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HBr emissions from volcanoes lead rapidly to the formation of BrO within volcanic plumes and have an impact on tropospheric chemistry, at least at the local and regional scales. The motivation of this paper is to prepare a framework for further 3D modelling of volcanic halogen emissions in order to determine their fate within the volcanic plume and then in the atmosphere at the regional and global scales. The main aim is to evaluate the ability of the model to produce a realistic partitioning of bromine species within a grid box size typical of MOCAGE (Model Of atmospheric Chemistry At larGE scale) 3D (0.5∘ × 0.5∘). This work is based on a 1D single-column configuration of the global chemistry-transport model MOCAGE that has low enough computational cost to allow us to perform a large set of sensitivity simulations. This paper uses the emissions from the Mount Etna eruption on 10 May 2008. Several reactions are added to MOCAGE to represent the volcanic plume halogen chemistry. A simple plume parameterisation is also implemented and tested. The use of this parameterisation tends to only slightly limit the efficiency of BrO net production. Both simulations with and without the parameterisation give results for the partitioning of the bromine species, of ozone depletion and of the BrO/SO2 ratio that are consistent with previous studies. A series of test experiments were performed to evaluate the sensitivity of the results to the composition of the emissions (primary sulfate aerosols, Br radical and NO) and to the effective radius assumed for the volcanic sulfate aerosols. Simulations show that the plume chemistry is sensitive to all these parameters. We also find that the maximum altitude of the eruption changes the BrO production, which is linked to the vertical variability of the concentrations of oxidants in the background air. These sensitivity tests display changes in the bromine chemistry cycles that are generally at least as important as the plume parameterisation. Overall, the version of the MOCAGE chemistry developed for this study is suitable to produce the expected halogen chemistry in volcanic plumes during daytime and night-time.

Volcanoes are known to be important emitters of atmospheric gases and aerosols, which for certain volcanoes can include halogen gases and in particular HBr. HBr emitted in this way can undergo rapid atmospheric oxidation chemistry (known as the bromine-explosion) within the volcanic emission plume leading to the production of bromine oxide (BrO) and ozone depletion. In this work, we present the results of a modelling study of a volcanic eruption from Mt Etna that occurred around Christmas 2018 that lasted 6 days. The aims of this study are to demonstrate and evaluate the ability of the regional 3D Chemistry Transport Model MOCAGE to simulate the volcanic halogen chemistry in this case study, to analyse the variability of the chemical processes during the plume transport, and to quantify its impact on the composition of the troposphere at a regional scale over the Mediterranean basin. The comparison of the tropospheric SO2 and BrO columns from 25 to 30 December 2018 from the MOCAGE simulation with the columns derived from the TROPOMI satellite measurements shows a very good agreement for the transport of the plumeand a good consistency for the concentrations if considering the uncertainties in the flux estimates and the TROPOMI columns. The analysis of the bromine species’ partitioning and of the associated chemical reaction rates provides a detailed picture of the simulated bromine chemistry throughout the diurnal cycle and at different stages of the volcanic plume’s evolution. The partitioning of the bromine species is modulated by the time evolution of the emissions during the 6 days of the eruption, by the meteorological conditions, and by the distance of the plume from the vent/the time since the emission. As the plume travels further from the vent, the halogen source gas HBr becomes depleted, BrO production in the plume becomes less efficient, and ozone depletion (proceeding via the Br + O3 reaction followed by the BrO self-reaction) decreases. The depletion of HBr relative to the other prevalent hydracid HCl leads to a shift in the relative concentrations of the Br− and Cl− ions, which in turn leads to reduced production of Br2 relative to BrCl. The MOCAGE simulations show a regional impact of the volcanic eruption on the oxidants OH and O3 with a reduced burden of both gases that is caused by the chemistry in the volcanic plume. This reduction in atmospheric oxidation capacity results in a reduced CH4 burden. Finally, sensitivity tests on the composition of the emissions carried out in this work show that the production of BrO is higher when the volcanic emissions of sulfate aerosols are increased but occurs very slowly when no sulfate and Br radicals are assumed to be in the emissions. Both sensitivity tests highlight a significant impact on the oxidants in the troposphere at the regional scale of these assumptions. All the results of this modelling study are consistent with the previous studies carried out on the volcanic halogens modelling.

Well constrained volcanic emissions inventories in chemistry transport models are necessary to study the impacts induced by these sources on the tropospheric sulfur composition and on sulfur species concentrations and depositions at the surface. In this paper, the changes induced by the update of the volcanic sulfur emissions inventory are studied using the global chemistry transport model MOCAGE (MOdele de Chimie Atmospherique a Grande Echelle). Unlike the previous inventory ( Andres and Kasgnoc , 1998 ) , the updated one ( Carn et al. , 2016 , 2017 ) uses more accurate information and includes contributions from both passive degassing and eruptive emissions. Eruptions are provided as daily total amounts of sulfur dioxide ( SO2 ) emitted by volcanoes in the Carn et al. ( 2016 , 2017 ) inventories, and degassing emissions are provided as annual averages with the related mean annual uncertainties of those emissions by volcano. Information on plume altitudes is also available and has been used in the model. We chose to analyze the year 2013, for which only a negligible amount of eruptive volcanic SO2 emissions is reported, allowing us to focus the study on the impact of passive degassing emissions on the tropospheric sulfur budget. An evaluation against the Ozone Monitoring Instrument (OMI) SO2 total column and MODIS (Moderate-Resolution Imaging Spectroradiometer) aerosol optical depth (AOD) observations shows the improvements of the model results with the updated inventory. Because the global volcanic SO2 flux changes from 13 Tg yr−1 in Andres and Kasgnoc ( 1998 ) to 23.6 Tg yr−1 in Carn et al. ( 2016 , 2017 ) , significant differences appear in the global sulfur budget, mainly in the free troposphere and in the tropics. Even though volcanic SO2 emissions represent 15 % of the total annual sulfur emissions, the volcanic contribution to the tropospheric sulfate aerosol burden is 25 %, which is due to the higher altitude of emissions from volcanoes. Moreover, a sensitivity study on passive degassing emissions, using the annual uncertainties of emissions per volcano, also confirmed the nonlinear link between tropospheric sulfur species content with respect to volcanic SO2 emissions. This study highlights the need for accurate estimates of volcanic sources in chemistry transport models in order to properly simulate tropospheric sulfur species.

Volcanoes are known to be important emitters of atmospheric gases and aerosols, both through explosive eruptions and persistent quiescent degassing (von Glasow et al., 2009). The most abundant gases in volcanic emissions are H2O, CO2, SO2 and halogens (HCl, HBr, HF). In general, halogens play an important role in the atmosphere by modifying air composition and oxidizing capacity in the troposphere (von Glasow et al., 2004). The chemical processes occurring within the plume lead to the formation of BrO following the ‘bromine explosion’ mechanism as evidenced from both observations and modelling (e.g. Bobrowski et al., 2003; Roberts et al., 2009). Oxidized forms of bromine (BrO) are formed during daytime within the plume due to heterogeneous reactions of HBr on volcanic aerosols leading to ozone depletion. So far, modelling studies mainly focused on spatial scales ranging from 10m to ~1km and processes occurring within a few hours after eruption.The objective of this study is to go a step further by analysing the impact at the regional scale namely over the whole Mediterranean basin of a single Mt Etna eruption event in December 2018. For this, we have further developed the MOCAGE model (Guth et al., 2016), a chemistry transport model run at a resolution of 0.2°× 0.2°, to quantify the impacts of the halogen species emitted by the volcano on air composition. We selected here the case of the eruption of Mt Etna around Christmas 2018 characterised by large amounts of emissions over several days. The results show that MOCAGE represents the halogen chemistry in the volcanic plume quite well. The bromine-explosion cycle takes place during the day of the eruption, with a rapid increase in BrO concentration leading to a strong depletion in ozone and NO₂ concentrations across the Mediterranean as well as to changes in the air composition in particular for bromine compounds such as Br, HOBr, BrONO₂, Br2 and BrCl. Adding to this, BrO is formed again on the following day (25/12/2018) during daytime from the bromine reservoir species from night time leading to additional ozone depletion.The comparison of the tropospheric columns of BrO and SO2 retrievals from the TROPOMI spaceborne instrument with the MOCAGE simulations shows that the tropospheric BrO and SO₂ columns have the same order of magnitude and that the locations of the simulated and observed plumes are overall in good agreement during the main eruption period and the following six days. The comparison shows also the similarity of the order of magnitude of the BrO/SO2 ratio between MOCAGE and TROPOMI, especially for the 25th of December 2018.

We report on an evaluation of tropospheric ozone and its precursor gases in three atmospheric chemistry versions as implemented in the European Centre for Medium-Range Weather Forecasts (ECMWF) Integrated Forecasting System (IFS), referred to as IFS(CB05BASCOE), IFS(MOZART) and IFS(MOCAGE). While the model versions were forced with the same overall meteorology, emissions, transport and deposition schemes, they vary largely in their parameterisations describing atmospheric chemistry, including the organics degradation, heterogeneous chemistry and photolysis, as well as chemical solver. The model results from the three chemistry versions are compared against a range of aircraft field campaigns, surface observations, ozone-sondes and satellite observations, which provides quantification of the overall model uncertainty driven by the chemistry parameterisations. We find that they produce similar patterns and magnitudes for carbon monoxide (CO) and ozone (O3), as well as a range of non-methane hydrocarbons (NMHCs), with averaged differences for O3 (CO) within 10 % (20 %) throughout the troposphere. Most of the divergence in the magnitude of CO and NMHCs can be explained by differences in OH concentrations, which can reach up to 50 %, particularly at high latitudes. There are also comparatively large discrepancies between model versions for NO2, SO2 and HNO3, which are strongly influenced by secondary chemical production and loss. Other common biases in CO and NMHCs are mainly attributed to uncertainties in their emissions. This configuration of having various chemistry versions within IFS provides a quantification of uncertainties induced by chemistry modelling in the main CAMS global trace gas products beyond those that are constrained by data assimilation.

Halogen halides emitted by volcanoes are known to rapidly convert within plumes into BrO while depleting ozone, as clearly shown by observations and models over the past 2 decades (e.g. review by Gutmann et al., 2018). So far, most of the modelling studies have focused on the plume processes occurring in the first few hours after the emission. The only study at the regional scale is that of Jourdain et al. (2016). They assessed the impact of volcanic halogens for a period of strong degassing of the Ambrym volcano, showing in particular its effect on the atmospheric oxidizing capacity and methane lifetime.A step further would be to quantify the impact of volcanic halogens at the global scale using global chemistry models. This type of model uses a horizontal resolution (greater than 50 km) that is much coarser than the plume size. This raises the issue of, whether at this resolution, it is possible to represent the chemistry occurring under high concentrations within the plume. To assess this, a sub-grid scale parameterization is proposed. It has been tested in the 1D version of MOCAGE global and regional chemistry transport model for a short eruption of Mt Etna on the 10th of May 2008. The results show that while using the subgrid-scale plume parameterization or not does change the timing of when the maximum BrO occurs but does not affect the predicted maximum concentration. The same finding is made when using a range of different settings in the parameterization regarding dilution of the plume with its environment. The 1D model results show a sensitivity of BrO formation to parameters other than the sub-grid scale effects: composition of the plume at the vent, injection height of the emissions, and time of the day when the eruption takes place.

Volcanic eruptions are events that can eject several tons of material into the atmosphere. Among these emissions, sulfur dioxide is the main sulfurous volcanic gas. It can form sulfate aerosols that are harmful to health or, being highly soluble, it can condense in water particles and form acid rain. Thus, volcanic eruptions can have an environmental impact on a regional scale.The Mediterranean region is very interesting from this point of view because it is a densely populated region with a strong anthropogenic activity, therefore polluted, in which Mount Etna is also located. Mount Etna is the largest passive SO2 emitter in Europe, but it can also sporadically produce strong eruptive events. It is then likely that the additional input of sulfur compounds into the atmosphere by volcanic emissions may have effects on the regional atmospheric sulfur composition.We are particularly investigating the eruption of Mount Etna on December 24, 2018 [Corradini et al, 2020]. This eruption took place along a 2 km long breach on the side of the volcano, thus at a lower altitude than its main crater. About 100 kt of SO2 and 35 kt of ash were released in total, between December 24 and 30. With the exception of the 24th, the quantities of ash were always lower than the SO2.The availability of the TROPOMI SO2column estimates, at fine spatial resolution (7 km x 3.5 km at nadir) and associated averaging kernels, during this eruptive period made it also an excellent case study. It allows us to follow the evolution of SO2 in the volcanic plume over several days.Using the CNRM MOCAGE chemistry-transport model (CTM), we aim to quantify the impact of this volcanic eruption on atmospheric composition, sulfur deposition and air quality at the regional scale. The comparison of the model with the TROPOMI observation data allows us to assess the ability of the model to properly represent the plume. In spite of a particular meteorological situation, leading to a complex plume transport, MOCAGE shows a good agreement with TROPOMI observations. Thus, from the MOCAGE simulation, we can evaluate the impact of the eruption on the regional concentrations of SO2 and sulfate aerosols, but also analyse the quantities of dry and wet deposition, and compare it to surface measurement stations.

Numerical dispersion models are used operationally worldwide to mitigate the effect of volcanic ash on aviation. In order to improve the representation of the horizontal dispersion of ash plumes and of the 3D concentration of ash, a study was conducted using the MOCAGE model during the European Natural Airborne Disaster Information and Coordination System for Aviation (EUNADICS-AV) project. Source term modelling and assimilation of different data were investigated. A sensitivity study of source term formulation showed that a resolved source term, using the FPLUME plume rise model in MOCAGE, instead of a parameterised source term, induces a more realistic representation of the horizontal dispersion of the ash plume. The FPLUME simulation provides more concentrated and focused ash concentrations in the horizontal and the vertical dimensions than the other source term. The assimilation of Moderate Resolution Imaging Spectroradiometer (MODIS) aerosol optical depth has an impact on the horizontal dispersion of the plume, but this effect is rather low and local compared to source term improvement. More promising results are obtained with the continuous assimilation of ground-based lidar profiles, which improves the vertical distribution of ash and helps in reaching realistic values of ash concentrations. Using this configuration, the effect of assimilation may last for several hours and it may propagate several hundred kilometres downstream of the lidar profiles.

The contribution of volcanic emissions is argued as non-linear on the sulfur species burden. Thus, well constraining volcanic emissions inventories is necessary to better study the impacts induced by these pollution sources on the troposheric sulfur composition, as well as on sulfur species concentrations and depositions at the global surface. In this paper, the changes induced by the update of the volcanic sulfur emissions inventory on the global chemistry-transport model MOCAGE (MOdèle de Chimie Atmosphérique à Grande Échelle) are studied. Unlike the current inventory [Andres and Kasgnoc (1998)], the new inventory [Carn et al. (2016, 2017)] includes contributions from both passive degassing and eruptive emissions with more accu- rate information. Eruptions are provided as daily total amounts of sulfur dioxide (SO2) emitted by volcanoes, while degassing are provided as annual averages with annual uncertainties by volcanoes. Information on plumes altitudes is also available and has been used in the model. The choice is made to look at the year 2013, when a neglieable amount of eruptive volcanic SO2 emissions is referenced, allowing us to focus the study on the impact of passive degassing emissions on the tropospheric sulfur budget. A validation against GOME-2 SO2 total column and MODIS AOD observations shows the improvements of the model results with the new inventory. Because the global volcanic SO2 flux changes from 13 Tg.yr−1 in the current inventory to 23.6 Tg.yr−1 in the new inventory, the updated inventory shows significant differences in the global sulfur budget, mainly in the free troposphere and in the tropics. Even though volcanic SO2 emissions represent 15 % of the total annual sulfur emissions, the volcanic contribution to the tropospheric sulfate aerosol burden is 27 %. Moreover, a sensitivity study on passive degassing emissions, using the annual uncertainties of emissions per volcanoes, also confirmed the non-linear link between tropospheric sulfur species and volcanic emissions. This study highlights the necessity of using accurate estimates of volcanic sources in chemistry-transport models in order to properly simulate tropospheric sulfur species.

Constraining emission inventories into chemistry-transport models (CTM) is essential. In addition to anthropogenic emissions, natural sources of pollutants must be considered. Among them, volcanoes are large emitters of gases, including sulfur dioxide (SO2), a volatile species, causing environmental and health issues.Volcanic SO2 emission inventories are usually integrated in global CTMs, in order to improve the modelling of chemical species in the atmosphere. Here, we use the model MOCAGE, developed at CNRM, which currently uses Andres & Krasgnoc’s inventory (1998); a temporal average of emission on some 40 volcanoes, monitored through the synergy of satellite data and surface remote sensing instruments, for 25 years (from 1970’s to 1997). However, this inventory is now quite old and is therefore no longer sufficiently accurate.Thanks to the development of new satellite observations, it has become possible to produce such inventories with an improved accuracy. The global coverage and higher sensitivity of these instruments has allowed to reference more emission sources (hard-to-access volcanoes, small eruptions or even passive degassing). Hence, a new inventory of Carn et al (2016,2017) based on satellite observations has been implemented in MOCAGE. Besides being recent (from 1978 up to 2015), it combines eruption and passive degassing over more than 160 volcanoes. Passive degassing fluxes are provided as annual averages and eruption fluxes as daily total quantities (in case of events). In addition, information on volcanoes vent altitude and eruptive plume heights is available, which has been used to better constraints the model.We focus our study at the global scale. The years 2013 and 2014 were chosen as the years with the lowest and highest total eruptive emissions respectively, in Carn's inventory. Thus, 2013 highlights mainly the impact of passive degassing, while 2014 provides additional information on eruptions.For each of the years studied, the sulfur species budget in MOCAGE simulation is increased when the inventory is updated and therefore the relative contribution of volcanic sulfur emissions is larger. We note the global increase in sulfur dioxide and sulfate aerosol burdens; an increase even more significant when the injection heights of the emissions are taken into account.

Since the first International Cooperative for Aerosol Prediction (ICAP) multi‐model ensemble (MME) study, the number of ICAP global operational aerosol models has increased from five to nine. An update of the current ICAP status is provided, along with an evaluation of the performance of ICAP‐MME over 2012–2017, with a focus on June 2016–May 2017. Evaluated with ground‐based Aerosol Robotic Network (AERONET) aerosol optical depth (AOD) and data assimilation quality MODerate‐resolution Imaging Spectroradiometer (MODIS) retrieval products, the ICAP‐MME AOD consensus remains the overall top‐scoring and most consistent performer among all models in terms of root‐mean‐square error (RMSE), bias and correlation for total, fine‐ and coarse‐mode AODs as well as dust AOD; this is similar to the first ICAP‐MME study. Further, over the years, the performance of ICAP‐MME is relatively stable and reliable compared to more variability in the individual models. The extent to which the AOD forecast error of ICAP‐MME can be predicted is also examined. Leading predictors are found to be the consensus mean and spread. Regression models of absolute forecast errors were built for AOD forecasts of different lengths for potential applications. ICAP‐MME performance in terms of modal AOD RMSEs of the 21 regionally representative sites over 2012–2017 suggests a general tendency for model improvements in fine‐mode AOD, especially over Asia. No significant improvement in coarse‐mode AOD is found overall for this time period., International Cooperative for Aerosol Predictions (ICAP) model 550 nm total AOD RMSE of the 72 h forecast versus corresponding mean AODs for AERONET sites listed in Table 2. Large black dots are ICAP multi‐model ensemble consensus means. Individual models are in small coloured dots. Validation of fine‐ and coarse‐modal AODs and dust AOD is also available in Figure 2.

We report on an evaluation of tropospheric ozone and its precursor gases in three atmospheric chemistry versions as implemented in ECMWF’s Integrated Forecasting System (IFS), referred to as IFS(CB05BASCOE), IFS(MOZART) and IFS(MOCAGE). While the model versions were forced with the same overall meteorology, emissions, transport and deposition schemes, they vary largely in their parameterizations describing atmospheric chemistry, including the organics degradation, heterogeneous chemistry and photolysis, as well as chemical solver. The model results from the three chemistry versions are compared against a range of aircraft field campaigns, ozone sondes and satellite observations, which provides quantification of the overall model uncertainty driven by the chemistry parameterizations. We find that they produce similar patterns and magnitudes for carbon monoxide (CO) and ozone (O3), as well as a range of non-methane hydrocarbons (NMHCs), with averaged differences for O3 (CO) within 10 % (20 %) throughout the troposphere. Most of the divergence in the magnitude of NMHCs can be explained by differences in OH concentrations, which can reach up to 50 % particularly at high latitudes. Also comparatively large discrepancies between model versions exist for NO2, SO2 and HNO3, which are strongly influenced by secondary chemical production and loss. Other, common biases in CO and NMHCs are mainly attributed to uncertainties in their emissions. This configuration of having various chemistry versions within IFS provides a quantification of uncertainties induced by chemistry modeling in the main CAMS global trace gas products beyond those that are constrained by data-assimilation.

International audience; The Mediterranean Basin (MB) is at the crossroad of pollutant emissions from Western and Central Europe and of mineral dust from major sources in the Sahara and Arabian deserts. Several studies (e.g. Formenti et al., J. Geophys. Res., 2002; Pace et al., J. Geophys. Res., 2005; Ancellet et al., Atmos. Chem. Phys., 2016) have also shown the occurrence over the MB of long-range transport of air masses polluted by biomass burning aerosols. In the present study, we report two cases of long-range intercontinental transport of biomass burning products in the free troposphere over the MB in August 2014, identified with in situ measurements, and evaluate their impact on trace gas concentrations using modelling The Gradient in Longitude of Atmospheric constituents above the Mediterranean basin (GLAM) airborne campaign occurred in August 2014 (Ricaud et al., BAMS, 2018), as part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) project. It aimed at studying the tropospheric chemical variability of gaseous pollutants and aerosols along a West-East transect above the MB. During the GLAM campaign, several instruments were deployed onboard the Falcon-20 research aircraft (SAFIRE, INSU & Météo-France) including an infrared laser spectrometer (SPIRIT, LPC2E) able to detect weak variations in the concentration of pollutants. During two flights on 6 and 10 August, increases in CO, O3 and aerosols were measured over Sardinia at 5.4 and 9.7 km above sea level, respectively. To assess the origin of the air masses, 20-day backward trajectories were calculated with a nested-grid regional scale Lagrangian particle dispersion model (FLEXPART; Stohl et al., Atmos. Chem. Phys., 2005). Combined with emissions coming from the Global Fire Assimilation System (GFAS) inventory (Kaiser et al., Biogeosci., 2012), this allows us to quantify the biomass burning contribution to CO aircraft measured values. Biomass burning products came on 10 August from the northern American continent with air masses transported during 5 days before arriving over the MB. On 6 August biomass burning products came from Siberia with air masses travelling during 12 days and enriched in fire emission products above Canada 5 days before arriving over the MB. By estimating the injection height of the model and amplifying emission fluxes, FLEXPART was able to reproduce the contribution of those fires to CO enhancements. Our measurements show that long-range transport of biomass burning induced, at the local scale, an increase by a factor of 1.7 to 3.7 of O3 and CO with background mixing ratios of ∼25 and ∼70 ppbv respectively. To assess the biomass burning effect on ozone level at the regional scale over the MB, its tropospheric increase is estimated by using the chemical transport model MOCAGE.

In the frame of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), we analyse the budget of primary aerosols and secondary inorganic aerosols over the Mediterranean Basin during the years 2012 and 2013. To do this, we use two year-long numerical simulations with the chemistry-transport model MOCAGE validated against satellite- and ground-based measurements. The budget is presented on an annual and a monthly basis on a domain covering 29 to 47° N latitude and 10° W to 38° E longitude. The years 2012 and 2013 show similar seasonal variations. The desert dust is the main contributor to the annual aerosol burden in the Mediterranean region with a peak in spring, and sea salt being the second most important contributor. The secondary inorganic aerosols, taken as a whole, contribute a similar level to sea salt. The results show that all of the considered aerosol types, except for sea salt aerosols, experience net export out of our Mediterranean Basin model domain, and thus this area should be considered as a source region for aerosols globally. Our study showed that 11 % of the desert dust, 22.8 to 39.5 % of the carbonaceous aerosols, 35 % of the sulfate and 9 % of the ammonium emitted or produced into the study domain are exported. The main sources of variability for aerosols between 2012 and 2013 are weather-related variations, acting on emissions processes, and the episodic import of aerosols from North American fires. In order to assess the importance of the anthropogenic emissions of the marine and the coastal areas which are central for the economy of the Mediterranean Basin, we made a sensitivity test simulation. This simulation is similar to the reference simulation but with the removal of the international shipping emissions and the anthropogenic emissions over a 50 km wide band inland along the coast. We showed that around 30 % of the emissions of carbonaceous aerosols and 35 to 60 % of the exported carbonaceous aerosols originates from the marine and coastal areas. The formation of 23, 27 and 27 %, respectively of, ammonium, nitrate and sulfate aerosols is due to the emissions within the marine and coastal area.

The Gradient in Longitude of Atmospheric constituents above the Mediterranean basin (GLAM) campaign was set up in August 2014, as part of the Chemistry and Aerosol Mediterranean Experiment (ChArMEx) project. This campaign aimed to study the chemical variability of gaseous pollutants and aerosols in the troposphere along a west–east transect above the Mediterranean Basin (MB). In the present work, we focus on two biomass burning events detected at 5.4 and 9.7 km altitude above sea level (a.s.l.) over Sardinia (from 39∘12′ N–9∘15′ E to 35∘35′ N–12∘35′ E and at 39∘30′ N–8∘25′ E, respectively). Concentration variations in trace gas carbon monoxide (CO), ozone (O3) and aerosols were measured thanks to the standard instruments on board the Falcon 20 aircraft operated by the Service des Avions Français Instrumentés pour la Recherche en Environnement (SAFIRE) and the Spectromètre InfraRouge In situ Toute Altitude (SPIRIT) developed by LPC2E. Twenty-day backward trajectories with Lagrangian particle dispersion model FLEXPART (FLEXible PARTicle) help to understand the transport processes and the origin of the emissions that contributed to this pollution detected above Sardinia. Biomass burning emissions came (i) on 10 August from the North American continent with air masses transported during 5 days before arriving over the MB, and (ii) on 6 August from Siberia, with air masses travelling during 12 days and enriched in fire emission products above Canada 5 days before arriving over the MB. In combination with the Global Fire Assimilation System (GFAS) inventory and the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite fire locations, FLEXPART reproduces well the contribution of those fires to CO and aerosols enhancements under adjustments of the injection height to 10 km in both cases and application of an amplification factor of 2 on CO GFAS emissions for the 10 August event. The chemistry transport model (CTM) MOCAGE is used as a complementary tool for the case of 6 August to confirm the origin of the emissions by tracing the CO global atmospheric composition reaching the MB. For this event, both models agree on the origin of air masses with CO concentrations simulated with MOCAGE lower than the observed ones, likely caused by the coarse model horizontal resolution that yields the dilution of the emissions and diffusion during transport. In combination with wind fields, the analysis of the transport of the air mass documented on 6 August suggests the subsidence of CO pollution from Siberia towards North America and then a transport to the MB via fast jet winds located at around 5.5 km in altitude. Finally, using the ratio ΔO3 ∕ ΔCO, the plume age can be estimated and the production of O3 during the transport of the air mass is studied using the MOCAGE model.

The Gradient in Longitude of Atmospheric constituents above the Mediterranean basin (GLAM) campaign was set up in August 2014, as part of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx) project. This campaign aimed at studying the chemical variability of gaseous pollutants and aerosols in the troposphere along a West-East transect above the Mediterranean Basin (MB). In the present work, we focus on two biomass burning events detected at 5.4 and 9.7 km altitude above sea level (asl) above Sardinia (from 39°12 N–9°15 E to 35°35 N–12°35 E and at 39°30 N–8°25 E, respectively). Concentration variations in trace gas carbon monoxide (CO) and aerosols were measured thanks to the standard instruments on-board the Falcon-20 aircraft operated by the Service des Avions Français Instrumentés pour la Recherche en Environnement (SAFIRE) and the Spectromètre InfraRouge In situ Toute Altitude (SPIRIT) developed by LPC2E. 20-day backward trajectories with Lagrangian particle dispersion model FLEXPART (FLEXible PARTicle) help understanding the transport processes and the origin of the emissions that contributed to these pollutions detected above Sardinia. Biomass burning emissions came (i) on 10 August from the Northern American continent with air masses transported during 5 days before arriving over the MB, and (ii) on 6 August from Siberia with air masses travelling during 12 days and enriched in fire emission products above Canada 5 days before arriving over the MB. In combination with the Global Fire Assimilation System (GFAS) inventory and the Moderate Resolution Imaging Spectroradiometer (MODIS) satellite fire locations, FLEXPART reproduces well the contribution of those fires to CO and aerosols enhancements under adjustments of the injection height to 10 km in both cases, and application of an amplification factor of 2.5 on CO GFAS emissions for the 10 August event. The chemistry transport model (CTM) MOCAGE is used as a complementary tool for the case of 6 August to confirm the origin of the emissions by tracing the CO global atmospheric composition reaching the MB. For this event, both models agree on the origin of air masses with CO concentrations simulated with MOCAGE lower than the observed ones, likely caused by the coarse model horizontal resolution that yields the dilution of the emissions and diffusion during transport. In combination with wind fields, the analysis of the transport of the air mass documented on 6 August suggests the subsidence of CO pollution from Siberia towards North America and then a transport to the MB via fast jet winds located at around 5.5 km in altitude.

Atmospheric pollution is an environmental problem our modern societies have to face with. The Mediterranean basin is a sensible region to atmospheric pollution, especially for air quality issues.

In the frame of the Chemistry-Aerosol Mediterranean Experiment (ChArMEx), we analyse the budget of primary aerosols and secondary inorganic aerosols over the Mediterranean basin during the years 2012 and 2013. To do this, we use a two-years long numerical simulation with the Chemistry-Transport Model MOCAGE validated against satellite and ground based measurements. The budget is presented on an annual and a monthly basis on a domain covering 29° North to 47° North latitude and 10° West to 38° East longitude. The years 2012 and 2013 show similar seasonal variations. The desert dust is the main contributor to the annual burden in the Mediterranean region with a peak in spring. The secondary inorganic aerosols, taken as a whole, also contribute significantly as well as sea salts. Sulphate aerosols have a maximum in summer and sea salts in winter, while nitrate and ammonium aerosols do not exhibit large seasonal changes. The results show that all the considered types of aerosols, except for sea salt aerosols, have a net import/export term that is negative, meaning that aerosols emitted and chemically produced within the domain are transported out, with high values for some of them. For example, around 40 % of the emitted black carbon are exported. The main sources of changes between 2012 and 2013 are wind variations acting on the desert dust emissions and the import of aerosols from North American fires. In order to assess the importance of the emissions of the marine and the coastal areas, we made a sensitivity test simulation. This simulation is similar to the first one but with the removal of the anthropogenic emissions over the sea and over a 50 km wide band inland along the coast. It shows that about a third of the aerosols emitted and chemically produced and about a half of the exported part in the Mediterranean basin originate from the marine and coastal area, meaning that anthropogenic air pollution from primary aerosols and secondary inorganic aerosols in this region mainly comes from local emissions.

In this study we develop a secondary inorganic aerosol (SIA) module for the MOCAGE chemistry transport model developed at CNRM. The aim is to have a module suitable for running at different model resolutions and for operational applications with reasonable computing times. Based on the ISORROPIA II thermodynamic equilibrium module, the new version of the model is presented and evaluated at both the global and regional scales. The results show high concentrations of secondary inorganic aerosols in the most polluted regions: Europe, Asia and the eastern part of North America. Asia shows higher sulfate concentrations than other regions thanks to emission reductions in Europe and North America. Using two simulations, one with and the other without secondary inorganic aerosol formation, the global model outputs are compared to previous studies, to MODIS AOD retrievals, and also to in situ measurements from the HTAP database. The model shows a better agreement with MODIS AOD retrievals in all geographical regions after introducing the new SIA scheme. It also provides a good statistical agreement with in situ measurements of secondary inorganic aerosol composition: sulfate, nitrate and ammonium. In addition, the simulation with SIA generally gives a better agreement with observations for secondary inorganic aerosol precursors (nitric acid, sulfur dioxide, ammonia), in particular with a reduction of the modified normalized mean bias (MNMB). At the regional scale, over Europe, the model simulation with SIA is compared to the in situ measurements from the EMEP database and shows a good agreement with secondary inorganic aerosol composition. The results at the regional scale are consistent with those obtained from the global simulations. The AIRBASE database was used to compare the model to regulated air quality pollutants: particulate matter, ozone and nitrogen dioxide concentrations. Introduction of the SIA in MOCAGE provides a reduction in the PM2.5 MNMB of 0.44 on a yearly basis and up to 0.52 for the 3 spring months (March, April, May) when SIAs are at their maximum.

MOCAGE is the 3D global off-line chemistry transport model (CTM) run at Meteo-France since 2005 for air quality operational forecasts. Three nested domains are used, with decreasing resolutions (globe, Europe, and France), and 47 vertical levels (from the surface to 5 hPa). For the global and the European domain, input meteorological forcing fields are Meteo-France ARPEGE forecasts. For France, and for the first day of forecast, MOCAGE uses the operational outputs of Meteo-France non-hydrostatic AROME model. This high-resolution (2.5 km) meteorological model is supposed to better represent urban processes (e.g., the urban heat island), which are of strong interest for air quality applications. The purpose of this study is to test the increase of resolution of the CTM MOCAGE over France from 0.1° to 0.025° (i.e. the native resolution of the input meteorological fields).

In this study we develop a Secondary Inorganic Aerosol (SIA) module for the chemistry transport model MOCAGE developed at CNRM. Based on the thermodynamic equilibrium module ISORROPIA II, the new version of the model is evaluated both at the global scale and at the regional scale. The results show high concentrations of secondary inorganic aerosols in the most polluted regions being Europe, Asia and the eastern part of North America. Asia shows higher sulfate concentrations than other regions thanks to emissions reduction in Europe and North America. Using two simulations, one with and the other without secondary inorganic aerosol formation, the model global outputs are compared to previous studies, to MODIS AOD retrievals, and also to in situ measurements from the HTAP database. The model shows a better agreement in all geographical regions with MODIS AOD retrievals when introducing SIA. It also provides a good statistical agreement with in situ measurements of secondary inorganic aerosol composition: sulfate, nitrate and ammonium. In addition, the simulation with SIA gives generally a better agreement for secondary inorganic aerosols precursors (nitric acid, sulfur dioxide, ammonia) in particular with a reduction of the Modified Normalised Mean Bias (MNMB). At the regional scale, over Europe, the model simulation with SIA are compared to the in situ measurements from the EMEP database and shows a good agreement with secondary inorganic aerosol composition. The results at the regional scale are consistent with those obtained with the global simulations. The AIRBASE database was used to compare the model to regulated air quality pollutants being particulate matter, ozone and nitrogen dioxide concentrations. The introduction of the SIA in MOCAGE provides a reduction of the PM2.5 MNMB of 0.44 on a yearly basis and even 0.52 on a three spring months period (March, April, May) when SIA are maximum.

This paper describes the pre-operational analysis and forecasting system developed during MACC (Monitoring Atmospheric Composition and Climate) and continued in the MACC-II (Monitoring Atmospheric Composition and Climate: Interim Implementation) European projects to provide air quality services for the European continent. This system is based on seven state-of-the art models developed and run in Europe (CHIMERE, EMEP, EURAD-IM, LOTOS-EUROS, MATCH, MOCAGE and SILAM). These models are used to calculate multi-model ensemble products. The paper gives an overall picture of its status at the end of MACC-II (summer 2014) and analyses the performance of the multi-model ensemble. The MACC-II system provides daily 96 h forecasts with hourly outputs of 10 chemical species/aerosols (O3, NO2, SO2, CO, PM10, PM2.5, NO, NH3, total NMVOCs (non-methane volatile organic compounds) and PAN+PAN precursors) over eight vertical levels from the surface to 5 km height. The hourly analysis at the surface is done a posteriori for the past day using a selection of representative air quality data from European monitoring stations. The performance of the system is assessed daily, weekly and every 3 months (seasonally) through statistical indicators calculated using the available representative air quality data from European monitoring stations. Results for a case study show the ability of the ensemble median to forecast regional ozone pollution events. The seasonal performances of the individual models and of the multi-model ensemble have been monitored since September 2009 for ozone, NO2 and PM10. The statistical indicators for ozone in summer 2014 show that the ensemble median gives on average the best performances compared to the seven models. There is very little degradation of the scores with the forecast day but there is a marked diurnal cycle, similarly to the individual models, that can be related partly to the prescribed diurnal variations of anthropogenic emissions in the models. During summer 2014, the diurnal ozone maximum is underestimated by the ensemble median by about 4 μg m−3 on average. Locally, during the studied ozone episodes, the maxima from the ensemble median are often lower than observations by 30–50 μg m−3. Overall, ozone scores are generally good with average values for the normalised indicators of 0.14 for the modified normalised mean bias and of 0.30 for the fractional gross error. Tests have also shown that the ensemble median is robust to reduction of ensemble size by one, that is, if predictions are unavailable from one model. Scores are also discussed for PM10 for winter 2013–1014. There is an underestimation of most models leading the ensemble median to a mean bias of −4.5 μg m−3. The ensemble median fractional gross error is larger for PM10 (~ 0.52) than for ozone and the correlation is lower (~ 0.35 for PM10 and ~ 0.54 for ozone). This is related to a larger spread of the seven model scores for PM10 than for ozone linked to different levels of complexity of aerosol representation in the individual models. In parallel, a scientific analysis of the results of the seven models and of the ensemble is also done over the Mediterranean area because of the specificity of its meteorology and emissions. The system is robust in terms of the production availability. Major efforts have been done in MACC-II towards the operationalisation of all its components. Foreseen developments and research for improving its performances are discussed in the conclusion.

This paper deals with recent improvements to the global chemical transport model of Météo-France MOCAGE (Modèle de Chimie Atmosphérique à Grande Echelle) that consists of updates to different aerosol parameterizations. MOCAGE only contains primary aerosol species: desert dust, sea salt, black carbon, organic carbon, and also volcanic ash in the case of large volcanic eruptions. We introduced important changes to the aerosol parameterization concerning emissions, wet deposition and sedimentation. For the emissions, size distribution and wind calculations are modified for desert dust aerosols, and a surface sea temperature dependant source function is introduced for sea salt aerosols. Wet deposition is modified toward a more physically realistic representation by introducing re-evaporation of falling rain and snowfall scavenging and by changing the in-cloud scavenging scheme along with calculations of precipitation cloud cover and rain properties. The sedimentation scheme update includes changes regarding the stability and viscosity calculations. Independent data from satellites (MODIS, SEVIRI), the ground (AERONET, EMEP), and a model inter-comparison project (AeroCom) are compared with MOCAGE simulations and show that the introduced changes brought a significant improvement on aerosol representation, properties and global distribution. Emitted quantities of desert dust and sea salt, as well their lifetimes, moved closer towards values of AeroCom estimates and the multi-model average. When comparing the model simulations with MODIS aerosol optical depth (AOD) observations over the oceans, the updated model configuration shows a decrease in the modified normalized mean bias (MNMB; from 0.42 to 0.10) and a better correlation (from 0.06 to 0.32) in terms of the geographical distribution and the temporal variability. The updates corrected a strong positive MNMB in the sea salt representation at high latitudes (from 0.65 to 0.16), and a negative MNMB in the desert dust representation in the African dust outflow region (from −1.01 to −0.22). The updates in sedimentation produced a modest difference; the MNMB with MODIS data from 0.10 in the updated configuration went to 0.11 in the updated configuration only without the sedimentation updates. Yet, the updates in the emissions and the wet deposition made a stronger impact on the results; the MNMB was 0.27 and 0.21 in updated configurations only without emission, and only without wet deposition updates, respectively. Also, the lifetime, the extent, and the strength of the episodic aerosol events are better reproduced in the updated configuration. The wet deposition processes and the differences between the various configurations that were tested greatly influence the representation of the episodic events. However, wet deposition is not a continuous process; it has a local and episodic signature and its representation depends strongly on the precipitation regime in the model.

Since the beginning of the 21st century, anthropogenic emissions of SO2 have been de- creasing. Therefore, the relative part of volcanic SO2 emissions in total sulfur emissions is increasing. However, this source of SO2 emissions is characterized by its hightemporal variability, mainly for eruptions. Moreover, there are different sources of uncertainties in the estimation of these emission fluxes. The objective of this thesis is to study the impact of volcanic emissions on the tropospheric budget of sulfur species, at global and regional scales. To do so, the chemistry-transport model MOCAGE (Modèle de Chimie Atmosphérique à Grande Echelle) was improved by taking into account the most recent estimates of volcanic SO2 emissions (passive and eruptive) and by developing a new parameterization representing the injection in altitude of volcanic emissions. Using two complementary studies on two separate years, one representative of a low eruptive year (2013) and the other representative of a high eruptive year (2014), we assess the respective impact of passive and eruptive emissions on global-scale sulfur species budgets. On one hand, we show that although the relative part of volcanic emissions is small compared to other sulfur sources, their relative contribution to the tropospheric SO2 burden is larger, particularly when there are eruptive emissions. Volcanic SO2 emitted by major eruptions is even dominant in the mid troposphere compared to other sources. On the other hand, the formation of sulfate aerosols by SO2 oxidation is less efficient in mid troposphere, where oxidants are scarcer. On a regional scale, the impact of a major volcanic eruption is even more important and can locally increase the concentrations of sulfur species at the surface, which can lead to a deterioration of air quality. Finally, a study of the Etna volcanic eruption of Christmas 2018, at the regional scale on the Mediterranean region, allows usto evaluate the uncertainties in the definition of the volcanic source in the model and the uncertainties in the retrieval of the volcanic SO2 by satellites.; Sachant que les émissions anthropiques sont décroissantes depuis le début du XXIe siècle, la part relative des émissions volcaniques de SO2 par rapport aux émissions totales de soufre augmente. Or, cette source d'émission de SO2 est caractérisée par l'importance de sa variabilité temporelle, principalement pour les éruptions. De plus, il y a différentes sources d'incertitudes dans l'estimation de ces flux d'émissions. L'objectif de cette thèse est d'étudier l'impact des émissions volcaniques sur le bilan troposphérique des espèces soufrées, à l'échelle globale et régionale. Pour ce faire, le modèle de chimie-transport MOCAGE (Modèle de Chimie Atmosphérique à Grande Échelle) a été amélioré en prenant en compte les estimations des émissions volcaniques de SO2 (passives et éruptives) les plus récentes et en développant une nouvelle paramétrisation d'injection en altitude des émissions volcaniques. À partir de deux études complémentaires sur deux années distinctes, l'une représentative d'une année peu éruptive (2013) et l'autre représentative d'une année très éruptive (2014), nous évaluons l'impact respectif des émissions passives et éruptives sur les bilans en espèces soufrées à l'échelle globale. Nous avons montré que bien que la part relative des émissions volcaniques soit faible par rapport aux autres sources de soufre, leur contribution relative à la charge troposphérique en SO2 est plus forte, d'autant plus si ce sont des émissions éruptives. Le SO2 volcanique émis par des éruptions majeures est même dominant dans la moyenne troposphère par rapport aux autres sources. En revanche, la formation d'aérosols sulfatés par l'oxydation du SO2 est moins efficace dans la moyenne troposphère, où les oxydants sont plus rares. À l'échelle régionale, l'impact d'une éruption volcanique majeure est encore plus important et peut ponctuellement augmenter les concentrations en espèces soufrées de surface, ce qui peut détériorer la qualité de l'air. Enfin, une étude à l'échelle régionale sur la Méditerranée, de l'éruption volcanique de l'Etna de Noël 2018, permet d'évaluer les incertitudes dans la définition de la source dans le modèle et les incertitudes de restitution du SO2 volcanique par les satellites.