide (DMS) emissions, additional schemes for secondary organic aerosol (SOA) formation with volatility basis set (VBS) and H2O, improved schemes for mineral dust, biomass burning, and sea-salt emissions. The NOx emissions from lightning are added. The model also includes the possibility to use the operator-splitting integration technique. The subgrid-scale variability calculation of concentrations due to emission activity sectors is now possible. Finally, a new vertical advection scheme has been implemented, which is able to simulate more correctly long-range transport of thin pollutant plumes.

Free tropospheric ozone (O3) trends in the Central East China (CEC) and export regions are investigated for 2008–2017 using the IASI (Infrared Atmospheric Sounding Interferometer) O3 observations and the LMDZ-OR-INCA model simulations, including the most recent Chinese emission inventory. The observed and modelled trends in the CEC region are −0.07 ± 0.02 and −0.08 ± 0.02 DU yr−1, respectively, for the lower free troposphere (3–6 km column) and −0.05 ± 0.02 and −0.06 ± 0.02 DU yr−1, respectively, for the upper free troposphere (6–9 km column). The statistical p value is smaller to 0.01 for all the derived trends. A good agreement between the observations and the model is also observed in the region, including the Korean Peninsula and Japan and corresponding to the region of pollution export from China. Based on sensitivity studies conducted with the model, we evaluate, at 60 % and 52 %, the contribution of the Chinese anthropogenic emissions to the trend in the lower and upper free troposphere, respectively. The second main contribution to the trend is the meteorological variability (34 % and 50 %, respectively). These results suggest that the reduction in NOx anthropogenic emissions that has occurred since 2013 in China led to a decrease in ozone in the Chinese free troposphere, contrary to the increase in ozone at the surface. We designed some tests to compare the trends derived by the IASI observations and the model to independent measurements, such as the In-service Aircraft for a Global Observing System (IAGOS) or other satellite measurements (Ozone Monitoring Instrument (OMI)/Microwave Limb Sounder (MLS)). These comparisons do not confirm the O3 decrease and stress the difficulty in analysing short-term trends using multiple data sets with various sampling and the risk of overinterpreting the results.

Up-to-date and accurate emission inventories for air pollutants are essential for understanding their role in the formation of tropospheric ozone and particulate matter at various temporal scales, for anticipating pollution peaks and for identifying the key drivers that could help mitigate their concentrations. This paper describes the Bayesian variational inverse system PYVAR-CHIMERE, which is now adapted to the inversion of reactive species. Complementarily with bottom-up inventories, this system aims at updating and improving the knowledge on the high spatiotemporal variability of emissions of air pollutants and their precursors. The system is designed to use any type of observations, such as satellite observations or surface station measurements. The potential of PYVAR-CHIMERE is illustrated with inversions of both carbon monoxide (CO) and nitrogen oxides (NOx) emissions in Europe, using the MOPITT and OMI satellite observations, respectively. In these cases, local increments on CO emissions can reach more than +50 %, with increases located mainly over central and eastern Europe, except in the south of Poland, and decreases located over Spain and Portugal. The illustrative cases for NOx emissions also lead to large local increments (> 50 %), for example over industrial areas (e.g., over the Po Valley) and over the Netherlands. The good behavior of the inversion is shown through statistics on the concentrations: the mean bias, RMSE, standard deviation, and correlation between the simulated and observed concentrations. For CO, the mean bias is reduced by about 27 % when using the posterior emissions, the RMSE and the standard deviation are reduced by about 50 %, and the correlation is strongly improved (0.74 when using the posterior emissions against 0.02); for NOx, the mean bias is reduced by about 24 % and the RMSE and the standard deviation are reduced by about 7 %, but the correlation is not improved. We reported strong non-linear relationships between NOx emissions and satellite NO2 columns, now requiring a fully comprehensive scientific study.

An incoherent broadband cavity-enhanced absorption spectroscopy (IBBCEAS) technique has been developed for the in situ monitoring of NO3 radicals at the parts per trillion level in the CSA simulation chamber (at LISA). The technique couples an incoherent broadband light source centered at 662 nm with a high-finesse optical cavity made of two highly reflecting mirrors. The optical cavity which has an effective length of 82 cm allows for up to 3 km of effective absorption and a high sensitivity for NO3 detection (up to 6 ppt for an integration time of 10 s). This technique also allows for NO2 monitoring (up to 9 ppb for an integration time of 10 s). Here, we present the experimental setup as well as tests for its characterization and validation. The validation tests include an intercomparison with another independent technique (Fourier-transform infrared, FTIR) and the absolute rate determination for the reaction trans-2-butene + NO3, which is already well documented in the literature. The value of (4.13 ± 0.45) × 10−13 cm3 molecule−1 s−1 has been found, which is in good agreement with previous determinations. From these experiments, optimal operation conditions are proposed. The technique is now fully operational and can be used to determine rate constants for fast reactions involving complex volatile organic compounds (VOCs; with rate constants up to 10−10 cm3 molecule−1 s−1).

Agriculture is the main source of ammonia (NH3) in France, an important gaseous precursor of atmospheric particulate matter (PM). National and global emission inventories are known to have difficulty representing the large spatial and temporal variability inherent to atmospheric NH3. In this study, we compare NH3 emissions in France during spring 2011 from one reference inventory, the TNO inventory, and two alternative inventories that account in different manners for both the spatial and temporal variabilities of the emissions: (i) the NH3SAT satellite-derived inventory based on IASI NH3 columns and (ii) the CADASTRE-CIT inventory that combines NH3 emissions due to nitrogen fertilization calculated with the mechanistic model VOLT'AIR on the database of the CADASTRE_NH3 framework and other source emissions from the CITEPA. The total spring budgets, from March to May 2011, at the national level are higher when calculated with both alternative inventories than with the reference, the difference being more marked with CADASTRE-CIT. NH3SAT and CADASTRE-CIT inventories both yield to large NH3 spring emissions due to fertilization on soils with high pH in the northeastern part of France (65 and 135 kt NH3, respectively, vs. 48 kt NH3 for TNO-GEN), while soil properties are not accounted for by the TNO-GEN methodology. For the other parts of France, the differences are smaller. The timing of fertilization and associated ammonia emissions is closely related to the nitrogen requirements and hence the phenological stage of the crops, and therefore to the crop year's specific weather conditions. Maximum emissions are observed in March for 2011 for some regions for both alternative inventories, while April is the period with maximum emissions for the reference inventory regardless of the region or the year. Comparing the inventories at finer temporal resolutions, typically at daily scale, large differences are found. The convergence of alternative, independent and complementary methods on the spatiotemporal representation of the spring NH3 emissions, particularly over areas where the contribution of mineral fertilizer spreading to the spring budget is strong, encourages further developments in both prospective complementary directions, as this will help improve national NH3 emission inventories.

Biomass burning emissions are a major source of trace gases and aerosols. Wildfires being highly variable in time and space, calculating emissions requires a numerical tool able to estimate fluxes at the kilometer scale and with an hourly time step. Here, the APIFLAME model version 2.0 is presented. It is structured to be modular in terms of input databases and processing methods. The main evolution compared to version 1.0 is the possibility of merging burned area and fire radiative power (FRP) satellite observations to modulate the temporal variations of fire emissions and to integrate small fires that may not be detected in the burned area product. Accounting for possible missed detection due to small fire results in an increase in burned area ranging from ∼5 % in Africa and Australia to ∼30 % in North America on average over the 2013–2017 time period based on the Moderate-Resolution Imaging Spectroradiometer (MODIS) Collection 6 fire products. An illustration for the case of southwestern Europe during the summer of 2016, marked by large wildfires in Portugal, is presented. Emissions calculated using different possible configurations of APIFLAME show a dispersion of 80 % on average over the domain during the largest wildfires (8–14 August 2016), which can be considered as an estimate of uncertainty of emissions. The main sources of uncertainty studied, by order of importance, are the emission factors, the calculation of the burned area, and the vegetation attribution. The aerosol (PM10) and carbon monoxide (CO) concentrations simulated with the CHIMERE regional chemistry transport model (CTM) are consistent with observations (good timing for the beginning and end of the events, ±1 d for the timing of the peak values) but tend to be overestimated compared to observations at surface stations. On the contrary, vertically integrated concentrations tend to be underestimated compared to satellite observations of total column CO by the Infrared Atmospheric Sounding Interferometer (IASI) instrument and aerosol optical depth (AOD) by MODIS. This underestimate is lower close to the fire region (5 %–40 % for AOD depending on the configuration and 8 %–18 % for total CO) but rapidly increases downwind. For all comparisons, better agreement is achieved when emissions are injected higher into the free troposphere using a vertical profile as estimated from observations of aerosol plume height by the Multi-angle Imaging SpectroRadiometer (MISR) satellite instrument (injection up to 4 km). Comparisons of aerosol layer heights to observations by the Cloud-Aerosol Lidar with Orthogonal Polarization (CALIOP) show that some parts of the plume may still be transported at too low an altitude. The comparisons of the different CTM simulations to observations point to uncertainties not only on emissions (total mass and daily variability) but also on the simulation of their transport with the CTM and mixing with other sources. Considering the uncertainty of the emission injection profile and of the modeling of the transport of these dense plumes, it is difficult to fully validate emissions through comparisons between model simulations and atmospheric observations.

Modelling of mineral dust is often done using one single mean species. But for biogeochemical studies, it could be useful to access to a more detailed information on differentiated mineral species and the associated chemical composition. Differentiating between mineral species would also induce different optical properties and densities and then different radiative impact, transport and deposition. In this study, the mineralogical differentiation is implemented in the CHIMERE regional chemistry-transport model, by using global databases. The results show that this implementation does not change the results much in terms of aerosol optical depth, surface concentrations and deposition fluxes. But the information on mineralogy, with a high spatial (a few kilometres) and temporal (1 h) resolution, is now available and is ready to be used for future biogeochemical studies.

The Sea Surface Microlayer (SML) is known to be enriched by trace metals relative to the underlying water and harbor diverse microbial communities (i.e., neuston). However, the processes linking metals and biota in the SML are not yet fully understood. The metal (Cd, Co, Cu, Fe, Ni, Mo, V, Zn and Pb) concentrations in aerosol samples in the SML (dissolved and total fractions) and in subsurface waters (SSWs; dissolved fraction at ∼1 m depth) from the western Mediterranean Sea were analyzed in this study during a cruise in May–June 2017. The composition and abundance of the bacterial community in the SML and SSW, the primary production, and Chl a in the SSW were measured simultaneously at all stations during the cruise. Residence times in the SML of metals derived from aerosol depositions were highly variable and ranged from minutes for Fe (3.6±6.0 min) to a few hours for Cu (5.8±6.2 h). Concentrations of most of the dissolved metals in both the SML and SSW were positively correlated with the salinity gradient and showed the characteristic eastward increase in the surface waters of the Mediterranean Sea (MS). In contrast, the total fraction of some reactive metals in the SML (i.e., Cu, Fe, Pb and Zn) showed a negative correlation with salinity and a positive correlation with microbial abundance, which might be associated with microbial uptake. Our results show a strong negative correlation between the dissolved and total Ni concentration and heterotrophic bacterial abundance in the SML and SSW, but we cannot ascertain whether this correlation reflects a toxicity effect or is the result of some other process.

Air pollution reaching hazardous levels in many Chinese cities has been a major concern in China over the past decades. New policies have been applied to regulate anthropogenic pollutant emissions, leading to changes in atmospheric composition and in particulate matter (PM) production. Increasing levels of atmospheric ammonia columns have been observed by satellite during recent years. In particular, observations from the Infrared Atmospheric Sounding Interferometer (IASI) reveal an increase of these columns by 15 % and 65 % from 2011 to 2013 and 2015, respectively, over eastern China. In this paper we performed model simulations for 2011, 2013 and 2015 in order to understand the origin of this increase and to quantify the link between ammonia and the inorganic components of particles: NH4(p)+/SO4(p)2-/NO3(p)-. Interannual change of meteorology can be excluded as a reason: year 2015 meteorology leads to enhanced sulfate production over eastern China, which increases the ammonium and decreases the ammonia content, which is contrary to satellite observations. Reductions in SO2 and NOx emissions from 2011 to 2015 of 37.5 % and 21 % respectively, as constrained from satellite data, lead to decreased inorganic matter (by 14 % for NH4(p)++SO4(p)2-+NO3(p)-). This in turn leads to increased gaseous NH3(g) tropospheric columns by as much as 24 % and 49 % (sampled corresponding to IASI data availability) from 2011 to 2013 and 2015 respectively and thus can explain most of the observed increase.

During the monsoon season, pollutants emitted by large coastal cities and biomass burning plumes originating from central Africa have complex transport pathways over southern West Africa (SWA). The Dynamics–Aerosol–Chemistry–Cloud Interactions in West Africa (DACCIWA) field campaign has provided numerous dynamical and chemical measurements in and around the super-site of Savè in Benin ( ≈ 185 km away from the coast), which allows quantification of the relative contribution of advected pollutants. Through the combination of in situ ground measurements with aircraft, radio-sounding, satellite, and high-resolution chemistry-transport modeling with the CHIMERE model, the source attribution and transport pathways of pollutants inland (here, NOx and CO) are carefully analyzed for the 1–7 July 2016 period. The relative contributions of different sources (i.e., emissions from several large coastal cities) to the air quality in Savè are characterized. It is shown that a systematic diurnal cycle exists with high surface concentrations of pollutants from 18:00 to 22:00 UTC. This evening peak is attributed to pollution transport from the coastal city of Cotonou (Benin). Numerical model experiments indicate that the anthropogenic pollutants are accumulated during the day close to the coast and transported northward as soon as the daytime convection in the atmospheric boundary layer ceases after 16:00 UTC, reaching 8° N at 21:00 UTC. When significant biomass burning pollutants are transported into continental SWA, they are mixed with anthropogenic pollutants along the coast during the day, and this mixture is then transported northward. At night, most of the coastal anthropogenic plumes are transported within the planetary boundary layer (below about 500 m above ground level), whereas the biomass burning pollutants are mostly transported above it, thus generally not impacting ground level air quality.

Continuous measurements between July 2012 and December 2015 at the Henties Bay Aerosol Observatory (HBAO; 22∘ S, 14∘05′ E), Namibia, show that, during the austral wintertime, transport of light-absorbing black carbon aerosols occurs at low level into the marine boundary layer. The average of daily concentrations of equivalent black carbon (eBC) over the whole sampling period is 53 (±55) ng m−3. Peak values above 200 ng m−3 and up to 800 ng m−3 occur seasonally from May to August, ahead of the dry season peak of biomass burning in southern Africa (August to October). Analysis of 3-day air mass back-trajectories show that air masses from the South Atlantic Ocean south of Henties Bay are generally cleaner than air having originated over the ocean north of Henties Bay, influenced by the outflow of the major biomass burning plume, and from the continent, where wildfires occur. Additional episodic peak concentrations, even for oceanic transport, indicate that pollution from distant sources in South Africa and maritime traffic along the Atlantic ship tracks could be important. While we expect the direct radiative effect to be negligible, the indirect effect on the microphysical properties of the stratocumulus clouds and the deposition to the ocean could be significant and deserve further investigation, specifically ahead of the dry season.

The simulation of fine organic aerosols with CTMs (chemistry–transport models) in the western Mediterranean basin has not been studied until recently. The ChArMEx (the Chemistry-Aerosol Mediterranean Experiment) SOP 1b (Special Observation Period 1b) intensive field campaign in summer of 2013 gathered a large and comprehensive data set of observations, allowing the study of different aspects of the Mediterranean atmosphere including the formation of organic aerosols (OAs) in 3-D models. In this study, we used the CHIMERE CTM to perform simulations for the duration of the SAFMED (Secondary Aerosol Formation in the MEDiterranean) period (July to August 2013) of this campaign. In particular, we evaluated four schemes for the simulation of OA, including the CHIMERE standard scheme, the VBS (volatility basis set) standard scheme with two parameterizations including aging of biogenic secondary OA, and a modified version of the VBS scheme which includes fragmentation and formation of nonvolatile OA. The results from these four schemes are compared to observations at two stations in the western Mediterranean basin, located on Ersa, Cap Corse (Corsica, France), and at Cap Es Pinar (Mallorca, Spain). These observations include OA mass concentration, PMF (positive matrix factorization) results of different OA fractions, and 14C observations showing the fossil or nonfossil origins of carbonaceous particles. Because of the complex orography of the Ersa site, an original method for calculating an orographic representativeness error (ORE) has been developed. It is concluded that the modified VBS scheme is close to observations in all three aspects mentioned above; the standard VBS scheme without BSOA (biogenic secondary organic aerosol) aging also has a satisfactory performance in simulating the mass concentration of OA, but not for the source origin analysis comparisons. In addition, the OA sources over the western Mediterranean basin are explored. OA shows a major biogenic origin, especially at several hundred meters height from the surface; however over the Gulf of Genoa near the surface, the anthropogenic origin is of similar importance. A general assessment of other species was performed to evaluate the robustness of the simulations for this particular domain before evaluating OA simulation schemes. It is also shown that the Cap Corse site presents important orographic complexity, which makes comparison between model simulations and observations difficult. A method was designed to estimate an orographic representativeness error for species measured at Ersa and yields an uncertainty of between 50 and 85 % for primary pollutants, and around 2–10 % for secondary species.

Carbon monoxide, CO, and fine atmospheric particulate matter, PM2.5, are analyzed over the Guinean Gulf coastal region using the WRF-CHIMERE modeling system and observations during the beginning of the monsoon 2006 (from May to July), corresponding to the Africa Multidisciplinary Monsoon Analysis (AMMA) campaign period. Along the Guinean Gulf coast, the contribution of long-range pollution transport to CO or PM2.5 concentrations is important. The contribution of desert dust PM2.5 concentration decreases from ∼ 38 % in May to ∼ 5 % in July. The contribution of biomass burning PM2.5 concentration from Central Africa increases from ∼ 10 % in May to ∼ 52 % in July. The anthropogenic contribution is ∼ 30 % for CO and ∼ 10 % for PM2.5 during the whole period. When focusing only on anthropogenic pollution, frequent northward transport events from the coast to the Sahel are associated with periods of low wind and no precipitation. In June, anthropogenic PM2.5 and CO concentrations are higher than in May or July over the Guinean coastal region. Air mass dynamics concentrate pollutants emitted in the Sahel due to a meridional atmospheric cell. Moreover, a part of the pollution emitted remotely at the coast is transported and accumulated over the Sahel. Focusing the analysis on the period 8–15 June, anthropogenic pollutants emitted along the coastline are exported toward the north especially at the beginning of the night (18:00 to 00:00 UTC) with the establishment of the nocturnal low level jet. Plumes originating from different cities are mixed for some hours at the coast, leading to high pollution concentration, because of specific disturbed meteorological conditions.

Measurements of the global surface solar irradiation and its direct and diffuse components performed at three Egyptian sites (Aswan, Cairo, and Port Said) are used to test the ability of two published decomposition models to estimate the hourly direct normal irradiance from the measured global horizontal one in cloud-free conditions. The tested models failed to reproduce the temporal variability of the measurements, which we show to be partly induced by the large variability of the atmospheric content in aerosols. We propose a revised formulation of the decomposition models that takes into account the aerosol optical depth (AOD) at 1000 nm derived from onsite measurements. It leads to a significant reduction of the bias and root mean square deviation of the original models and this at the three Egyptian sites. However, because the AOD is rarely measured at the meteorological stations, we also quantify the performance of the revised models when the AOD is either derived from the MODIS observations or obtained by the products from Copernicus Atmospheric Monitoring Service (CAMS). Probably because of their finer temporal resolution that makes them more apt to reproduce the rapid variations of the AOD, the best results are obtained with the CAMS products. Therefore, we recommend using a combination of the revised decomposition models and these CAMS products to estimate the hourly direct normal irradiance in areas such as Egypt where aerosols are ubiquitous. Note that the improved decomposition models are generally applicable in all-sky conditions, although their benefit has been demonstrated to be significant, and probably limited to, cloud-free conditions.

Current national pledges to reduce greenhouse gas emissions track to a temperature rise of about 3 °C. Here the authors use future projections to show that 3 °C warming under a business as usual scenario would result in large increases in ozone concentrations, off-setting any benefits from mitigation policies.

CHIMERE is a chemistry-transport model designed for regional atmospheric composition. It can be used at a variety of scales from local to continental domains. However, due to the model design and its historical use as a regional model, major limitations had remained, hampering its use at hemispheric scale, due to the coordinate system used for transport as well as to missing processes that are important in regions outside Europe. Most of these limitations have been removed in the CHIMERE-2017 version, allowing its use in any region of the world and at any scale, from the scale of a single urban area up to hemispheric scale, with or without polar regions included. Other important improvements have been made in the treatment of the physical processes affecting aerosols and the emissions of mineral dust. From a computational point of view, the parallelization strategy of the model has also been updated in order to improve model numerical performance and reduce the code complexity. The present article describes all these changes. Statistical scores for a model simulation over continental Europe are presented, and a simulation of the circumpolar transport of volcanic ash plume from the Puyehue volcanic eruption in June 2011 in Chile provides a test case for the new model version at hemispheric scale.

For the identification of regional springtime ozone episodes, rural European Monitoring and Evaluation Programme (EMEP) ozone measurements from countries surrounding the western Mediterranean (Spain, France, Switzerland, Italy, Malta) have been examined with emphasis on periods of high ozone-mixing ratios, according to the variation of the daily afternoon (12:00–18:00) ozone values. For two selected high ozone episodes in April and May 2008, composite NCEP/NCAR reanalysis maps of various meteorological parameters and/or their anomalies (geopotential height, specific humidity, vertical wind velocity omega, vector wind speed and temperature) at various tropospheric pressure levels have been examined together with the corresponding satellite Infrared Atmospheric Sounding Interferometer (IASI) ozone measurements (at 3 and 10 km), CHIMERE simulations, vertical ozone soundings and HYSPLIT back trajectories. The observations show that high ozone values are detected in several countries simultaneously over several days. Also, the examined spring ozone episodes over the western Mediterranean and in central Europe are linked to synoptic meteorological conditions very similar to those recently observed in summertime ozone episodes over the eastern Mediterranean (Kalabokas et al., 2013, 2015; Doche et al., 2014), where the transport of tropospheric ozone-rich air masses through atmospheric subsidence significantly influences the boundary layer and surface ozone-mixing ratios. In particular, the geographic areas with observed tropospheric subsidence seem to be the transition regions between high-pressure and low-pressure systems. During the surface ozone episodes IASI satellite measurements show extended areas of high ozone in the lower- and upper-troposphere over the low-pressure system areas, adjacent to the anticyclones, which influence significantly the boundary layer and surface ozone-mixing ratios within the anticyclones by subsidence and advection in addition to the photochemically produced ozone there, resulting in exceedances of the 60 ppb standard.

A simple and complementary model evaluation technique for regional chemistry transport is discussed. The methodology is based on the concept that we can learn about model performance by comparing the simulation results with observational data available for time periods other than the period originally targeted. First, the statistical indicators selected in this study (spatial and temporal correlations) are computed for a given time period, using colocated observation and simulation data in time and space. Second, the same indicators are used to calculate scores for several other years while conserving the spatial locations and Julian days of the year. The difference between the results provides useful insights on the model capability to reproduce the observed day-to-day and spatial variability. In order to synthesize the large amount of results, a new indicator is proposed, designed to compare several error statistics between all the years of validation and to quantify whether the period and area being studied were well captured by the model for the correct reasons.

In this study, the performance of two types of source apportionment models was evaluated by assessing the results provided by 40 different groups in the framework of an intercomparison organised by FAIRMODE WG3 (Forum for air quality modelling in Europe, Working Group 3). The evaluation was based on two performance indicators: z-scores and the root mean square error weighted by the reference uncertainty (RMSEu), with pre-established acceptability criteria. By involving models based on completely different and independent input data, such as receptor models (RMs) and chemical transport models (CTMs), the intercomparison provided a unique opportunity for their cross-validation. In addition, comparing the CTM chemical profiles with those measured directly at the source contributed to corroborate the consistency of the tested model results. The most commonly used RM was the US EPA- PMF version 5. RMs showed very good performance for the overall dataset (91% of z-scores accepted) while more difficulties were observed with the source contribution time series (72% of RMSEu accepted). Industrial activities proved to be the most difficult sources to be quantified by RMs, with high variability in the estimated contributions. In the CTMs, the sum of computed source contributions was lower than the measured gravimetric PM10 mass concentrations. The performance tests pointed out the differences between the two CTM approaches used for source apportionment in this study: brute force (or emission reduction impact) and tagged species methods. The sources meeting the z-score and RMSEu acceptability criteria tests were 50% and 86%, respectively. The CTM source contributions to PM10 were in the majority of cases lower than the RM averages for the corresponding source. The CTMs and RMs source contributions for the overall dataset were more comparable (83% of the z-scores accepted) than their time series (successful RMSEu in the range 25% - 34%). The comparability between CTMs and RMs varied depending on the source: traffic/exhaust and industry were the source categories with the best results in the RMSEu tests while the most critical ones were soil dust and road dust. The differences between RMs and CTMs source reconstructions confirmed the importance of cross validating the results of these two families of models. Keywords: Source apportionment, PM10, Receptor models, Chemical transport models, Intercomparison, Lens

The aerosol speciation and size distribution is modeled during the summer 2013 and over a large area encompassing Africa, Mediterranean and western Europe. The modeled aerosol is compared to available measurements such as the AERONET aerosol optical depth (AOD) and aerosol size distribution (ASD) and the EMEP network for surface concentrations of particulate matter PM2.5, PM10 and inorganic species (nitrate, sulfate and ammonium). The main goal of this study is to quantify the model ability to realistically model the speciation and size distribution of the aerosol. Results first showed that the long-range transport pathways are well reproduced and mainly constituted by mineral dust: spatial correlation is ≈ 0.9 for AOD and Ångström exponent, when temporal correlations show that the day-to-day variability is more difficult to reproduce. Over Europe, PM2.5 and PM10 have a mean temporal correlation of ≈ 0.4 but the lowest spatial correlation ( ≈ 0.25 and 0.62, respectively), showing that the fine particles are not well localized or transported. Being short-lived species, the uncertainties on meteorology and emissions induce these lowest scores. However, time series of PM2.5 with the speciation show a good agreement between model and measurements and are useful for discriminating the aerosol composition. Using a classification from the south (Africa) to the north (northern Europe), it is shown that mineral dust relative mass contribution decreases from 50 to 10 % when nitrate increases from 0 to 20 % and all other species, sulfate, sea salt, ammonium, elemental carbon, primary organic matter, are constant. The secondary organic aerosol contribution is between 10 and 20 % with a maximum at the latitude of the Mediterranean Sea (Spanish stations). For inorganic species, it is shown that nitrate, sulfate and ammonium have a mean temporal correlation of 0.25, 0.37 and 0.17, respectively. The spatial correlation is better (0.25, 0.5 and 0.87), showing that the mean values may be biased but the spatial localization of sulfate and ammonium is well reproduced. The size distribution is compared to the AERONET product and it is shown that the model fairly reproduces the main values for the fine and coarse mode. In particular, for the fine mode, the model overestimates the aerosol mass in Africa and underestimates it in Europe.

The organic fraction of atmospheric aerosols has proven to be a critical element of air quality and climate issues. However, its composition and the aging processes it undergoes remain insufficiently understood. This work builds on laboratory knowledge to simulate the formation of oligomers from biogenic secondary organic aerosol (BSOA) in the troposphere at the continental scale. We compare the results of two different modeling approaches, a first-order kinetic process and a pH-dependent parameterization, both implemented in the CHIMERE air quality model (AQM) (www.lmd.polytechnique.fr/chimere), to simulate the spatial and temporal distribution of oligomerized secondary organic aerosol (SOA) over western Europe. We also included a comparison of organic carbon (OC) concentrations at two EMEP (European Monitoring and Evaluation Programme) stations. Our results show that there is a strong dependence of the results on the selected modeling approach: while the irreversible kinetic process leads to the oligomerization of about 50 % of the total BSOA mass, the pH-dependent approach shows a broader range of impacts, with a strong dependency on environmental parameters (pH and nature of aerosol) and the possibility for the process to be reversible. In parallel, we investigated the sensitivity of each modeling approach to the representation of SOA precursor solubility (Henry's law constant values). Finally, the pros and cons of each approach for the representation of SOA aging are discussed and recommendations are provided to improve current representations of oligomer formation in AQMs.

The Mediterranean basin is characterized by large concentrations of aerosols from both natural and anthropogenic sources. These aerosols affect tropospheric photochemistry by modulating the photolytic rates. Three simulations of the atmospheric composition at basin scale have been performed with the CHIMERE chemistry-transport model for the period from 6 June to 15 July 2013 covered by the ADRIMED campaign, a campaign of intense measurements in the western Mediterranean basin. One simulation takes into account the radiative effect of the aerosols on photochemistry, the second one does not, and the third one is designed to quantify the model sensitivity to a bias in the ozone column. These simulations are compared to satellite and ground-based measurements, with a particular focus on the area of Lampedusa. Values of the aerosol optical depth (AOD) are obtained from the MODIS instrument on the AQUA and TERRA satellites as well as from stations in the AERONET network and from the MFRSR sun photometer deployed at Lampedusa. Additional measurements from instruments deployed at Lampedusa either permanently or exceptionally are used for other variables: MFRSR sun photometer for AOD, diode array spectrometer for actinic fluxes, LIDAR for the aerosol backscatter, sequential sampler for speciation of aerosol and Brewer spectrophotometer for the total ozone column. It is shown that CHIMERE has a significant ability to reproduce observed peaks in the AOD, which in Lampedusa are mainly due to dust outbreaks during the ADRIMED period, and that taking into account the radiative effect of the aerosols in CHIMERE considerably improves the ability of the model to reproduce the observed day-to-day variations of the photolysis rate of ozone to O2 and O(1D), J(O1D), and that of NO2 to NO and O(3P), J(NO2). While in the case of J(O1D) other variation factors such as the stratospheric ozone column are very important in representing correctly the day-to-day variations, the day-to-day variations of J(NO2) are captured almost completely by the model when the optical effects of the aerosols are taken into account. Finally, it is shown that the inclusion of the direct radiative effect of the aerosols in the CHIMERE model leads to reduced J(O1D) and J(NO2) values over all the simulation domain, which range from a few percents over continental Europe and the north-east Atlantic Ocean to about 20 % close to and downwind from Saharan dust sources. The effect on the modelled ozone concentration is 2-fold: the effect of aerosols leads to reduced ozone concentrations over the Mediterranean Sea and continental Europe, close to the sources of NOx, but it also leads to increased ozone concentrations over remote areas such as the Sahara and the tropical Atlantic Ocean.

In the Mediterranean area, aerosols may originate from anthropogenic or natural emissions (biogenic, mineral dust, fire and sea salt) before undergoing complex chemistry. In case of a huge pollution event, it is important to know whether European pollution limits are exceeded and, if so, whether the pollution is due to anthropogenic or natural sources. In this study, the relative contribution of emissions to surface PM10, surface PM2.5 and total aerosol optical depth (AOD) is quantified. For Europe and the Mediterranean regions and during the summer of 2012, the WRF and CHIMERE models are used to perform a sensitivity analysis on a 50 km resolution domain (from −10° W to 40° E and from 30° N to 55° N): one simulation with all sources (reference) and all others with one source removed. The reference simulation is compared to data from the AirBase network and two ChArMEx stations, and from the AERONET network and the MODIS satellite instrument, to quantify the ability of the model to reproduce the observations. It is shown that the correlation ranges from 0.19 to 0.57 for surface particulate matter and from 0.35 to 0.75 for AOD. For the summer of 2012, the model shows that the region is mainly influenced by aerosols due to mineral dust and anthropogenic emissions (62 and 19 %, respectively, of total surface PM10 and 17 and 52 % of total surface PM2.5). The western part of the Mediterranean is strongly influenced by mineral dust emissions (86 % for surface PM10 and 44 % for PM2.5), while anthropogenic emissions dominate in the northern Mediterranean basin (up to 75 % for PM2.5). Fire emissions are more sporadic but may represent 20 % of surface PM2.5, on average, during the period near local sources. Sea salt mainly contributes for coastal sites (up to 29 %) and biogenic emissions mainly in central Europe (up to 20 %). The same analysis was undertaken for the number of daily exceedances of the European Union limit of 50 μg m−3 for PM10 (over the stations), and for the number of daily exceedances of the WHO recommendation for PM2.5 (25 μg m−3), over the western part of Europe and the central north. This number is generally overestimated by the model, particularly in the northern part of the domain, but exceedances are captured at the right time. Optimized contributions are computed with the observations, by subtracting the background bias at each station and the specific peak biases from the considered sources. These optimized contributions show that if natural sources such as mineral dust and fire events are particularly difficult to estimate, they were responsible exclusively for 35.9 and 0.7 %, respectively, of the exceedances for PM10 during the summer of 2012. The PM25 recommendation of 25 μg m−3 is exceeded in 21.1 % of the cases because of anthropogenic sources exclusively and in 0.02 % because of fires. The other exceedances are induced by a mixed contribution between mainly mineral dust (49.5–67 % for PM10 exceedance contributions, 4.4–13.8 % for PM2.5), anthropogenic sources (14.9–24.2 % and 46.3–80.6 %), biogenic sources (4.1–15.7 % and 12.6–30 %) and fires (2.2–7.2 % and 1.6–12.4 %).

We investigate how the representation of the boundary layer in a climate model impacts the representation of the near-surface wind and dust emission, with a focus on the Sahel/Sahara region. We show that the combination of vertical turbulent diffusion with a representation of the thermal cells of the convective boundary layer by a mass flux scheme leads to realistic representation of the diurnal cycle of wind in spring, with a maximum near-surface wind in the morning. This maximum occurs when the thermal plumes reach the low-level jet that forms during the night at a few hundred meters above surface. The horizontal momentum in the jet is transported downward to the surface by compensating subsidence around thermal plumes in typically less than 1 h. This leads to a rapid increase of wind speed at surface and therefore of dust emissions owing to the strong nonlinearity of emission laws. The numerical experiments are performed with a zoomed and nudged configuration of the LMDZ general circulation model coupled to the emission module of the CHIMERE chemistry transport model, in which winds are relaxed toward that of the ERA-Interim reanalyses. The new set of parameterizations leads to a strong improvement of the representation of the diurnal cycle of wind when compared to a previous version of LMDZ as well as to the reanalyses used for nudging themselves. It also generates dust emissions in better agreement with current estimates, but the aerosol optical thickness is still significantly underestimated.

During the months of June and July 2013, over the Euro–Mediterranean area, the ADRIMED (Aerosol Direct Radiative Impact on the regional climate in the MEDiterranean region) project was dedicated to characterize the ozone and aerosol concentrations in the troposphere. It is first shown that this period was not highly polluted compared to previous summers in this region, with a moderate ozone production, no significant vegetation fire events and several precipitation periods scavenging the aerosol. The period is modeled with the WRF (Weather Research and Forecasting) and CHIMERE models, and their ability to quantify the observed pollution transport events is presented. The CHIMERE model simulating all kinds of sources (anthropogenic, biogenic, mineral dust, vegetation fires); the aerosol speciation, not available with the measurements, is presented: during the whole period, the aerosol was mainly constituted by mineral dust, sea salt and sulfates close to the surface and mainly by mineral dust in the troposphere. Compared to the AERONET (Aerosol Robotic Network) size distribution, it is shown that the model underestimates the coarse mode near mineral dust sources and overestimates the fine mode in the Mediterranean area, highlighting the need to improve the model representation of the aerosol size distribution both during emissions, long-range transport and deposition.

Measurements of gaseous and particulate organic carbon were performed during the MEGAPOLI experiments, in July 2009 and January–February 2010, at the SIRTA observatory in suburban Paris. Measurements comprise primary and secondary volatile organic compounds (VOCs), of both anthropogenic and biogenic origins, including C12–C16 n-alkanes of intermediate volatility (IVOCs), suspected to be efficient precursors of secondary organic aerosol (SOA). The time series of gaseous carbon are generally consistent with times series of particulate organic carbon at regional scale, and are clearly affected by meteorology and air mass origin. Concentration levels of anthropogenic VOCs in urban and suburban Paris were surprisingly low (2–963 ppt) compared to other megacities worldwide and to rural continental sites. Urban enhancement ratios of anthropogenic VOC pairs agree well between the urban and suburban Paris sites, showing the regional extent of anthropogenic sources of similar composition. Contrary to other primary anthropogenic VOCs (aromatics and alkanes), IVOCs showed lower concentrations in winter (< 5 ppt) compared to summer (13–27 ppt), which cannot be explained by the gas-particle partitioning theory. Higher concentrations of most oxygenated VOCs in winter (18–5984 ppt) suggest their dominant primary anthropogenic origin. The respective role of primary anthropogenic gaseous compounds in regional SOA formation was investigated by estimating the SOA mass concentration expected from the anthropogenic VOCs and IVOCs (I / VOCs) measured at SIRTA. From an integrated approach based on emission ratios and SOA yields, 38 % of the SOA measured at SIRTA is explained by the measured concentrations of I / VOCs, with a 2% contribution by C12–C16 n-alkane IVOCs. From the results of an alternative time-resolved approach, the average IVOC contribution to SOA formation is estimated to be 7%, which is half of the average contribution of the traditional aromatic compounds (15%). Both approaches, which are based on in situ observations of particular I / VOCs, emphasize the importance of the intermediate volatility compounds in the SOA formation, and support previous results from chamber experiments and modeling studies. They also support the need to make systematic the IVOCs' speciated measurement during field campaigns.

Nitrous acid measurements were carried out during the MEGAPOLI summer and winter field campaigns at SIRTA observatory in Paris surroundings. Highly variable HONO levels were observed during the campaigns, ranging from 10 ppt to 500 ppt in summer and from 10 ppt to 1.7 ppb in winter. Significant HONO mixing ratios have also been measured during daytime hours, comprised between some tenth of ppt and 200 ppt for the summer campaign and between few ppt and 1 ppb for the winter campaign. Ancillary measurements, such as NOx, O3, photolysis frequencies, meteorological parameters (pressure, temperature, relative humidity, wind speed and wind direction), black carbon concentration, total aerosol surface area, boundary layer height and soil moisture, were conducted during both campaigns. In addition, for the summer period, OH radical measurements were made with a CIMS (Chemical Ionisation Mass Spectrometer). This large dataset has been used to investigate the HONO budget in a suburban environment. To do so, calculations of HONO concentrations using PhotoStationary State (PSS) approach have been performed, for daytime hours. The comparison of these calculations with measured HONO concentrations revealed an underestimation of the calculations making evident a missing source term for both campaigns. This unknown HONO source exhibits a bell-shaped like average diurnal profile with a maximum around noon of approximately 0.7 ppb h−1 and 0.25 ppb h−1, during summer and winter respectively. This source is the main HONO source during daytime hours for both campaigns. In both cases, this source shows a slight positive correlation with J(NO2) and the product between J(NO2) and soil moisture. This original approach had, thus, indicated that this missing source is photolytic and might be heterogeneous occurring at ground surface and involving water content available on the ground.

Tropospheric trace gas and aerosol pollutants have adverse effects on health, environment and climate. In order to quantify and mitigate such effects, a wide range of processes leading to the formation and transport of pollutants must be considered, understood and represented in numerical models. Regional scale pollution episodes result from the combination of several factors: high emissions (from anthropogenic or natural sources), stagnant meteorological conditions, kinetics and efficiency of the chemistry and the deposition. All these processes are highly variable in time and space, and their relative contribution to the pollutants budgets can be quantified with chemistry-transport models. The CHIMERE chemistry-transport model is dedicated to regional atmospheric pollution event studies. Since it has now reached a certain level a maturity, the new stable version, CHIMERE 2013, is described to provide a reference model paper. The successive developments of the model are reviewed on the basis of published investigations that are referenced in order to discuss the scientific choices and to provide an overview of the main results.

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.

Chemical Ionisation Mass Spectrometer measurements of hydroxyl radical (OH) and the sum of hydroperoxy and organic peroxy (HO2+RO2) radicals were conducted during the MEGAPOLI summer field campaign at the SIRTA observatory near Paris, France, in July 2009. OH and (HO2+RO2) showed a typical diurnal variation with averaged daytime maxima values around 5×106 and 1.2×108 molecule cm−3, respectively. Simultaneously, a large number of ancillary measurements, such as NOx, O3, HONO, HCHO and other VOCs were also conducted. These data provide an opportunity to assess our understanding of the radical chemistry in a suburban environment by comparing the radical observations to calculations. First, OH mixing ratios were estimated by a simple Photo Stationary State (PSS) calculation. PSS calculations overestimate the OH mixing ratio by 50%, especially at NOx mixing ratios lower than 10 ppb, suggesting that some loss processes were missing in the calculation at low NOx. Then, a photochemical box model simulation based on the Master Chemical Mechanism (MCM) and constrained by ancillary measurements was run to calculate radical concentrations. Three different modelling procedures were tested, varying the way the unconstrained secondary species were estimated, to cope with the unavoidable lack of their measurements. They led to significant differences in simulated radical concentrations. OH and (HO2+RO2) concentrations estimated by two selected model version were compared with measurements. These versions of the model were chosen because they lead, respectively, to the higher and lower simulated radical concentrations and are thus the two extremes versions. The box model showed better results than PSS calculations, with a slight overestimation of 12% and 5%, for OH and (HO2+RO2) respectively, in average for the reference model, and an overestimation of approximately 20% for OH and an underestimation for (HO2+RO2) for the other selected model version. Thus, we can conclude from our study that OH and (HO2+RO2) radical levels agree on average with observations within the uncertainty range. Finally, an analysis of the radical budget, on a daily basis (06:00–18:00 UTC), indicates that HONO photolysis (~35%), O3 photolysis (~23%), and aldehydes and ketones photolysis (~16% for formaldehyde and 18% for others) are the main radical initiation pathways. According to the MCM modelling, the reactions of RO2 with NO2 (~19%), leading mainly to PAN formation, is a significant termination pathway in addition to the main net loss via reaction of OH with NO2 (~50%).